TW200844609A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal alignment agent and a liquid crystal display element showing a display property of high quality. The liquid crystal alignment agent makes a liquid crystal alignment film having high vertical alignment and high heat resistance, which is particularly suitable to apply to the vertical alignment mode liquid crystal display element. The liquid crystal alignment agent contains a polyamic acid and/or its imidized polymer, which is obtained through the reaction of (a) a tetracarboxylic acid dianhydride comprising a specific compound represented by 2,3,5-tricarboxylic cyclopentylacetic acid dianhydride and (b) a diamine comprising a specific compound represented by 1-(3,5-diaminophenyl)-3-octadecyl succinimide. The liquid crystal display element is provided with the liquid crystal alignment film made from the aforementioned liquid crystal alignment agent.

Description

200844609 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent and a liquid crystal display element having a liquid crystal alignment film. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having high vertical alignment properties and excellent heat resistance, and a liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent. [Prior Art] As a liquid crystal display device, a ΤΝ-type liquid crystal display element having a so-called 扭转 (twisted-to-parameter I) type liquid crystal cell is known, and a transparent conductive film such as germanium (indium oxide-tin oxide) is provided. A liquid crystal alignment film formed of polylysine, polyimine or the like is formed on the surface of the substrate, and as a substrate for a liquid crystal display element, two sheets of the substrate are opposed to each other, and a positive dielectric anisotropy is formed in the gap therebetween. The layer of the nematic liquid crystal constitutes a unit cell of a sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, an STN (Super Torsional Nematic) type liquid crystal display element having a higher contrast ratio and a smaller angular dependency than that of the ΤΝ-type liquid crystal display element has been developed. The STN type liquid crystal display element uses a liquid crystal in which a chiral agent as an optically active substance is blended 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. Further, in recent years, a horizontal electric field type liquid crystal display element has been proposed in which two electrodes for driving a liquid crystal are provided in a comb shape on one side substrate, and an electric field parallel to the substrate surface is generated to control liquid crystal molecules. This component is commonly referred to as the 200844609 in-plane switching type (IPS type) and is known to have excellent wide viewing angle performance. In particular, when the IPS type element and the optical compensation film are used, the viewing angle performance can be further improved, and the spectrescopic feature of the wide viewing angle which is comparable to that of the cathode ray tube which has no gray scale inversion and color tone change is obtained. In addition, a vertical alignment type liquid crystal display element called MVA (Multi-Domain Vertical Alignment) type or PVA (Patternized Vertical Alignment) type in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate has been proposed. (Refer to Patent Document 1 and Non-Patent Document 1). These vertical alignment type liquid crystal display elements are excellent not only in viewing angle and contrast, but also in the process of forming a liquid crystal alignment film, and are not required to be polished, and are excellent in process. * In recent years, in particular, in order to improve the quality of liquid crystal display elements used in television applications, the performance required for liquid crystal alignment films has become increasingly stringent in many respects. In particular, the requirements for improvement in vertical alignment and improvement in heat resistance are severe. That is to say, in the case of a vertically aligned liquid crystal display element, it is necessary to impart a true vertical alignment property, and since the liquid crystal panel is designed or even required in the process, for example, a substrate step difference, an ODF process, or the like is introduced as a vertical alignment. The technique of the factor of decline in properties is therefore required to impart a higher vertical alignment property to the liquid crystal alignment film. Further, in a liquid crystal television, by using a strong light source to improve display quality, it is necessary to have a liquid crystal alignment film having high durability against heat generated by a light source. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal capable of forming a liquid crystal alignment film having a suitable high vertical alignment property and high heat resistance, particularly for a vertical alignment type liquid crystal display element. An alignment agent, and a 'liquid crystal display element' having high-quality display performance. Other objects and advantages of the present invention can be seen from the following description. In order to achieve the above object, the inventors of the present invention have found that, as a component constituting the liquid crystal alignment film, a specific tetracarboxylic dianhydride having appropriate flexibility and a specific one having high hydrophobicity are used. The specific polymer obtained by the amine reaction can impart a good vertical alignment property and excellent heat resistance to the liquid crystal alignment film produced therefrom, thereby completing the present invention. Namely, the above object of the present invention, first, is achieved by a liquid crystal alignment agent containing (a) comprising a compound selected from the group consisting of the following formula (1)

And at least one of the group consisting of the compounds represented by the following formula (2), tetracarboxylic dianhydride (2) 200844609

(In the formula (2), R is independently an alkyl group having a carbon number of 1 to 10, η is an integer of 0 to 2), and (b) includes a compound selected from the following formulas (3) to (6). At least φ of one of the diamines 0

(In the formulae (3) to (6), R1 to R4 are each independently a linear, branched or cyclic alkyl group having a carbon number of 1 to 40 or a linear chain having a carbon number of 4 to 40; a branched or cyclic alkenyl group, wherein 1 to 15 of the hydrogen atoms of R1 to R4 may be substituted by a fluorine atom, and A1 and A2 are each independently a hydrogen atom or a methyl group. Proline and/or its quinone imidized polymer. The above object of the present invention, and secondly, is achieved by a liquid crystal display element having a liquid crystal alignment film produced from the above liquid crystal alignment agent. Since the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has good vertical alignment property and excellent heat resistance, when used in a vertical alignment type liquid crystal display element, there is no contrast drop caused by light leakage or the like, and even if The advantage of not degrading performance under high temperature conditions. The liquid crystal display element of the present invention having the liquid crystal alignment film as described above can be applied to various liquid crystal display devices such as a desktop computer, a watch, a clock, a mobile phone, a counting display panel, a word processor, a personal computer, a liquid crystal television, etc. Display device. [Embodiment] The liquid crystal alignment agent of the present invention contains tetracarboxylic dianhydride (a) comprising at least one selected from the group consisting of compounds represented by the above formula (i) and the above formula (2), and (b) a polylysine (hereinafter referred to as "specific poly-proline") obtained by a diamine reaction selected from at least one of the compounds represented by the above formulas (3) to (6) and/or a ruthenium thereof Aminated polymer. Hereinafter, the tetracarboxylic dianhydride and the diamine used for synthesizing the polymer contained in the liquid crystal alignment agent of the present invention will be described. <(a) Tetracarboxylic dianhydride> Thai 200844609 The (a) tetracarboxylic dianhydride used in the synthesis of a specific polyamic acid and/or its quinone imidized polymer includes a compound selected from the above formula (1) and At least one of the groups consisting of the compounds represented by the above formula (2) (hereinafter referred to as "specific tetracarboxylic dianhydride"). Specific examples of the compound represented by the above formula (2) include, for example, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl). -naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5-methyl-5(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, ^ 1,3,3&,4,5,91)-hexahydro-5-ethyl -5 (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91 )-Hexahydro-7-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3 ,3&,4,5,91)-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1 ,3-dione, l,3,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2 -c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxo-3- Furyl)-φ naphthalene [1,2-〇]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5,8-dimethyl-5 ( Tetrahydro-2,5-dioxo-3-furoyl)-naphthoquinone, 2-c]-furan-1,3-dione, and the like. In the synthesis of the specific polyamic acid, other tetracarboxylic dianhydrides may be used in addition to the specific tetracarboxylic dianhydride insofar as the effects of the present invention are not impaired. Examples of the other tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride (except for specific tetracarboxylic dianhydride), and aromatic tetracarboxylic dianhydride. Examples of the aliphatic tetracarboxylic dianhydride' include butane tetracarboxylic acid-10-200844609 acid dianhydride. The alicyclic tetracarboxylic dianhydride may, for example, be a compound represented by the following formula (7).

