TW201015177A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal aligning agent which a liquid crystal alignment film with pantoscopic property, high quality display, excellent afterimage phenomena and sticking property could be carried out by this liquid crystal aligning agent in the liquid crystal display element of transverse electrical filed. The solution of the present invention is a liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamidic acid and a polyimide, in which the said polyamidic acid is prepared by the reaction of tetracarboxylic acid with diamine having a structure represented by the following formula (A) and a compound with two amido; the said polyimide is obtained by the dehydrocycloization of said polyamidic acid.

Description

201015177 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, the liquid crystal alignment agent which is particularly suitable for forming a liquid crystal alignment film of a horizontal electric field type liquid crystal display element, and a horizontal electric field type liquid crystal display element which is excellent in afterimage performance and afterimage performance and which can realize high quality display. [Prior Art] A horizontal electric field type liquid crystal display element in which an electrode is formed only on one side of a pair of oppositely disposed substrates and an electric field is generated in a direction parallel to the base plate, and it is known to form an electrode on the two substrates and Compared with the old-fashioned vertical electric field type liquid crystal display element which generates an electric field in the vertical direction of the substrate, it has wider viewing angle performance and can realize higher quality display. Such a horizontal electric field type liquid crystal display element is described in, for example, Patent Documents 1 and 2 and Non-Patent Document 1. In the horizontal electric field type liquid crystal display element, since the liquid crystal molecules generate an electric field response only in the direction parallel to the substrate, there is no problem that the refractive index of the liquid crystal molecules changes in the long axis direction, even when the viewing angle is changed, observation © The contrast that can be discerned and the change in color depth of display are also small, so that high-quality display can be achieved regardless of the angle of view. In order to obtain such a beneficial effect, the dependence of the incident angle of the incident polarized light is small, and therefore, in the lateral electric field type liquid crystal display element, it is desirable that the pretilt angle in the initial alignment performance when no electric field is applied is small. However, in the case of a horizontal electric field type liquid crystal display element, there are cases where afterimage and afterimage problems occur, and improvement in this respect is required. On the other hand, in Patent Document 3, a method of improving afterimage performance and afterimage performance by using a liquid crystal alignment film of 201015177 composed of a polymer having a high ratio of aromatic structure has been proposed. However, if a liquid crystal alignment film containing a high ratio of aromatic structure is used, the pretilt angle is inevitably increased, thereby reducing the above-described advantageous effects of the lateral electric field type display element. In the horizontal electric field type liquid crystal display device, it is not known that a liquid crystal alignment agent capable of exhibiting the above-described advantageous effects and exhibiting improved afterimage performance and afterimage performance, and thus it is urgent to provide such a liquid crystal. An aligning agent.

[Patent Document 1] US Patent No. 005928733A [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a wide-angle-type liquid crystal display device capable of achieving both wide viewing angle performance and high-quality display and good disability. A liquid crystal alignment agent for a liquid crystal alignment film like performance and afterimage performance. Another object of the present invention is to provide a horizontal electric field type liquid crystal display element which has both wide viewing angle performance and high quality display and good afterimage performance and afterimage performance. 201015177 Other objects and advantages of the present invention can be solved by the following description. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent comprising a tetracarboxylic acid selected from An anhydride consisting of a polylysine obtained by reacting a structure represented by the formula (Α) with a compound having two amine groups, and a polyimine which is obtained by dehydration of the polyglycine At least one of the polymers, known. , obtained by containing a lower amine

(eight)

(In the formula (A), "expressed as a bonding bond". The above objects and advantages of the present invention, and second, a liquid crystal alignment agent of the present invention comprising a liquid crystal alignment film having a liquid crystal alignment film formed of an upper alignment agent, When used for a horizontal electric field type liquid crystal display, it is possible to form a liquid crystal alignment film capable of achieving afterimage performance and afterimage performance having both wide viewing angle performance and high quality display. Therefore, the present invention having a liquid crystal alignment film formed by a liquid crystal alignment agent The horizontal electric field type liquid element has both wide viewing angle performance, high quality display and good afterimage residual image performance, and can be suitable as various liquid crystal display elements, such as a bell-type game machine, a word processor, a notebook type personal computer, a steam meter. The liquid crystal display element used in a display device such as a camera, a PDA, a digital camera, a mobile phone, or a liquid crystal television, etc., is the best mode for carrying out the invention. The liquid crystal alignment agent of the present invention comprises a tetracarboxylic dianhydride selected from the above. a polylysine obtained by reacting a structure represented by the formula (A) with a compound having two amine groups, and dehydrating the polylysine to liquid crystal Achieved with at least one of the group consisting of the crystal display and the performance of the watch, the car navigation device, and the polyamine containing 201015177 containing the diamine. <Polyproline> The polylysine in the liquid crystal alignment agent of the present invention may be composed of a tetracarboxylic dianhydride and a compound having the structure represented by the above formula (A) and a compound having two amine groups. [Tetracarboxylic acid dianhydride] As a tetracarboxylic dianhydride for synthesizing polyglycine in the liquid crystal alignment agent of the present invention, an alicyclic tetracarboxylic dianhydride or an aliphatic tetracarboxylic acid can be cited. Acid dianhydride and aromatic tetracarboxylic dianhydride β ❹ As specific examples of the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 2 ·Dimethylcyclobutanine tetraresidic acid-liver, 1,3·-methyl-1,2,3,4-cyclobutanine tetradecanoic acid dianhydride, ι,3_ monochloro-1,2,3, 4-cyclobutylene tetraphthalic acid dianhydride, iota, 2,3,4-tetramethyl 4,2,34-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, U4 5-cyclohexane tetracarboxylic dianhydride, 3,3,,4,4 _Dicyclohexyltetracarboxylic dianhydride, cis_3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5_ Tricarboxycyclopentyl acetic acid dianhydride, 5·(2,5-dioxotetrahydrofuranyl)3methyl-3-cyclohexylH2-diphthalic anhydride, 3,5,6-curry-carboxy-norbornanoic acid Dianhydride, • Furyl)-naphthalene-2:3,5:6-dianhydride, 2,3,4,5_tetrahydrofurantetra 1,3,38,4,5,91?