(In the formula (7), R5 is independently a hydrogen atom, a halogen atom or a monovalent organic group), and a compound represented by the following formula (8) or (9)

(In the formulae (8) and (9), R6 and R8 represent a divalent organic group having an aromatic ring, R7 and R9 represent a hydrogen atom or an alkyl group, and a plurality of R7 and R9 present may be the same or different) 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Acid dianhydride, 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxyl Norbornane-2-acetic acid dianhydride, tetracyclo[4.4.0.12'5.17'1()]dodecane-3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5-four Hydrogen fur 200844609 tetrahydro acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexan-1,2-dicarboxylic anhydride, bicyclo [ 2.2.2] _oct-4·ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, etc. The halogen atom of R5 in the above formula (7) may, for example, be a chlorine atom, a bromine atom or an iodine atom, and the monovalent organic group of R5 may, for example, be an alkyl group having 1 to 10 carbon atoms or an alkoxy group. Specifically, for example, a methyl group, an ethyl group, a methoxy group or the like can be given. Specific examples of the compound represented by the above formula (7) can be exemplified

Such as 1,2,3,4-cyclobutane tetracarboxylic dianhydride, hydrazine, 2-methyl-1,2,3,4-:feTk tetradecanoic acid dihydrogen, 1,2-diethyl- 12,3, deducted butyl sulfonate tetracarboxylic dianhydride' 丨, 3 dimethyl dimethyl 1,2,3,4-cyclobutane tetracarboxylic dianhydride, hydrazine, 3_ethyl-1,2,3 4, butane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid monohydride 1,2,3,4-tetramethyl-1,2 , 3,4-cyclobutane tetramine acid, and the like. For β, for example, pyromellitic acid can be used as the above-mentioned aromatic tetracarboxylic acid, and 1 to 1 is a boric acid, 3, 44'-biphenyl dianhydride, 3, 3, 4, 4 , - benzophenone tetracarboxylic acid / town ' ' ', said / anhydride, 2 3 6 7 - naphthalenetetracarboxylic acid ditetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid a * ' ' ' ^ gx , 〇〇 * 44' - dimethyl anhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic acid ' ' 'diphenyl (tetra) four off: @ΐ, 3,3'彳, 4' · tetraphenyltetraphthalic acid dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4' --(3'4_ monoterpene basic series 1 base) diphenyl sulfide Dianhydride, 4,4,-bis(3,4 di residue phenoxy)diphenyl Feng Erxuan, 4,4,-bis(3,4-di residue benzene gas) diphenyl propyl Erxuan, 3,3,,4,4,-perfluoroisopropylidene diphthalic acid anhydride, 2,2 '3,3 biphenyltetracarboxylic dianhydride, 3,3,,4,4, _Biphenyltetracarboxylic acid monoanhydride, one (present one methyl-12-200844609 acid) phenylphosphine oxide dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di (dehydrated trimellitic acid) Ester), 1,4-butanediol-di(dehydrated trimellitate), 1,6-hexanediol - bis (dehydrated trimellitate), 1,8-octanediol-di (hydrogen trimellitate), 2,2-bis(4-hydroxyphenyl)propane-di(dehydrated trimellitic acid) Ester), a compound represented by the following formulas (10) to (13), and the like.

Yan /CH3

-13- 200844609 These other tetracarboxylic dianhydrides may be used alone or in combination of two or more. The (a) tetradecanoic dianhydride used in the synthesis of the specific polyamine includes the specific tetracarboxylic dianhydride described above, and the total amount of the specific tetracarboxylic dianhydride accounts for the ratio of all tetradecanoic dianhydrides, from the polymerization reactivity and The heat resistance of the obtained liquid crystal alignment film is preferably 80 mol% or more, more preferably 85 to 100 mol%. (b) Diamine> Diamine used in the synthesis of a specific polyamine At least one selected from the compounds represented by the above formulas (3) to (6) (hereinafter also referred to as "specific diamine") is included. In the diamine represented by the above formulas (3) to (6), examples of the linear alkyl group having 1 to 40 carbon atoms represented by R1 to R4 include n-hexyl group, n-octyl group and n-decyl group. N-dodecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-icosyl, etc.; as a branched alkyl group, for example, a methylhexyl group, a hexyl hexyl group, and 2 -methylhexyl, 2-ethylhexyl '1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 1,2-dimethylhexyl, 1,2-diethylhexyl, 1,2-dimethyloctyl, 1,2-diethyloctyl, 1-methylindenyl, 1-ethylindenyl, 2-methylindenyl, 2-ethylindenyl, etc.; The cyclic alkyl group may, for example, be obtained by removing one hydrogen atom from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornane, bicyclooctane, dicycloundecane or adamantane. a group having a group of a steroid skeleton. Examples of the group having a steroid skeleton include a group obtained by removing one hydrogen atom from a steroid compound such as cholesterol, -14 - 200844609 cholesterol, lanosterol or 24 dehydroesterol. The linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms represented by R1 to R4 is exemplified by one or more of the carbon-carbon bonds of the above-exemplified alkyl group. Group. The specific diamine is preferably a diamine in which the groups R1 to R4 in the above formulas (3) to (6) are a group having a steroid skeleton, or the above formula (3), and R1 is a carbon number. It is a linear, branched or cyclic alkyl group of 1 to 20 or a linear, branched or cyclic alkenyl group diamine having a carbon number of 4 to 20. In the synthesis of a specific polyamine, other diamines may be used in addition to the above specific diamines. Examples of the other diamine include an aliphatic or alicyclic diamine, a diamine having a two-stage amine group in the molecule, and a nitrogen atom other than the amine group of the first-order amine group, a diamine-based organic decane, and a fragrance. Group of diamines and the like. Examples of the aliphatic or alicyclic diamine include 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, and decanediamine. 4-Diaminoheptyldiamine, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)-bicyclo[2.2.1]heptane, 1,4-bis(aminopropyl) -bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3·di(aminopropyl)cyclohexane Alkane, m-xylylenediamine, p-xylylenediamine, isophoronediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methylene dimethylene diamine, tricyclic [6.2·1.02'7]-Exedecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), etc.; as the above molecule having two primary amine groups and the 1 The diamine having a nitrogen atom other than -15-200844609 may, for example, be 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4. -diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6- Dimethylamino-1,3,5-triazine, 1,4-bis(3.aminopropyl) Pyridazine, 2,4-extremity-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-di Pyrazine, 2,4-diamino-6-phenyl-1,3,5-trione, 2,4-diamino-6-methyl-s-diazine, 2,4-diamino- i,3,5-triazine, 4,6-diamino-2-vinyl