-hexahydro-5-(four Hydrogen-2,5-dioxo-[l,2-c]-furan-1,3·dione ' 13,3&, 4,5,91)_hexaoxy-methyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene nc].furanedione, 1,3,3&,4,5,91)-hexahydro-5-ethyl_5_(tetrahydro- 2,5-di every 仏*-3-furanyl)·naphthalene [l,2-c]-furan-1,3-dione, ^33,4,5,91)-six-synthesis 1 - 7. Methyl-5-(tetra 201015177 hydrogen · 2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a, 4,5,9b-hexahydro-7.ethyl_5_(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione , 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-( :]-furan-1,3-dione, 1,3,3&,4,5,9 Hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphthalene [l,2-c]-furan-indole, 3-dione, 1, 3,3&,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c ]-furan-1,3·dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene fluorene-1,2-di-residic acid, double ring [2.2. 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxaxanthene t3.2·1]octane-2,4-dione·6-spiro·3 , -(tetrahydrofuran-2',5'-dione), a compound represented by the following formula (Τ-Ι) or (Τ-ΙΙ);

(In the formulae (Τ-I) and (Τ-II), R1 and R3 each are a divalent organic group having an aromatic ring, and R2 and R4 are each a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may each The same 'may be different'. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butane tetracarboxylic dianhydride. 201015177 Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4,-diphthalic dianhydride, and 3,3',4,4,-benzophenone. Tetracarboxylic dianhydride, 3,3',4,4,-diphenyl maple tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3,4,4,-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3 , 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 12,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Phenyl sulfide dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenyl maple dianhydride, 4,4'-bis(3,4.dicarboxyphenoxy)diphenyl Propane dianhydride, 3,3,,4,4,-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4,-biphenyltetracarboxylic dianhydride, di(o) Phthalic phosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, di(three) Phenylphthalic acid)-4,4'-diphenyl ether dianhydride, two (three Phenylphthalic acid)_4,4,-diphenylmethane dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di(hydrogen trimellitate), hydrazine, 4 butyl Alcohol-di(hydrogen trimellitate), 16-hexanediol-di(hydroper trimellitate), 1,8-octanediol-di(anhydrotrimellitic acid ester), 2,2- Bis(4-hydroxyphenyl)propane·di(hydrogen trimellitate) and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. The tetracarboxylic dianhydride used for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention preferably contains pyromellitic acid selected from the group consisting of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. A tetracarboxylic dianhydride of at least one of a group consisting of dianhydride and 4,4'-diphthalic dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride"). As the specific tetracarboxylic dianhydride, it is preferably selected from 1,2,3,4-cyclobutane IV 201015177 carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutylene. Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dihydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydro-3-hydrogenyl)-3-methyl-3-cyclohexene-1, 2-Dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cis-3,7-dibutyl ring Oct-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-l,3- Diketone, 1,3,3a,4,5,9b-nonylhexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2- c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, bicyclo[2_2.2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(four a furan-2',5'-dione), a compound represented by the following formula (T-1) to (T-3) in the compound represented by the above formula (T-I), and the above formula (Τ - II) At least one of the compounds represented by the following formula (T-4), pyromellitic dianhydride, and 4,4'-diphthalic dianhydride in the compound represented by the group, -10- 201015177

(Τ-1) (Τ-2) (Τ-3) Ο Ο is particularly preferably selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3&, 4, 5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(;]-furan-1,3-di At least one of the group consisting of a ketone, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, pyromellitic dianhydride, and 4,4,-diphthalic dianhydride. The polycarboxylic acid tetracarboxylic dianhydride contained in the liquid crystal alignment agent is preferably contained in an amount of 60 mol% or more, more preferably 80 mol% or more, based on the total tetracarboxylic dianhydride. Specific tetracarboxylic dianhydride [Diamine] The diamine used for the synthesis of the poly-proline in the liquid crystal alignment agent of the present invention is a compound having the structure represented by the above formula (Α) and having two amine groups (below - 11-201015177 A diamine which is called "compound (A)"). The compound (A) is, for example, a compound represented by the following formula (A-1).

(A-1) (In the formula (A-1), each of U is a methylene group, a carbon atom number of 2 to 6, a stretching group, a stretching phenyl group, a stretching naphthyl group, a cyclohexylene group, a pyrimidyl group or a stretching group. The plurality of u in which the well group 'n is an integer of 1 to 5' may be the same or different. Specific examples of U in the above formula (A-1) include, for example, a 1,3-dienyl group, a 1,4-cyclohexylene group, an i,4-phenylene group, and a naphthalene-1,5-diyl group. , chelate pyridine-2,5-diyl, tri-trap-2,4-diyl and the like. Specific examples of the compound represented by the above formula (A-1) include N,N'-bis(3-aminopropyl)fluorene trap and n,N'-bis(4-aminocyclohexane group). Anthracene, N,N'-bis(4-aminophenyl) hydrazine, etc., among which n, N,-bis(4-aminophenyl) hydrazine is preferred. As the diamine which is used for synthesizing the poly-proline in the liquid crystal alignment agent of the present invention, the compound (A) may be used alone or in combination with the other diamine. As other diamines which can be used in the present invention, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane can be mentioned. , 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl milling, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4, 4,-Diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4,-diamine linkage Benzene, 5-amino-1-(4'-aminophenyl)-l,3,3-trimethylindan, -12- 201015177 6-amino-l-(4'-aminophenyl )-l,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone , 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxyl) Phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]pluta, 1, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9- Bis(4-aminophenyl)-10-hydrogen , 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5 '-O tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3' -dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(inter)phenyldiisopropene Diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2' - bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-fluorenylmethyl)phenoxy]-octafluorobiphenyl, bis(4-aminophenyl)benzidine , 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine, a compound such as a compound represented by the following formulas (D-1) and (D-2) Group diamine,

(D-2) (wherein y in the formula (D-1) is an integer of 2 to 12, and z in the formula (D-2) is an integer of 1 to 5); -13- 201015177 1,1-diphenylene Methylamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-diaminocyclohexane, isophorone Diamine, tetrahydrodicyclopentadienediamine, tricyclo[6.2.1.0 2'7]undecylalkyldiamine, 4,4'-methylenebis(cyclohexylamine), 1 An aliphatic or alicyclic diamine such as 3-di(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-Diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrrole, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4·diamino-6 · dimethylamino-1,3,5-tri-trap, 1,4-decanedi(3-aminopropyl)fluorene trap, 2,4-diamino-6-isopropoxy-1,3 , 5-three tillage, 2.4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamino-6-phenyl-1,3,5-tri-trap, 2 ,4-diamino-6-methyl-8-three tillage, 2,4-diamino-1,3,5-three tillage, 4,6-diamino-2-vinyl-s-three Well, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-Diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxy acridine Lactic acid ester, 3,8. diamino-6-phenylphenanthridine, 1,4-diamine hydrazine, 3,6-diamino acridine, bis(4-aminophenyl)phenyl Amine, 1-(3,5-diaminophenyl)-3-mercaptoarene® amine, 1-(3,5-diaminophenyl)-3-octadecyl succinylamine, under a diamine having two primary amino groups in the molecule such as a compound represented by the formula (D-I) and a nitrogen atom other than the primary amino group,

(DI) (In the formula (D-I), X each is a divalent organic group-14-201015177 group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple trap, and acridine R5 is a divalent organic group, each of R6 is an alkyl group having a carbon number of *, and each a is an integer of 〇~3, and a plurality of X groups present may be the same or different, and when there are a plurality of R6 Each of them may be the same or different); a diamine-based organooxane such as a compound represented by the following formula (D-II);

〇❹ (In the formula (D-II), each of R7 is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R7 groups may be the same or different, each p is an integer of 〜3, and q is 1~ An integer of 20). These diamines may be used alone or in combination of two or more. The benzene ring of the above aromatic diamine may be substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. R6 in the above formula (D-I) is preferably a methyl group, and a each is preferably 0 or 1, more preferably 0. Preferred examples of the diamines of these diamines include p-phenylenediamine, 4,4,-diaminodiphenylmethane and 4,4,-diaminodiphenyl sulfide in the above aromatic diamine. 1,5.Diaminonaphthalene, 2,7-diaminophenanthrene, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)benzene Propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di(4) -aminophenyl)hexafluoropropane, 4,4,-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(meta-phenyldiisopropylidene)diphenylamine, 1, 4·bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-Diaminopyrimidine, 3,6-diaminoacridine, 1-(4--15- 201015177 aminophenyl)-l,3,3-trimethyl-1H-segment-5- An amine or a compound represented by the above formula (d-1) or (D-2); 1, Cyclohexanediamine or 4,4,_methylenebis(cyclohexylamine) in the above alicyclic diamine a compound represented by the following formula (D-3) in the compound represented by the above formula (D-I);

0 1,3-bis(3-aminopropyl)tetramethyldioxane in the compound represented by the above formula (D-II). The diamine used for synthesizing the poly-proline in the liquid crystal alignment agent of the present invention preferably contains 1 mol% or more, more preferably 1 mol% or more, and particularly preferably 10% of the total diamine. 80 mol%, especially good contains 15~50 mol% of compound (A). The diamine for synthesizing the poly-proline in the liquid crystal alignment agent of the present invention preferably contains an aromatic diamine in addition to the compound (A), and more preferably a chemical complex (A) and an aromatic diamine. Further, a compound represented by the above formula (D-π) is further contained. When the diamine for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention contains an aromatic diamine, the use ratio thereof is preferably from 20 to 99 mol%, more preferably from 50 to 90 mol%, Further preferably, it is 50 to 85 mol%. When the diamine used for the synthesis of the poly-proline in the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (D-II), the use ratio thereof is preferably 0.1 to 10 mol%, more preferably 1 ~8 moer. /. Further, it is preferably 3 to 7 mol%. -16-201015177 [Synthesis of Polylysine] The polylysine in the liquid crystal alignment agent of the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound (A). The ratio of use of the tetradecanoic dianhydride to the diamine supplied to the polyamic acid synthesis reaction is preferably '1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of ojkU equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, preferably for 1 to 72 hours. The better system is carried out for 3 to 48 hours. Here, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the produced polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. N,N-dimethylformamide, 3-butoxy-oxime, Ν·dimethylpropanamide, 3-methoxy-oxime, Ν-dimethylpropanamide, 3-hexyloxy - anthraquinone compounds such as guanidine, guanidine-dimethylpropionamide, dimethyl sulfite, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol , phenolic compounds such as dimethyl phenol, phenol, and halogenated phenol. The amount of the organic solvent (α: when the organic solvent is used together with the poor solvent described below, it means the total amount thereof), and usually, it is preferable to make the total amount (0) of the tetracarboxylic dianhydride and the diamine relative to The total amount of the reaction solution (α + 々) is an amount of 0.1 to 30% by weight. In the above organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons which are generally considered to be poor solvents of polyproline are used in a range in which the produced polyamine acid is not precipitated. Classes, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexa-17-.201015177 alcohol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1 , 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, acetic acid Ethyl ester, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene Alcohol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro Butane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate Diisoamyl ether, etc.When the organic solvent is used in combination with the poor solvent as described above, the amount of the poor solvent may be appropriately set within a range in which the formed polyaminic acid is not precipitated, and preferably the total amount of the solvent is 30. The weight% or less is more preferably 20% by weight or less. ^ As described above, a reaction solution in which polylysine is dissolved is obtained. The reaction solution may be directly supplied to a liquid crystal alignment agent, or may be obtained by separating a polyamic acid contained in the reaction solution and then supplying it to a liquid crystal alignment agent. Alternatively, the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is then supplied. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the reaction solution by an evaporator under reduced pressure. And proceed. Further, the polypyridic acid can be re-dissolved in the organic solvent 18-201015177, and then precipitated by a poor solvent, or subjected to a step of distilling off one or several times with an evaporator under reduced pressure. Proline. <Polyimine> The polyimine in the liquid crystal alignment agent of the present invention can be obtained by imidating the poly-guanidic acid as described above. The polyimine contained in the liquid crystal alignment agent of the present invention may be a fully ruthenium imine compound in which the proline structure of the precursor glycine acid is dehydrated and closed, or only a part of the proline structure may be dehydrated. A closed-loop, partially ruthenium imide that coexists with a ruthenium quinone ring structure. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 40% or more, more preferably 50 to 90%. By using a polyimine having a ruthenium iodide ratio of 40% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a shorter afterimage erasing time can be obtained. The above ruthenium amide ratio is a total amount of the guanidine structure and the number of quinone ring structures in the polyimine, and the ratio of the number of quinone ring structures is expressed as a percentage. At this time, a part of the quinone imine ring may also be an oxime ring. The ruthenium imidization rate can be obtained by dissolving the polyimine in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) with tetramethyl decane as the reference material 'at room temperature (for example, 25 ° C) 1H-NMR was measured, and the measurement result was obtained by the following formula (1). Brewing imidization rate (%) = (1 - A^/A^a )xl00 (i) (In equation (i), A1 is the peak area derived from the NH matrix near the chemical shift of 10 ppm, and A2 is From the peak area of other protons, α is the ratio of -19 to 201015177 relative to the other protons of one sulfhydryl group in the precursor of poly(imine). Dehydration ring closure of polylysine, preferably (i.) by heating poly-proline, or (Π) by dissolving poly-proline in an organic solvent, adding dehydrating agent and dehydration ring closure to the solution The catalyst is carried out according to the method of heating as needed. The reaction temperature in the method of heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. The reaction time is preferably from 1 to 8 hours, more preferably from 3 to 5 hours. When the reaction temperature is less than 50 °C, the dehydration enthalpy ring closure reaction cannot be sufficiently carried out. When the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyimine is lowered. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic 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 mole of the prolinic acid structure of the polyglycolic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per 100 parts of the dehydrating agent used. The more the amount of the above dehydrating agent and the dehydration ring-closing agent, the higher the yield of hydrazine. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as an organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150. (: The reaction time is preferably from 1 to 8 hours, more preferably from 3 to 5 hours. The polyimine prepared in the above method (i) can be directly supplied to the liquid -20-201015177 crystal alignment agent. Alternatively, the obtained polyimine may be purified and then supplied to a liquid crystal alignment agent. Further, in the above method (π), a reaction solution containing a polyimine may be obtained. The reaction solution may be directly used. The preparation of the liquid crystal alignment agent may be carried out by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then supplying the liquid crystal alignment agent, or separating the polyimine from the liquid crystal alignment agent, or may be separated. After the polyimine is refined, it is supplied to a liquid crystal alignment agent, and the dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and for example, a solvent may be used to replace the ruthenium. The separation and purification of the polyimine may be carried out as described above. The same operation as described for the separation and purification method of polylysine. [End-modified polymer] Polyamine which may be contained in the liquid crystal alignment agent of the present invention Further, the polyimine may be a terminal-modified polymer having a molecular weight adjusted by using a terminal-modified polymer, and the coating property of the liquid crystal alignment agent or the like can be further improved without impairing the effects of the present invention. The terminal-modified polymer can be obtained by adding a molecular weight modifier to the polymerization reaction system during the synthesis of the poly-proline. Examples of the molecular weight modifier include a monoanhydride, a monoamine compound, a monoisocyanate compound, and the like. The monoanhydride may, for example, be maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride or 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 Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecane-21- 201015177 Aminobenzene decanoic acid cyanide, as an example, the amines are listed in the eight to ten, Amine alkylated heptadecanoic acid, n-fluoride, iso-amine monoalkane, six-upper ten, positive, o-amine, etc., isocyanate isocyanate, etc. The use ratio of the molecular weight modifier is relative to 100 parts by weight of polyfluorene The total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the amino acid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. [Solid viscosity] Polylysine or polyfluorene prepared as above The imine, preferably having a solution concentration of 10% by weight, has a solution viscosity of 20 to 800 mPa's, more preferably a solution viscosity of 30 to 500 mPai. The solution viscosity (mPa's) of the above polymer, Is a polymer solution prepared by using a good solvent (for example, r-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer at a concentration of 10% by weight, measured by an E-type rotational viscometer at 25t. value. <Other components> The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyammonium® acid as described above and polyamidene obtained by dehydration and ring closure thereof. As an essential component, other components may be contained as needed. As such other components, for example, other polymers, adhesion enhancers, and the like can be given. [Other Polymers] The above other polymers can be used for the purpose of improving solution properties and electrical properties. The other polymer is a poly-proline which is obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound (A) and a polyazide obtained by dehydrating the polyglycolic acid to -22-201015177. Examples of the polymer other than the amine include polyglycine (hereinafter referred to as "other poly-proline") obtained by reacting tetracarboxylic dianhydride with a diamine containing no compound (A), and the polymerization is carried out. Polyimine (hereinafter referred to as "other polyimine"), polyglycolate, polyester, polyamine, polyoxyalkylene, cellulose derivative, poly Acetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. Among them, other polyamines or other polyimines are preferred. As the tetracarboxylic acid ruthenium anhydride for synthesizing other polyamic acid or other polyimine, the above tetracarboxylic acid can be exemplified as a polyamine or polyimine which is an essential component for synthesizing the liquid crystal alignment agent of the present invention. The same tetracarboxylic dianhydride as dianhydride. Among them, tetracarboxylic dianhydride containing alicyclic tetracarboxylic dianhydride is particularly preferred as 1,2,3,4-cyclobutanetetracarboxylic dianhydride. The tetracarboxylic dianhydride for synthesizing other polyaminic acid or other polyimine, preferably contains 30 mol% or more, more preferably 50 mol% or more, based on the total tetracarboxylic dianhydride. Cyclic tetracarboxylic dianhydride. As a diamine for synthesizing other polyphosphonic acid or other polyimine, ^ is exemplified as other diamine which can be used for synthesizing polyamine or polyimine which is an essential component of the liquid crystal alignment agent of the present invention. The same diamine. Among them, preferred are diamines containing an aromatic diamine, and particularly preferred are selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenylmethane. 