-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamine tomb-1,3-dimethyluracil, 3,5 -diamino-l,2,4-triazole, 6,9-diamino-2.ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, anthracene, 4-diamine-pyridazine, 3,6-diamino acridine, bis(4-aminophenyl)phenylamine, etc.; as the above-mentioned diamine-based organic chopping house, for example, the following formula ( 1 4) Compounds represented by 31〇)1〇Ί H2N—R11—Si Ό—S'r R11—NH2 (14) 10

R (in the formula (14), a plurality of Ri() independently represent a hydrogen atom or a monovalent organic group, and a plurality of R11 present independently of each other are a methylene group or an alkylene group having a carbon number of 2 to 20, p is an integer of 1 to 20); examples of the aromatic diamine include p-phenylenediamine, 2-methyl-indole-phenylenediamine, 2-ethyl-1,4-phenylenediamine, and 2 ,5·Dimethyl-1,4-phenylenediamine, 2,5-diethyl-indole, 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 Maple, -16 - 200844609 3,3'-Dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidil, 4,4 '-Diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'diaminobiphenyl, 5-amino-M4'-aminophenyl )-1,3,3-trimethylindan, 6-amino-1(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diamine Diphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-di[4 -(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminobenzene) Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-di( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-di Aminoguanidine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5,-tetrachloro-4 , 4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 1,4,4'-(p-phenylisopropylene)diphenylamine, 4,4'-(meta-phenylisopropylene)diphenylamine, 2, 2'-bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl) Biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4-(4-n-heptylcyclohexyl)phenoxy-2 , 4-diaminobenzene, a compound represented by the following formulas (15) to (17), etc. -17- (16) (15) 200844609 (16) (15) h2n

H2N

^~〇—( C2H4 )q -〇

H2n (In the formulae (15) to (17), X1 is independently a single bond, -C〇〇-, -〇C〇-, -NHC〇-, -CONH-, -S-, and Methylene-6 An alkyl group or a phenyl group, and R12 is a monovalent organic group having a fluorine atom-containing monovalent organic group of 20 to 20 and having 4 to 40 carbon atoms having an alicyclic skeleton, and R13 is a carbon number. The divalent organic group of the alicyclic skeleton or the divalent organic group of the fluorine atom 30, q is an integer of 1 to 20). Examples of the diamine represented by the above formula (15) include a compound represented by the examples (32), and (17) *NH 2 -〇-, -C〇-, a group, an alkyl group having 2 carbon atoms, and a carbon number. Or the carbon number of 6 to 4 0 has a carbon number of 5~ as in the following formula (1 8 ) -18- 200844609

H2n

(3 1) h2n

H2n h2n

COCM^KOCO (30)coo-<^)~ooo (3 2) 19 200844609 Further, examples of the compound represented by the above formula (16) include compounds represented by the following formulas (33) to (37). ,

hJh;ch2)3<'