2,2'-trifluoromethyl-4,4'-diaminobiphenyl and 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine A diamine of at least one of the constituent groups. The diamine used for the synthesis of other polyaminic acid or other polyimine is preferably contained in an amount of 5 mol% or more based on the entire diamine, and more preferably contains 1 mol% or more of aromatic-23-201015177 Diamine. Other polyamines and other polyimines can be synthesized in the same manner as described above for the synthesis of polyamine or polyimine which is an essential component of the liquid crystal alignment agent of the present invention. When the liquid crystal alignment agent of the present invention contains another polymer, it is selected from the above-mentioned polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound (A), and the polyglycine is dehydrated and closed. The ratio of use of at least one of the polymers of the group of the obtained polyimines is relative to the total amount of the polymerized chelates (refers to the reaction of the tetracarboxylic dianhydride with the diamine containing the compound (A) The total amount of the polylysine obtained and the polyamidene obtained by dehydration of the polyglycolic acid and other polymers are the same as the following, preferably 1% by weight or more, more preferably 3~ 50% by weight, particularly preferably 5 to 45% by weight. [Adhesive Enhancer] The above-mentioned adhesiveness enhancer can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the surface of the substrate. As such an adhesion enhancer, for example, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, or the like can be given. Examples of the epoxy group compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, -24- .201015177 N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidol Aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. The use ratio of the epoxy group as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymer. The functional decane compound may, for example, be 3, aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropylphosphonium trimethoxynonane or 2-aminopropylpropane. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3.aminopropylmethyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxy Decane-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diaza壬® based acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3·aminopropyltrimethoxydecane, N-benzyl- 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-di ( Oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like. The use ratio of the functional decane compound as described above is preferably 2 parts by weight or less, more preferably 0.01 to 0.2 parts by weight, based on the total amount of the 100 parts by weight of the polymer. -25- 201015177 <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is a polyamic acid selected from the group consisting of a tetracarboxylic dianhydride and a diamine containing the compound (A) as described above, and The polymer of at least one of the group consisting of the polyamidene obtained by dehydration of the polyamic acid and the other additives optionally blended as needed are preferably dissolved in an organic solvent. Examples of the organic solvent which can be used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, anthraquinone, hydrazine-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxy Ethyl propyl propionate, 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, B Glycol diethyl 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 Ester, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylhydrazine Acrylic amine and the like. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 1 () The range of % by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below. It is preferred to form a coating film as a liquid crystal alignment film by heating. When the solid content concentration is less than 1% by weight, the thickness of the coating film is caused. Too small to obtain a good liquid crystal alignment film; on the other hand, when the solid concentration of -26-201015177 exceeds ίο重量%, 'the coating film thickness is too thick to obtain a good liquid crystal alignment film, and the liquid crystal alignment agent The viscosity increases, resulting in poor coating properties. A particularly preferable solid content concentration range ' differs depending on the method used when the liquid crystal alignment agent is coated on the substrate. For example, when the spin coating method is employed, the specific solid content concentration is in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is preferable to set the solid content concentration to a range of 3 to 9 % by weight, whereby the solution viscosity can be made to fall within the range of 12 to 50 mPa's. When the ink jet enthalpy method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 wt%, whereby the solution viscosity can be made to fall within the range of 3 to 15 mPa_s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. The liquid crystal alignment agent of the present invention obtained as above can be particularly suitably used for forming a liquid crystal alignment film of a transverse electric field type liquid crystal display element. <Horizontal electric field type liquid crystal display element> The horizontal electric field type liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The horizontal electric field type liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). (1) First, a coating film is formed on a substrate by applying the liquid crystal alignment agent of the present invention onto a substrate and then heating the coated surface. Here, as the substrate, a conductive film forming surface of a substrate provided with a transparent conductive film forming a comb-tooth pattern and a substrate having no conductive film disposed therebetween are used as a pair, and preferably a roll coating method or a spin coating method is used. Or inkjet printing -27-201015177 brushing method, respectively, on the conductive film forming surface of the substrate provided with the transparent conductive film forming the comb-tooth pattern, and on the side of the substrate (opposing substrate) on which the conductive film is not provided The liquid crystal alignment agent of the present invention is then heated to form a coating film on each coated surface. As a material constituting the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether mill, polycarbonate, poly (fat) can be used. Ring olefin) and other plastics. As the transparent conductive film provided on one surface of the one-side substrate, an NESA film (registered trademark of PPG, Inc., USA) made of tin oxide (Sn02), an ITO film made of indium oxide-tin oxide (Ιη203-Sn02), or the like can be used. The pattern of the transparent conductive film can be obtained, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound or a functional titanium may be preliminarily coated on the surface of the substrate on which the coating film is to be formed. Pretreatment of compounds and the like. The heating temperature after coating the liquid crystal alignment agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes. The thickness of the formed coating film is preferably 0.001 to 1 / ζ ηη, more preferably 0.005 to 0.5 yUm. The liquid crystal alignment agent of the present invention forms a coating film as an alignment film by coating after removing the organic solvent as described above, and when the liquid crystal alignment agent of the present invention contains polyamic acid or a polyimine structure having a quinone ring structure and a proline structure In the case of quinone imine, it is also possible to carry out a dehydration process by dehydration 28-201015177 by further heating after forming a coating film to form a further yttrium-imided coating film. (2) Then, the coating film surface formed as described above is subjected to a rubbing treatment in a certain direction by a roll wrapped with a cloth made of a fiber such as nylon, rayon, or cotton. Thus, the alignment energy of the liquid crystal molecules can be generated on the coating film to form a liquid crystal alignment film. In the liquid crystal alignment film formed as described above, a part of the liquid crystal alignment film shown in the patent document 4 (JP-A-6-222366) or the patent document 5 (JP-A-6-281937) a process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating the ultraviolet ray, or forming a resist film on the surface of the liquid crystal alignment film portion as shown in Patent Document 6 (JP-A No. 5-107544) The treatment for removing the resist film after the rubbing treatment is performed in a direction different from the previous rubbing treatment, so that each region of the liquid crystal alignment film has a different liquid crystal alignment energy, which can improve the field of view performance of the obtained liquid crystal display element. (3) A liquid crystal cell is produced by providing liquid crystal in a gap between a pair of substrates on which a liquid crystal alignment film is formed as described above. At this time, the two substrates are disposed such that the liquid crystal alignment films each having ® are opposed to each other and the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other. For the production of the liquid crystal cell, for example, the following two methods can be mentioned. The first method 'is a previously known method. First, the two substrates are placed opposite each other through the gap (box gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together with a sealant to the cell gap surrounded by the substrate surface and the sealant. After filling the liquid crystal with the internal injection, the injection hole is closed, and the liquid crystal cell can be obtained. • 29- 201015177 The second method is called the ODF (One Drop Fill) method. For example, an ultraviolet curable sealant material is applied to a predetermined portion of the two substrates in the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal is dropped on the liquid crystal alignment film surface, and then the other substrate is bonded to make the liquid crystal alignment film relatively The liquid crystal cell can be obtained by irradiating the entire surface of the substrate with ultraviolet rays to harden the sealant. When any of the above first and second methods is employed, it is necessary to eliminate the flow alignment of the liquid crystal by heating the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase and then slowly cooling to room temperature. . Then, the transverse electric field type liquid crystal display element of the present invention can be obtained by laminating a polarizer on the outer surface of the liquid crystal cell. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator, and the like can be used. Examples of the liquid crystal include nematic liquid crystal and disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff's domain liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, a ® ester liquid crystal, a terphenyl liquid crystal, or a combination can be used. Phenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, or the like. Further, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals; and the trade names "C-l5" and "CB-15" (manufactured by Merck) A chiral agent sold; used for ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutyl cinnamate. The polarizer which is bonded to the outer surface of the liquid crystal cell may be a polarizer which is obtained by stretching the polyethylene-30-201015177 enol to simultaneously absorb iodine and is referred to as a "ruthenium film, which is sandwiched between the cellulose acetate protective film. Or a polarizer. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, and the present invention is not limited to these examples. Further, N, N'- in the following synthesis examples Bis(4-aminophenyl)anthracene is directly used as a commercial product of Wakayama Seiki Chemical Co., Ltd. Ο In addition, the solution viscosity of the polymer in each synthesis example is a £-type viscosity meter at 25 ° C. Determined enthalpy. <Synthesis of Polyimine> Synthesis Example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 2 24 g (1.0 liter), as a diamine of p-phenylene Amine 40.5 g (0.38 mol), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2 g (0.20 mol), 3,3'- (Tetramethyldioxane-1,3-diyl)di(propyl-amine) 12.4 g (0.050 mol) and N,N'-bis(4-aminophenyl)anthracene 100.5 g ( 0.375 mol was dissolved in 2440 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. Take a small amount of the obtained polyamidamine solution, add N-methyl-2-pyrrolidone to dilute, and prepare a solution having a polyglycine concentration of 10% by weight, and determine the solution viscosity to be 75 mPa·s. Then, in the obtained polyfluorene 2500 g of N-methyl-2-pyrrolidone was added to the amine acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at -31 to 201015177 at 110 °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system. Then, it was concentrated to obtain 2500 g of a solution containing 15% by weight of a polyimine (A-1) having a ruthenium iodide ratio of about 51%. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 25 mPa·s. Synthesis Example 2 224 g (l. oxime) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 40.5 g (0.38 mol) of p-phenylenediamine as a diamine. , 1-(4-Aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2 g (0.20 mol), 2,2'-trifluoromethyl-4,4 '-Diaminobiphenyl 16.0 g (0.050 mol) and N,N'-bis(4-aminophenyl)fluorene trap l〇〇.5 g (0.375 mol) dissolved in 2460 g N-methyl- The 2-pyrrolidone was allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. Take a small amount of the obtained polyamidamine solution, add N-methyl-2-pyrrolidone for dilution, and prepare a solution of polyglycine with a concentration of 10% by weight of the solution, and measure the viscosity of the solution to 60 mPa.s. 2500 g of N-methyl-2-pyrrolidone was added to the polyamine solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added at 11 Torr. Underarm for 4 hours dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-izzarone, and then concentrated to obtain 2500 g of a polyfluorene containing 15% by weight of a ruthenium iodide ratio of about 51%. A solution of an imine (A-2). A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution had a viscosity of -32-201015177 degrees of 22 mPa_s. Synthesis Example 3 A solvent of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride is treated with a "mole" as a diamine of p-phenylenediamine. Aminophenyl)-1,3,3_trimethyl_111_茚-5_amine 53.2 to 〇2〇莫耳), 4,4'-diaminodiphenylmethane 2^(0" Ear), 3,3,_(tetramethyldioxane-1,3-diyl)di(propylamine)l2.4g (〇.〇5〇莫耳) and N,N,二(4_ Aminophenyl) 呱 87.lg (0.3 25 moles) was dissolved in 246 〇g N_methyl _2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The solution. A small amount of the obtained polyamine solution was added, and N-methyl-2-pyrrolidone was added to fr-diluted into a solution having a concentration of polyfee acid of ίο% by weight, and the viscosity of the solution was determined to be 70 mPa*s. Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 1 g of acetic anhydride were added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2500 g of 15% by weight of quinone imine. A solution of about 51% polyethylenimine (A-3). A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight. The solution viscosity was 24 mPa·s. Synthesis Example 4 2,3,5-tricarboxycyclopentylacetic acid dianhydride 2248 (1. oxime) as tetracarboxylic dianhydride, p-phenylenediamine as diamine 358 (0.33 mol), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2 g (0.20 mol), -33- 201015177 4,4 '--Amino-Phenyl Courtyard 23g (0.1 mol), 2,2'-trifluoromethyl-4,4,-diaminobiphenyl 16_0g (0.050 mol) and n, N, - (4-Aminophenyl) 88.7 g (0.325 mol) was dissolved in 2460 g of N-methyl-2-pyrrolidone, and allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyamine solution is diluted with N-methyl-2-pyrrolidone to form a solution. The brewing solution: the solution having a acid concentration of 10% by weight/〇 has a solution viscosity of 58 mPa·S °. Then, 2500 g of N-methyl-Ιο 耻略院酮 is added to the obtained polyaminic acid solution, and then 80.2 is added. g卩 ratio steep and i〇3g acetic anhydride, 4 hours dehydration ring closure reaction at 〇 ° ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, Then, it was concentrated to obtain 2600 g of a solution containing 15% by weight of polyamidiamine (A-4) having a ruthenium iodide ratio of about 53 %. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to form a polypeptone. A solution having an imine concentration of 6.0% by weight, the measured solution viscosity was 21 mPa's. Synthesis Example 5 ® 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 224 g (1.0 mol) , p-phenylenediamine as a diamine 35g (0.33 mol), ι·(4_aminophenyl)-1,3,3-trimethyl-1H-p--5-amine 53.2 g (0.20 mol) 4,4'-diaminodiphenyl ether 20g (0.1 mole), 3,3'-(tetramethyl oxalate-1,3-diyl) bis(propylamine) 12.4g ( 〇.〇50 Mo) and n,N,-di(4-amine 87.1 g (0.325 mol) of phenyl) foxhole was dissolved in 245 g of N-methyl-2-indole-s-alkanone and allowed to react at room temperature for 6 hours to obtain a solution containing poly-proline. Take a small amount of the obtained polyamidamine solution, add N-methyl-2-Jialy, and dilute it to -34-.201015177, and prepare a solution with poly-proline concentration of ίο% by weight. The measured solution viscosity is 73 mPa· s. Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 80.2 g of pyridine and i3 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under not. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine containing 15% by weight of a ruthenium iodide (about 54%). A-5) solution. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 26 mPa-s. Synthesis Example 6 202 g (0.90 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 22 g (0.01 mol) of pyromellitic dianhydride as a diamine pair Phenyldiamine 35g (0.33 mole), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2g (0.20 mole), 4,4' -diaminodiphenylmethane 23g (0.1 mole), 2,2'-trifluoromethyl-4,4'.diaminobiphenyl 16.0g (0.050 © Moer) and N,N'-II (4-Aminophenyl) hydrazine trap 87. lg (0.325 mol) was dissolved in 2450 g of N-methyl-2-pyrrolidone, and allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyamine solution was added and diluted with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 59 mP a·s. Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at 11 Torr. After the dehydration ring closure reaction, the solvent in the system-35-201015177 " was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a 15% by weight hydrazine imidization rate of about 51%. A solution of the brewed imine (A-6). A small amount of this solution was taken, and N_methyl-2_radosalone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 22 mPa-s. Synthesis Example 7 As a tetradecanoic acid-wild 2,3,5-trisole cyclopentyl acetic acid dianhydride 202 g (〇_90 mol) and pyromellitic dianhydride 22 g (0.01 mol) and as two P-phenylenediamine 35 g (0.33 mol), 1-(4-aminophenyl).13,3-trimethyl-1H-member-5-amine 53.2 g (0-20 mol), 4, 4'-Diaminodiphenyl ether 2〇g (〇.l Moer), 2,2'-trifluoromethyl-4,4,-diaminobiphenyl 16.〇g(〇〇5〇 .8 gram and N,N'-bis(4-aminophenyl) oxime trap 87.1 g (0.3 25 mol) dissolved in 2450 g of N-methyl-2-pyrrolidone and allowed to react at room temperature 6 In hours, a solution containing polylysine was obtained. A small amount of the obtained polyamine solution was diluted and added with N_methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 60 mP a·s. Then, 2500 g of N-methyl.2_pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at u〇-cT. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine containing 15% by weight of ruthenium iodide (about 51%). A-7) solution. A small amount of this solution was added, and N-methyl-2 lysine was added to prepare a solution having a polyethylenimine concentration of 6. 〇% by weight, and the solution viscosity was determined to be 24 mPa-s. -36-201015177 Synthesis Example 8 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 202 g (0.90 mol) and i,3,3a,4,5,9b-hexahydrogen -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphthalene [i,2-c]-furan-1,3-dione 32.0 g (〇.l〇 Mohr), p-phenylenediamine as a diamine 35g (0.33 mol), 1-(4-aminophenyl)-1,3,3-trimethyl-111-indol-5-amine 53.2§ ( 0.20 moles, 4,4'-diaminodiphenylmethane 23g (〇.l mole), 2,2,-trifluoromethyl-4,4,-diaminobiphenyl 16.0g ( 0.050 mol) and N,N,-bis(4-aminophenyl)fluorene trap © 87.lg (〇.325 mol) dissolved in 2530 g of N-methyl-2-pyrrolidone' at room temperature The reaction was carried out for 6 hours to obtain a solution containing poly-proline. Take a small amount of the obtained polyamidamine solution, add N-methyl-2-pyrrolidone to dilute, and prepare a solution having a polyglycine concentration of 10% by weight, and determine the viscosity of the solution to be 58 mPa·S 0. Then, in the obtained polyfluorene To the amino acid solution, 2500 g of N-methyl-2-pyrrolidone was added, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system W was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polybendimimine containing 15% by weight of a ruthenium iodide ratio of about 51%. (A-8) solution. A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 23 mPa·s. Synthesis Example 9 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 202 g (0.90 mol) and 1,3,3&,4,5,91)-hexahydro-8 -Methyl-5-(tetrahydro-2,5--37-.201015177 dioxo-3-furanyl^naphthalene^丨2^furan 4,3-dione 32 0g (010 mol), as Diamine p-phenylenediamine 35g (0.33 mol), 1-(4·aminophenyl)-1,3,3-trimethyl·1Η-茚_5_amine 5 3 2g (〇.2〇 Molar), 4,4'-diaminodiphenyl ether 20g (0.l mole), 2,2, ·trifluoromethyl-4,4'-diaminobiphenyl 16.0g (0.050 Mo 8)g (0.325 moles) of ν,Ν'-bis(4-aminophenyl)fluorene trap dissolved in 253〇g 甲基•methyl-2_pyrrolidone' reacted at room temperature for 6 hours A solution containing poly-proline is obtained. A small amount of the obtained polyamine solution is diluted with Ν-methyl-2-pyrrolidone to form a solution having a concentration of polyfluorene phthalic acid of 10% by weight, and the viscosity of the solution is determined. 56 mPa. S ° Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 1 g of acetic anhydride were further added, and the dehydration ring-closure reaction was carried out for 4 hours at 1101. After the water ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine containing 15% by weight of ruthenium iodide (about 51%). Solution of A-9). Take a small amount of this solution and add N-methyl-2-laololone's solution to a concentration of 6.0% by weight of polyimine. The viscosity of the solution is 2 1 mP a· s. <Synthesis of Other Polylysine> Synthesis Example 10 A pyromellitic dianhydride as a tetracarboxylic dianhydride I96 g (0.90 mol) and 1,2,3,4-cyclobutanetetracarboxylic acid The dianhydride is 19.6 g (0.10 mol) and the p-phenylenediamine 22 g (0-20 mol) as a diamine and the 4,4'-diaminodiphenyl acid l8 g (y.8 mol) are soluble. 2400g of NMP was reacted at 6 (TC for 4 hours - 38 - 201015177 to obtain about 2700 g of a solution containing 15% by weight of polyglycine (B-1). The solution viscosity of the polyaminic acid solution was 200 mPa. .s. <Synthesis of Other Polyimine> Synthesis Example 1 1 2,3,5-tricarboxycyclopentylacetic acid diacetate as a tetracarboxylic dianhydride 224 g (l. oxime) and as a diamine P-phenylenediamine 81g (0_75 mol), 1-(4-aminophenyl)-l,3,3-trimethyl-1H-indole-5-amine 53.2g (0.20 mol) and 3, 3'-(Tetramethyldioxane-1,3_diyl)di(propylamine)i2.4g (0.050