In the synthesis of a specific polyamine, when a specific diamine is used together with another diamine, the use ratio of the specific diamine is preferably 1 mol% or more, and particularly preferably 5, based on the entire diamine. More than Mole. &lt;Synthesis of Specific Polylysine&gt; 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 polylysine may be preferably in an organic solvent, preferably at -2, by reacting the above specific tetracarboxylic dianhydride and, as the case, other tetracarboxylic dianhydride with a specific diamine and, if necessary, other diamines. 0 ° C ~ 1 50 ° C, more preferably 0 ~ 10 (TC temperature, preferably reacted for 0.5 to 72 hours to synthesize. Supply of specific poly-proline acid synthesis reaction of tetracarboxylic dianhydride And the ratio of the diamine to -20-200844609, preferably the ratio of the amine group of one equivalent of the amine, the acid anhydride group of the tetradecanoic dianhydride is 0.5 to 2 equivalents, more preferably The ratio of 当量·7 to 丨. 2 equivalents. Here, the organic solvent is not particularly limited as long as it can dissolve the specific polyamic acid synthesized, and examples thereof include hydrazine-methylpyrrolidone and N. N-dimethylacetamide, ν, Ν-dimethylformamide, 3-butoxy-oxime, Ν-dimethylpropanamide, 3-methoxy-oxime, Ν-dimethyl A guanamine solvent such as acrylamide, 3-hexyloxy-oxime, guanidine-dimethylpropionamide; dimethyl hydrazine, γ ® - butyrolactone, tetramethyl urea, hexamethylphosphonium Amine Protic polar solvent; phenolic solvent such as m-methylphenol, xylenol, phenol, halogenated phenol, etc. The amount of the organic solvent (α) is preferably the total amount of the tetracarboxylic dianhydride and the diamine compound (/ 3) The ratio (mole concentration) to the total amount (α + θ ) of the reaction solution is 0.1 to 30% by weight. In the above organic solvent, in the range in which the specific polyamine produced is not precipitated' It is also possible to use alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. of a poor solvent of a specific polyamine. As a specific example of such a poor solvent, For example, methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate Ethyl ethoxypropionate, Ethyl Ethyl, Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Ethyl Diether, hydroxy ether propyl ethethylene glycol diacid diol diethylene dipropylene, ethylene glycol, ether, ester ether ethyl ethane glycol butyrate diethanol ethanol-21- 200844609 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, tetrahydrofuran, Dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutyl, dichloroethane, chlorobenzene, o-dichlorobenzene, hexa, gengyuan, xinyuan, benzene, toluene, xylene , isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, etc. 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 can be re-dissolved in an organic solvent, and then subjected to a process of precipitating with a poor solvent once or several times or by distillation under reduced pressure with an evaporator, thereby purifying a specific polyamine. &lt;Synthesis method of quinone imidized polymer of specific polyamic acid&gt; Next, a method for synthesizing a quinone imidized polymer of a specific polyamine which can be contained in the liquid crystal alignment agent of the present invention will be described. The quinone imidized polymer of a specific polyamic acid can be synthesized by dehydrating and ring-closing some or all of the proline structure of the specific ® polylysine described above. 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") may be a portion less than 100%. Dehydration ring closure product. The ruthenium amination rate can be determined from the 1H-NMR of the polymer by the following formula (1): 醯 imidization ratio (%) = U-Al / A2xa) xl00 (1) (in the formula (1), A1 For the peak area near the chemical shift of 10 ppm from the NH proton, A2 'is the peak area near the chemical shift of the aromatic proton from 7 to 8 ppm -22- 200844609, and α is relative to the ruthenium reaction. The number of protons of one sulfhydryl group in the poly-proline, the number of aromatic protons). The dehydration ring-closure reaction of the specific polyamine can be carried out by (i) heating a specific poly-proline, or by 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 5 CTC, the dehydration ring-closure reaction cannot be sufficiently carried out, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided 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 from 0.01 to 20 moles per 1 mole of the repeating unit of the specific poly-proline. As the dehydration ring-closure catalyst, a tertiary amine 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. 〇 1 〜 1 〇 Mo Er relative to the dehydrating agent used for 1 mol. The higher the amount of the above dehydrating agent and the dehydration ring-closing catalyst, the higher the ruthenium amination rate. The organic solvent to be used in the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the solvent used in the synthesis of the specific polylysine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The obtained ruthenium iodide polymer can be purified by subjecting the reaction solution thus obtained to the same operation as in the specific polyamic acid purification method. -23- 200844609 &lt;Terminal-Modified Polymer&gt; 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 'monoisocyanate compound, or the like to the reaction system at the time of synthesis of a specific poly-proline. 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. Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. ^ <Solid viscosity of polymer> The specific polylysine and its quinone imidized polymer obtained as above, preferably have a viscosity of 20 to 800 mPa's when formulated into a 10% solution, more preferably 3 0~5 0 〇m P a · s viscosity. Further, the solution viscosity (mPrs) of the polymer was measured using a predetermined solvent, and the solution having a solid content concentration of 10% was measured at 25 Torr using an E-type rotational viscometer. &lt;Other Polymers&gt; -24- 200844609 In the liquid crystal alignment agent of the present invention, the above specific polyaminic acid or its quinone imidized polymer is selected from other polyfluorenes without impairing the present invention. At least one of the amine acid 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 an acid other than a specific polyaminic acid or a quinone imidized polymer thereof, and polyimidization obtained by reacting the above other tetracarboxylic dianhydride with another diamine is not particularly limited. polymer. The other tetracarboxylic acid II used herein is an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, a terpene cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride. As a synthesis of a diamine, preferably an aromatic diamine, and a particularly good 4,4'-diaminodiphenyl, other tetracarboxylic acid tareamine may be used instead of the specific tetracarboxylic dianhydride. The reaction with a specific diamine is carried out in the same manner as the synthesis of a specific quinone imidized polymer. When the liquid crystal alignment agent of the present invention contains another polymer, the use ratio thereof is preferably 30% by weight or less, or less by weight or less based on the total amount of the specific polyaminic acid and its ruthenium and other polymers. . &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains the above specific polyamine; the ruthenium iodide polymer is an essential component, but may be optionally contained. As such other additives, for example, a compound of an epoxidized functional decane or the like can be given. The epoxy compound may be a group of polyamines, preferably a compound or an anhydride thereof, in order to improve the effect of the obtained liquid crystal alignment effect, preferably the other ones used for the 1, 2, 3, 4: base group hospital. The dianhydride and its polyglycolic acid polymer are preferably added as a 25 acid and/or other compound having a film hardness of -25-200844609. Examples of the epoxy compound which may be contained in the liquid crystal alignment agent of the present invention include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Glycidyl 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, benzene-1,4-diol diglycidyl ether, 2-methylbenzene-1,4-diol diglycidyl ether, 2-B Benzene-1,4-diol diglycidyl ether, 2-n-hexylbenzene-1,4-diol dihydrate, glyceryl ether, 2-n-nonylbenzene 1,4-1,4-diol diglycidyl ether, a glycidyl ether epoxy compound such as 2-trifluoromethylbenzene-1,4-diol diglycidyl ether or 2,5-diethylbenzene-1,4-diol diglycidyl ether; ,Ν' ,Ν' ·tetraglycidyl-p-phenylenediamine, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-2-methyl-1,4-phenylenediamine, hydrazine, hydrazine, hydrazine ' ,Ν' -tetraglycidyl-2-n-propyl-1,4-benzene ,Ν,Ν,Ν,ΝΝ--tetraglycidyl-2-n-hexyl-1,4-phenylenediamine, ;^,^[,1^',^'-tetraglycidyl-2-di Fluoromethyl-1,4-phenylenediamine, anthracene, Ν'-tetraglycidyl-2,5-dimethyl-1,4-benzenediamine, hydrazine, hydrazine, hydrazine, hydrazine, - tetrahydration Glyceryl-m-xylylenediamine, hydrazine, hydrazine, hydrazine, hydrazine, tetraglycidyl-2,2,-dimethyl-4,4'-diaminobiphenyl, hydrazine, hydrazine, hydrazine, ,Ν,-tetraglycidyl 2,2, _diethyl-4,4, _diaminobiphenyl, hydrazine, hydrazine, hydrazine, hydrazine, -tetraglycidyl-3,3, _ Methyl-4,4,&quot;diaminobiphenyl, anthracene, anthracene, anthracene, anthracene, _tetraglycidyl-3,3,-diethyl- 4,4,-diaminobiphenyl, 2,2-bis[4-(indole, Ν-diglycidylaminophenoxy)phenyl]propane, hydrazine, hydrazine, hydrazine, Ν' _tetraglycidyl- 4,4,-diamine Diphenylmethane, hydrazine, hydrazine, hydrazine, hydrazine, _tetraglycidyl _4,4, _diaminodi-26 - 200844609 phenyl ether, 1,3 - bis (Ν, Ν· 缩) Glycerylaminomethyl)cyclohexane, n-di(N,N-diglycidylaminomethyl) ring Alkane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1, bis(N,N-diglycidylaminomethyl)benzene, 3-(N-allyl --N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, N,N-diglycidyl-benzylamine A glycidylamine type epoxy compound such as N,N-diglycidyl-aminomethylcyclohexane or the like. The use ratio of the epoxy compound in the liquid crystal alignment agent of the present invention is preferably 50 parts by weight or less, more preferably 0·1 to 40 parts by weight, based on the total amount of the polymer of 1 part by weight, more preferably 1 ~ 30 parts by weight. The functional decane-containing compound may be added in order to improve the adhesion of the obtained liquid crystal alignment film to the surface of the substrate. Specific examples of such a functional decane-containing compound include, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethoxydecane. , 2-aminopropyltriethoxydecane, Ν(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane , N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylidene Amine, 10-trimethoxydecylane-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecane Base-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Baseline, N-benzyl-3-aminopropyltriethoxyphosphonium-27- 200844609 alkane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl- 3-Aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxysulane, N-bis(oxyvinyl)-3-aminopropyltriethyl Oxydecane, 3-(N_丨Hipyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, etc. . The mixing ratio of these other functionally-containing compounds is preferably 10 parts by weight or less, more preferably 0.01 to 5 parts by weight, per 100 parts by weight of the polymer. &lt;Liquid Crystal Aligning Agent&gt;# The liquid crystal alignment agent of the present invention is prepared into a specific polyamic acid and/or its quinone imidized polymer, and any other component added is preferably dissolved in a solution state contained in an organic solvent. . The organic solvent used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the specific polyamine acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which is exemplified as a poor solvent which can be used in the specific polyamine acid synthesis reaction. As a particularly preferred organic solvent to be used in the liquid crystal alignment agent of the present invention, for example, N-methyl-2-pyrrolidone, 7-butyrolactone, γ-butyrolactam, hydrazine, hydrazine-dimethyl group can be mentioned. Formamide, hydrazine, hydrazine-dimethylacetamide, 4 hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionic acid Methyl ester, ethyl ethoxypropionate, 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 acetate 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, -28- 200844609 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-oxime , Ν-dimethylpropanamide, 3-hexyloxy-oxime, Ν·dimethylpropanamide, diethyl carbitol, ethyl carbitol acetate, butyl carbitol, three Glycol dimethyl ether, isoamyl isobutyrate, diisoamyl ether, and the like. They may be used singly or in combination of two or more. The concentration of the solid component in the liquid crystal alignment agent of the present invention (the total weight of the components other than the solvent in the liquid crystal alignment agent divided by the total weight of the liquid crystal alignment agent) is preferably 1 to 1 0 in consideration of viscosity, volatility, and the like. The range of the amount of %. Applying the liquid crystal alignment agent of the present invention 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 a good liquid crystal alignment film 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 deterioration of coating properties. The situation is therefore not good. The solid content concentration 値 of the liquid crystal alignment agent of the present invention differs depending on the method used when the liquid crystal alignment agent of the present invention is applied to a substrate. Example ® For example, when the spin coating method is employed, the solid content concentration 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 4 to 1% by weight, so that the solution viscosity can be made to fall within the range of 10 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 2 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa*s. The surface tension of the liquid crystal alignment agent of the present invention is preferably from 2 5 to 4 0 m N / m. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 -29 to 2008 44 609 ° C, more preferably from 20 ° C to 60 ° C. &lt;Liquid Crystal Display Element&gt; 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 described above. The liquid crystal display element of the present invention can be produced, for example, by the following processes (1) to (4). (1) Applying the liquid crystal alignment agent of the present invention to a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a lithography method, a spin coating method, or an inkjet printing method, and then, A coating film is formed by heating the coated surface. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, or the like may be formed of plastic. Transparent substrate, etc. As the transparent conductive film provided on one side of the substrate, a NES A film (registered trademark of PPG, USA) formed of tin oxide (Sn〇2), and indium oxide-tin oxide (In2〇3-Sn〇2) can be used. The formed ITO film or the like is formed by a photolithography method or a method of using a mask in advance when forming a transparent conductive film. 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 compound containing a functional decane, a compound containing a functional titanium, or the like 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 250 ° C. Further, the liquid crystal alignment agent of the present invention removes an organic solvent by coating 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 further be heated to give a guanamine The acid structure is subjected to dehydration ring closure to form a coating film of further oxime imidization -30-.200844609. The thickness of the formed coating film is preferably 0.001 to 1 // m, more preferably 0.005 to 0.5 M m 〇 (2). Next, the coating film formed as described above is wrapped with, for example, nylon, rayon, cotton. The roller of the cloth formed by the fiber is subjected to a rubbing treatment in a certain direction, or a method of irradiating the surface of the coating film with a polarized ultraviolet ray or a method of irradiating the surface of the coating film with an ion beam, thereby causing an alignment energy of the liquid crystal molecule on the coating film. Thereby, a liquid crystal alignment film can be obtained. (3) The liquid crystal alignment film obtained as described in the above (1) to (2) may be cleaned as needed. As the washing solvent, for example, water, acetone, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate can be used. , tetrahydrofuran, hexane, heptane, octane, and the like. In order to improve the cleaning efficiency, a surfactant may be added to the cleaning solvent, or a method of washing with a heating solvent, a method of scrubbing, and a method of using ultrasonic waves. After washing, it can be used directly, or it can be rinsed with a suitable solvent. After that, it can be dried by heating as needed. (4) Two substrates on which the liquid crystal alignment film is formed are formed, and the two substrates are placed opposite to each other with a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other, and the peripheral portions of the two substrates are used. The sealant is bonded, and a liquid crystal is injected into the cell gap which is separated from the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizer is attached to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, so that the polarizing direction and the liquid crystal alignment film formed on one side of the substrate are polished -31-, 200844609 The liquid crystal display element is produced in a uniform or vertical direction. Here, as the sealant, for example, an alumina ball-containing epoxy resin as a curing agent and a spacer may be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, or a cuba liquid crystal. In addition, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and under the trade names "C-15" and "CB-15" (Merck) It is used as a chiral agent for sale. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate may also be used. The polarizer to be bonded to the outer surface of the liquid crystal may be a polarizer or a ruthenium film obtained by sandwiching a polarizing film called a ruthenium film obtained by stretching a polyvinyl alcohol while absorbing iodine, and sandwiching it on a cellulose acetate protective film. A polarizer made. ® [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples, but the invention is not limited to the examples. In the following examples and comparative examples, the evaluation of the prepared liquid crystal alignment agent was carried out in the following manner. [Evaluation of Vertical Alignment] Prefabricated two glass substrates having a transparent conductive film formed of a ΪΤ0 film on one side and having a film thickness of 1 mm were subjected to spin coating to each example or a ratio of -32 to 200844609. The prepared liquid crystal alignment agent solution was applied onto the transparent conductive film of each substrate, and heated at 200 ° C for 60 minutes to obtain two substrates having a film thickness of 0.06 / / m. Then, the substrate was subjected to a rubbing treatment on a substrate by a sander equipped with a roll of a nylon-made cloth to obtain a liquid crystal alignment film. The grinding conditions were: roller speed 400 rpm, table movement speed 30 mm/sec, and fluff length 0.4 m m. On each of the outer edges of the substrate having the liquid crystal alignment film, in addition to the liquid crystal injection/inlet, an epoxy resin® adhesive having an alumina ball of 5.5 // m diameter is applied, and then the liquid crystal alignment film is made inside. And the grinding direction is reversed