A ^ Mo) was dissolved in 2440 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyamine solution was added and diluted with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 73 mPa·s. Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added thereto at 11 Torr. (: 4 hours dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced by a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 25 00 g of 15% by weight of quinone imine. A solution of about 51% polyethylenimine (A-10). A small amount of this solution was added, and N_methyl-2_pyrrolidone was added to form a solution having a polyamidene concentration of 6.0% by weight. The measured solution viscosity was 23 mPa·s. Synthesis Example 1 2 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 224 g (l. oxime) and a pair as a diamine Phenyldiamine 81g (〇75mol), 1-(4.aminophenyl)_1,3,3-trimethyl"^茚-pamine 53.2g (0.20 mole) -39- 201015177 and 2, 16.0 g (0.05 0 mol) of 2'-trifluoromethyl-4,4'-diaminobiphenyl was dissolved in 2 46 0 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours. A solution containing poly-proline is obtained. A small amount of the obtained polyamidamine solution is diluted with N-methyl-2-pyrrolidone to form a solution having a polyglycine concentration of 1% by weight, and the viscosity of the solution is determined. 60 mPa_s. Then, at the office 2500g of N-methyl-2-pyrrolidone was added to the polyaminic acid solution, and 80.2g of pyridine and 103g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours under the step of dehydration ring closure reaction. The solvent was replaced with a new N-methyl-2-pyrrolidone solvent and then concentrated to obtain 2500 g of a solution containing 15% by weight of a polyamidimide (A-11) having a ruthenium iodide ratio of about 51%. A small amount of this solution was added, and N-methyl-2-lanole was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the measured solution viscosity was 22 mPa_se. Synthesis Example 1 3 As a tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 2 24 g (l-〇mole) and p-phenylenediamine as a diamine 35 g (〇33 mol), 1-(4-aminophenyl) -1,3,3-trimethyl-1H-member-5-amine 53.2g (〇.2〇莫耳), 4,4'-diaminodiphenylmethane 96g (0.425 mol) and 3 , 3,_(tetramethyl oxalate-1,3-diyl) bis(propylamine) 12.4 g (0.050 mol) dissolved in 2460 g of N-methyl-2-pyrrolidone at room temperature The reaction was allowed to proceed for 6 hours to obtain a solution containing poly-proline. The polyamine solution was obtained, diluted with N_methyl-2-pyrrolidone, and formulated into a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 70 mPa·s. Then, the obtained polylysine was obtained. 25 00 g of N-methyl-2-40-201015177 pyrrolidone was added to the solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under not. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2500 g of a polyimine containing 15% by weight of ruthenium iodide (about 50%). A — 12) solution. A small amount of this solution was added, N-methyl-2-pyrrolidone was added, and a solution having a polythenimine concentration of 6.0% by weight was prepared, and the measured solution viscosity was 24 mPa·s. » Synthesis Example 1 4 〇 will be used as tetracarboxylic acid 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 224 g (l_0 mol) of acid dianhydride, p-phenylenediamine 35 g (0-33 mol), 1-(4-aminophenyl) as diamine -1,3,3-trimethyl-1H-member-5-amine 53.2 g (0.20 mol), 4,4'-diaminodiphenylmethane 96 g (0.425 mol) and 2,2'- 16.0 g (0.050 mol) of trifluoromethyl-4,4'-diaminobiphenyl was dissolved in 2460 g of N-methyl-2-pyrrolidone, and allowed to react at room temperature for 6 hours to obtain polydecylamine. Acid solution. A small amount of the obtained polyamine solution was added and diluted with N-methyl-2·pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the viscosity of the solution solution was determined to be 58 mPa's. Then, 2500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 260 0 g of a polyfluorene containing 15% by weight of ruthenium iodide of about 53%. A solution of the amine (A-13). A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polythenimine concentration of 6.0% by weight, and the solution had a viscosity of -41 to 201015177 degrees of 21 mPa-s. Synthesis Example 1 5, 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 224 g (l. oxime) and p-phenylenediamine as a diamine 35 g (〇33 mol) , 1-(4-Aminophenyl)_1,3,3-trimethyl-1H-indole-5-amine 53.2 g (0.20 mol), 4,4'-diaminodiphenyl ether 85 g ( 0.425 mol and 3,3'-(tetramethyldioxane-1,3-diyl)di(propylamine) 12.4 g (0.050 mol) dissolved in 2450 g of N-methyl-2-pyrrolidone The reaction was carried out for 6 hours at room temperature to obtain a solution containing poly-proline. A small amount of the obtained polyamine solution was added and diluted with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 71 mPa·s. Then, 25 μg of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 80.2 g of pyridine and 1 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyfluorene amine having a 15% by weight hydrazine imidization rate of about 54%. (A-8) solution. A small amount of this solution was added, and N-methyl-2-pyrrolidine was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 24 mPa·s. Synthesis Example 16 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 202 g (0.90 mol) and pyromellitic dianhydride 22 g (0.01 mol) and a pair as a diamine Phenylenediamine 35g (0.33 mole), 1-(4-aminophenyl)trimethyl-1H-indole-5-amine 53.2g (0.20 mole), 4,4'-diaminodiphenyl A-42-201015177 96g (0_42 5 moles) and 2,2'-trifluoromethyl-4,4'-diaminobiphenyl 16.0g (0.05 0 moles) dissolved in 2450g N-methyl- The 2-pyrrolidone was allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. Take a small amount of the obtained polyamidamine solution, add N-methyl-2-pyrrolidone to dilute, and prepare a solution having a polyglycine concentration of 10% by weight. The measured solution viscosity is 57 mPa·S 0 and then the resulting poly 2500 g of N-methyl-2-pyrrolidone was added to the proline solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and the mixture was subjected to a dehydration ring-closure reaction at ll ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine containing 15% by weight of ruthenium iodide (about 51%). A- 15) solution. A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the solution viscosity was determined to be 20 mPa_s. Synthesis Example 1 7 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride © 202 g (0.90 mol) and pyromellitic dianhydride 22 g (0.01 mol) as a diamine P-phenylenediamine 35g (〇.33 mol), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53, 2g (0.20 mol) 4,4,-diaminodiphenyl ether 85g (0.425 mol) and 2,2'-trifluoromethyl-4,4'-diaminobiphenyl 16.0 g (0-050 mol) dissolved in 2450 g The N-methyl-2-pyrrolidone was reacted at room temperature for 6 hours to obtain a polyglycine-containing solution. Take a small amount of the obtained polyamine solution, add N-methyl-2-pyrrolidone to dilute, and prepare a solution with a polyglycine concentration of 10% by weight. The measured solution viscosity is 58 mPa. -43- 201015177 Then, in the obtained 