and the weight is combined and pressed to cure the adhesive. Next, a nematic liquid crystal (negative type, manufactured by Merck & Co., MLC-6608) is filled between the substrates through a liquid crystal injection port, and then the liquid crystal injection port is closed with an acrylic photocurable adhesive, and bonded on both sides of the substrate. A polarizer is used to form a liquid crystal display element. The pretilt angle was measured by the crystal rotation method for the liquid crystal display element. [Evaluation of voltage holding ratio] φ The surface of the liquid crystal to be used is not subjected to the polishing treatment after the heating, and the type of the liquid crystal used is nematic liquid crystal (negative type, manufactured by Merck & Co., MLC-6683), and the above [vertical alignment property] Evaluation] A liquid crystal display element was produced in the same manner. A voltage of 5 V was applied to the liquid crystal display element at a time interval of 16.7 msec at 60 ° C for a voltage application time of 6 〇 microseconds, and then the voltage holding ratio from the voltage release to 167 ms was measured. [Evaluation of heat resistance] A liquid crystal display element produced in the same manner as the above [Evaluation of voltage holding ratio] was subjected to a temperature stress of 1 Torr at 100 ° C, and a temperature of -33 - 200844609 before and after stress was applied. When the change in the retention ratio is less than 1%, it is judged as "good", and when it is 1% or more, the evaluation is "poor". Synthesis example &lt;Synthesis Example of Specific Diamine&gt; 'Synthesis Example b-1 (Synthesis of 1-(3,5-Diaminophenyl)-3-octadecylsuccinimide) to ventilate by nitrogen Into a 300 ml three-necked flask, 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid were added, and while stirring with nitrogen gas, the solid matter was dissolved. 24.64 g (0.07 mol) of octadecyl succinic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After the reaction solution was cooled to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The precipitated solid component was filtered, washed with methanol and dried to give 30 g (yield: 83%) of 1-(3,5-dinitrophenyl)-3-octadecyl amber. Then, to a 500 ml flask ventilated with nitrogen, 30 g (0.058 mol) of 1-(3,5-dinitrophenyl)-3-octadecylsuccinimide synthesized above, 100 ml of ethanol, 100 ml of tetrahydrofuran (THF) and 25 g of a reduction catalyst palladium on carbon (Pd/C) were stirred at 70 ° C for 1 hour. 42.5 ml (43.7 5 g) of hydrazine monohydrate was added thereto, 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 then recrystallized by cooling to obtain 14.6 g (0.032 mol, yield 55%) of the desired product 1-(3,5-diaminophenyl)- 3-octadecyl amber imine. The same operation was carried out three times to ensure that the desired product of the following polymer synthesis was obtained. ^ -34- 200844609 Synthesis Example b-2 (Synthesis of 1-(3,5-diaminophenyl)_3-dodecysuccinimide) In addition to the use of 18.76 g (0.07 mol) of dodecyl amber The anhydride was replaced by 2 4.6 4 g (0 · 0 7 πι ο 1), except for the octanoyl group, and the same procedure as in the synthesis example 匕 1 was carried out to obtain 1 1 g (0 · 0 3 0 m ο 1 , yield 5 1 %) 1 - (3,5-diaminophenyl)-3-dodecyl amber imine. Synthesis Example b-3 (Synthesis of 1-(3,5-diaminophenyl)_3_heptadecyl-4-methylmaleimide) Φ In a 2000 ml three-necked flask ventilated with nitrogen Add 3 1.5 g (0.25 mol) of dimethyl maleic anhydride, 8 9.0 g (0 · 5 m ο 1) of N-bromo oxime imine, 1.0 g (4.15 mmol) of benzamidine peroxide and 1 500 ml Carbon tetrachloride was heated to reflux for 5 hours. The reaction solution was cooled to room temperature, allowed to stand at room temperature overnight, and then filtered. After the filtrate was washed with water, the organic layer was concentrated on a rotary evaporator. The crude oily product obtained was distilled under high vacuum (120 to 125 ° C / 2 mmHg) to afford 20.0 g (0.1 mol, yield 39%) of intermediate 3-bromomethyl-4-methylmaleic acid. ® Then, to a 2000 ml three-necked flask ventilated with argon, 16.4 g (80 mmol) of 3-bromomethyl-4-methylmaleic anhydride obtained above, 1.52 g (8.0 mmol) of copper iodide, After 400 ml of diethyl ether and 160 ml of HMPA (hexamethylphosphonium trisamine), it was cooled to -5 to 0 ° C under argon gas. While stirring the mixture, a separately prepared solution of 4 〇〇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, 600 ml of 4N-sulfuric acid diluted with 600 ml of diethyl ether was added to make the solution to be acid -35-200844609. The separated aqueous layer was further washed with 600 ml of diethyl ether and combined with an organic layer. The organic layer was washed with water and water was evaporated over sodium sulfate. This crude product was purified in a cerium oxide gel column using a petroleum ether/ethyl acetate (19:1) mixed solution as a developing solvent to obtain 14.0 g (〇·〇4mQl, yield 50%) 3·10 Heptaalkyl-4-methyl maleic anhydride. Then, 6.4 g (0.03 5 mol) of 3,5-dinitroaniline and 35 ml of acetic acid were placed in a 200 ml three-necked flask which was purged with nitrogen. The solid substance was dissolved while stirring with nitrogen gas #. 12.3 g (0.03 5 m 〇l) of 3-heptadecyl-4-methyl maleic anhydride obtained above was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After the reaction solution was cooled 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-methylmale. Imine. Then, to a 300 ml flask ventilated with nitrogen, 13.4 g (0.026 mol) of 1-(3,5-dinitrophenyl)-3-heptadecyl-4-methylma® was added to the imine. 50 ml of ethanol, 50 ml of THF and 12.5 g of a reduction catalyst Pd/C were stirred at 7 (TC 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 react. Pd / C was filtered off. 'The filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating and recrystallized to give 6.6 g (0.015 mol, yield 56%) of the desired product 1 - (3 ,5-Diaminophenyl)-3-heptadecyl-4-methylmaleimide. Perform the same operation twice to ensure the following polymer synthesis is required -36- 200844609 Target product. Oral example b - 4 (1 - (3,5 - one-limbylphenyl)_3 -hexyloxymethyl_4 · methylmaleimine)) After adding 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 inl of acetic acid to a gas three-necked three-necked flask, the solid matter was dissolved while stirring with nitrogen gas, and 14.3 g (0.07 mol) was added thereto. ) and synthesis example b-3 The intermediate was synthesized in the same manner as 3-(bromomethyl)-4-methylmaleic anhydride, and refluxed under nitrogen for 2 hrs. • After cooling the reaction solution to room temperature, 70 ml of methanol was added and allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 18.9 g (0.051 m 〇1, yield 7.3 %) 1 - (3,5 -dinitrophenyl)-3 -bromomethyl-4 - Methyl maleimide. Next, 18.1 g (0.049 mol) of 1-(3,5-dinitrophenyl)-3-bromomethyl-4 was added to a 500 ml three-necked flask ventilated with nitrogen. -methylmaleimide, 12.9 g (0.049 mol) of sodium cetyl alcoholate and i〇0mi dimethyl hydrazine, and then reacted at 100 ° C for 1 hour to cause a reaction. After cooling to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered, washed with methanol and dried to give 20.8 g (0.039 mol, yield 80%) of l-(3,5-dinitrophenyl) )-3-hexadecyloxymethyl-4-methylmaleimide. Then, to a 300 ml flask ventilated with nitrogen, 13.8 g (0.026 mol) of 1-(3,5 - one was added. ►Nitrophenyl)-3-hexadecanyloxymethyl-4-methylmaleimide, 50ml ethanol, 5 0 ml of THF and 12.5 g of a reducing catalyst Pd/C were stirred at 70 ° C for 1 hour, and 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-37-200844609 methyl-2-pyrrolidone by heating, and recrystallized by cooling to obtain 8.2 g (0.018 mol, yield 67%) of the desired product 1-(3,5-diaminobenzene. ))-3-hexadecyloxymethyl-4-methylmaleimide. The same operation was carried out three times to ensure that the desired product of the following polymer synthesis was obtained. &lt;Synthesis of Polymer&gt; Synthesis Example P-1 (Synthesis of a quinone imidized polymer of a specific polyamine) 2,3,5-tricarboxycyclopentyl group as a U) tetracarboxylic dianhydride Acetate dianhydride • 22.4 g (0.1 mol) and p-phenylenediamine 8.1 g (0.075 mol) as (b) diamine and 1-(3,5-diamino) synthesized in the above synthesis example b-1 Phenyl)-3-octadecylsuccinimide 11.4 g (0.025 mol) was dissolved in 168 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 34 g of the specific polyamine. 20 g of the obtained specific polyamic acid was dissolved in 380 g of N-methyl-2-pyrrolidone, and 9.4 g of pyridine and 12.2 g of acetic anhydride were added, and the product was subjected to a dehydration ring-closing reaction at 110 ° C for 4 hours, and then Precipitation, washing, and drying under reduced pressure were carried out in the same manner as above to obtain 1 2 · 1 g of a quinone imidized polymer (PI -1) having a ruthenium iodide ratio of 85 %. Synthesis Example P-2 (Synthesis of a quinone imidized polymer of a specific polyamic acid) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a U) tetracarboxylic dianhydride 22.4 g (0.1 mol) Ear) and 8.1 g (0. 〇75 mol) of p-phenylenediamine as (b) diamine and 1-(3,5-diaminophenyl)-3-de synthesized in the above synthesis example b-2 Dialkyl amber imine 9.3 g (0. 25 mol) was dissolved in i59 g of N-methyl-2-pyrrole-38-200844609 anthrone and allowed to react at 60 C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 4 CTC for 15 hours to obtain 36 g of the specific polyamine. 20 g of the obtained specific polyamic acid was dissolved in 380 g of N-methyl-2-pyrrolidone, and 9.9 g of pyridine and 12.8 g of acetic anhydride were added thereto, and the mixture was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours, and then the same as above. The precipitate was subjected to precipitation, washing and drying under reduced pressure to give 10.4 g of yttrium imidized polymer (PI-2) having a oxime imidation ratio of 83%. ® Synthesis Example P-3 (Synthesis of a quinone imidized polymer of a specific polyamic acid) 22.4 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as (a) tetracarboxylic dianhydride ( 0.1 mol) and 8.1 g (0.075 mol) of p-phenylenediamine as (b) diamine and 1-(3,5-diaminophenyl)-3-de synthesized in the above synthetic example b-3 17.4 g (0.025 mol) of heptaalkyl-4-methylmaleimine was dissolved in 168 g of N-methyl-2-pyrrolidone and allowed to react at 6 (TC for 4 hours. Next, the reaction solution was injected. The reaction product was precipitated in a large excess of methanol. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain mw to 32 g of the specific polyamine. 20 g of proline was dissolved in 3 80 g of N-methyl-2-pyrrolidone, and 9,4 g of pyridine and I2.2 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 11 °C for 4 hours, and then with the above The precipitation, washing and drying under reduced pressure were carried out in the same manner to obtain 1 1 · 1 g of a quinone imidized polymer (PI-3) having a ruthenium amination ratio of 85%. Synthesis Example P - 4 (Specific poly-proline Synthesis of ruthenium iodide polymer) will serve as (a) 2,3,5-tricarboxycyclopentyl acetic acid diterpene tetracarboxylic acid dianhydride 22.4 g (0.1 mol) and (b) diamine 4,4,-diaminodiphenyl ketone - 39- 200844609 14.9g (0.075 mol) and the 1-(3,5-diaminophenyl)-3 - 18-yard compound synthesized in the above synthesis example bl, 1 1 · 4 g (0 · 0 2 5 moles was dissolved in 195 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. Then, the reaction solution was poured into a large excess of methanol to obtain a reaction product. Precipitation. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 31 g of the specific poly-proline. The 20 g of the obtained specific polyamine was dissolved. 3 80 g of N-methyl-2-pyrrolidone, adding 8 · 1 g of pyridine and 1 〇. 5 g of acetic anhydride, and performing a dehydration ring-closing reaction at 110 ° C for 4 hours, in the same manner as the above Φ Precipitation, washing and drying under reduced pressure gave 13.1 g of a ruthenium iodide polymer (PI-4) having a ruthenium iodide ratio of 82%. Synthesis Example P-5 (Specific Polyamine) Synthesis of aminated polymer) as 1,3,3a,4 of (a) tetracarboxylic dianhydride 5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione 3 1.4 g (0.1 mol) and 14.9 g (0.075 mol) of 4,4'-diaminodiphenylmethane as (b) diamine and 1-(3,5-diamine synthesized in the above synthesis example bl 11.4 g (〇.025 mol) of phenyl)-3-octadecyl amber imine was dissolved in 231 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and allowed to stand at 40 under reduced pressure. (: Drying for 15 hours gave 29 g of the specific poly-proline. 20 g of the obtained specific polyamic acid was dissolved in 3 80 g of N-methyl-2-pyrrolidone, and 6.9 g of pyridine and 8.8 g of acetic anhydride were added to make it The dehydration ring-closure reaction was carried out for 4 hours at 110 ° C, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above to obtain a ruthenium iodide polymer (PI) having a ruthenium content of 89 g. -5- 200844609 Synthesis Example P-6 (Synthesis of a quinone imidized polymer of a specific poly-proline) 1,3,3, and 4,5,913 as (a) tetracarboxylic dianhydride -hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-indole]furan-1,3-dione 3 1.4 g (〇 1 mole) and 4,4'-diaminodiphenylmethane 14_9g (〇.〇75吴) as (b) diamine and 1-(3,5) synthesized in the above synthesis example b-4 - —* month-female phenyl)-3-hexadecyloxymethyl-4-methylmaleimide 11.8 g (0.025 mol) dissolved in 231 g of N-methyl-2-pyrrolidone It was reacted for 4 hours at 60 ° C. Next, the reaction solution was poured into a large excess of methanol to precipitate a product of the anti-Φ. By using the precipitate The alcohol was washed and dried under reduced pressure at 40 ° C for 15 hours to obtain 34 g of a specific poly-proline. 2 g of the obtained specific polyamic acid was dissolved in 3 80 g of N-methyl-2-pyrrolidone. In the above, 6.8 g of pyridine and 8.8 g of acetic anhydride were added, and the mixture was subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above to obtain a 12.2 g oxime imidization ratio of 89%. The ruthenium iodide polymer (PI-6). Synthesis Example P-7 (synthesis of a quinone imidized polymer of a specific poly-proline) 2, 3 as (a) tetracarboxylic dianhydride 5-tricarboxycyclopentyl acetic acid dianhydride • 18.02 (0.08 mol), 1,2,3,4-cyclobutane tetracarboxylic dianhydride 3.92 (0.02 mol) and as (b) diamine 4, 4'-Diaminodiphenylmethane 14.9 g (0.07 5 mol) and 1-(3,5-diaminophenyl)-3-hexadecyloxy group synthesized in the above Synthesis Example b-4 Base-4-methylmaleimide 11.4 g (0.025 mol) was dissolved in 193 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. Then, the reaction solution was injected into the large In an excess of methanol, the reaction product is allowed to pour. By washing the precipitate with methanol And drying it under reduced pressure at 40 ° C for 5 hours to obtain 31 g of the specific poly-proline. The -41- 200844609 20 g of the obtained specific polyamine was dissolved in 3 80 g of N-methyl- To the 2-pyrrolidone, 8.2 g of pyridine and 10.6 g of acetic anhydride were added, and the mixture was subjected to a dehydration ring-closure reaction at ll ° C for 4 hours, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above to obtain 12.7 g of ruthenium iodide. The rate is 83% of the ruthenium iodide polymer (ΡΊ-7). Synthesis Example P-8 (Synthesis of Polyproline) 10.9 g (0.05 mol) of 1,4,3,4-cyclobutanetetracarboxylic acid as pyromellitic dianhydride of tetradecanoic dianhydride Anhydride 9.8 g (0.05 mol) and 4,4'-diaminodiphenylmethane 20.4 g (0.1 mol) as a diamine were dissolved in 185 g and r-butyl φ lactone and 185 g N-methyl-2. In pyrrolidone, it was allowed to react at 40 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 33.8 g of polyamine (PA-1). Synthesis Example P-9 (Synthesis of oxime imidized polymer) 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-ring as tetracarboxylic dianhydride Hexene-1,2-dicarboxylic anhydride 26.4 g (0.1 mol) and p-phenylenediamine as a diamine 8.lg (0.075 mol) and octadecyloxy-2,4-aminophenylene® 9.6 g (0.025 mol) was dissolved in 184 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to give 3 7 g of polyamine. 20 g of the obtained polyamic acid was dissolved in 380 g of N-methyl-2-pyrrolidone', 9.7 g of pyridine and 12.6 g of acetic anhydride were added, and dehydrated at 11 ° C for 4 hours. The ring closure reaction was carried out. Precipitation, washing and drying under reduced pressure were carried out in the same manner as above to obtain 13.5 g of a ruthenium iodide polymer (ΡΊ-8) having a ruthenium iodide ratio of 89%. -42- 200844609 Synthesis Example P-10 (Synthesis of oxime imidized polymer) 5-(2,5-dioxotetrahydrofuranyl)_3_methyl-3-cyclohexene as tetracarboxylic dianhydride 1,2 -Dicarboxylic anhydride 26.4 g (0.1 mol) and 4,4'-diaminodiphenylmethane as diamine 14.9 g (0.075 mol) and octadecyloxy-2,4-di Aminobenzene 9 · 6 g (0 · 0 2 5 mol) was dissolved in 2 1 1 g of N · methyl-2-pyrrolidone, and allowed to react at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with a sputum and dried under reduced pressure at 40 ° C for 15 hours to obtain 3 3 g ® polylysine. 2 g of the obtained polyamic acid was dissolved in 3 80 g of N-methyl-2-pyrrolidone, and 8 · 3 g of pyridine and 1 g of acetic anhydride were added to carry out at 1 1 〇 ° C. The dehydration ring-closure reaction was carried out for 4 hours, and the same procedure as above was carried out, washing, and drying under reduced pressure to obtain 1 2 g of a ruthenium iodide polymer (PI-9) having a ruthenium iodide ratio of 9 %. Example 1 The ruthenium imidized polymer PI-1 obtained in Synthesis Example P-1 was dissolved in a mixed solution of 7-butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio • 40: In 30:30), a solution having a solid concentration of 4.0% by weight was prepared. The solution was visually observed to be a turbid transparent solution. The gluten solution was over-concentrated with a crucible having a pore size of 0 · 2 # m to obtain a liquid crystal alignment agent. Using this liquid crystal alignment agent, the evaluation of the vertical alignment property, the voltage retention ratio, and the heat resistance was carried out in accordance with the above method. The results are shown in Table 1. [Examples 2 to 1 1 and Comparative Examples 1 and 2] The liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 of -43-200844609 except that the type of the polymer used was as shown in Table 1. The evaluation results are shown in Table 1. In addition, in each of Examples 8 to 11, two polymers were used, and the use ratio (weight ratio) was as shown in the parentheses in Table 1. -44- 200844609 Table 1 Polymer (% by weight) State of the alignment agent solution (visual observation) Vertical alignment 滪 inclination) Voltage retention rate Heat resistance Initial application of temperature stress Example 1 PI-K100) No turbidity, transparent 89.0° &gt;99% &gt;99% Good Example 2 ΡΙ-2 (100) No turbidity, transparent 89.0° &gt; 99% &gt; 99% Good Example 3 ΡΙ-3 (100) No turbidity, transparent 89.5. &gt;99% &gt; 99% Good Example 4 ΡΙ-4(100) No turbidity, transparent 88.5. 99% 99% Good Example 5 PI-5 (100) No turbidity, transparent 88.0° &gt; 99% &gt; 99% Good Example 6 ΡΙ-6 (100) No turbidity, transparent 88.5. 99% 99% Good Example 7 ΡΙ-7(100) No turbidity, transparent 88.5. 99% 99% Good Example 8 ΡΙ-1/ΡΑ-Κ80/20) No turbidity, transparent 88.5° &gt; 99% &gt; 99% Good Example 9 ΡΙ-2/ΡΑ-Κ80/20) No turbidity, transparent 89.0° &gt; 99% &gt; 99% Good Example 10 ΡΙ-3/ΡΑ-Κ80/20) No turbidity, transparent 89.0° &gt; 99% &gt; 99% Good Example 11 ΡΙ-6/ΡΑ-Κ80/ 20) No turbidity, transparent 88.5. 99% 99% Good Comparative Example 1 ΡΙ-8 (100) No turbidity, transparent 84.0. 97% 95% Bad Comparative Example 2 ΡΙ-9(Ι00) No turbidity, transparent 83.0° 97% 94% Bad

[Simple description of the diagram] Μ 〇 j\\\ [Description of main component symbols]

-45-

Claims (1)

200844609 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a group consisting of (a) a compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); a polyamic acid prepared by reacting at least one of a tetracarboxylic dianhydride with (b) a diamine including at least one selected from the group consisting of compounds represented by the following formulas (3) to (6) and/or醯iminated polymer, In the formula (2), R is a single base with a carbon number of 1 〜 n is an integer of 〇 〜2 - 46 - 200844609 In the formulae (3) to (6), R1 to R4 are each independently a linear, branched or cyclic alkyl group having a carbon number of 1 to 40 or a linear or branched carbon number of 4 to 40. The chain or cyclic alkenyl group, 1 to 15 of the hydrogen 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. 2. The liquid crystal alignment agent of the first aspect of the invention, wherein the total amount of the compound represented by the above formula (1) and the compound represented by the above formula (2) is 80% by mole or more based on the total of the tetracarboxylic dianhydride. . 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine represented by the above formulas (3) to (6) has a group R1 to R4 having a steroid-47-200844609 (steroid) skeleton. Group. 4. The liquid crystal alignment agent according to claim 1 or 2, wherein (b) the diamine is represented by the above formula (3), and R1 is a linear, branched or cyclic group having a carbon number of 1 to 20. An alkyl group or a linear, branched or cyclic alkenyl diamine having 4 to 20 carbon atoms. A liquid crystal display element characterized by having a liquid crystal alignment film produced by the liquid crystal alignment agent according to any one of claims 1 to 4. -48 - 200844609 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 y\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: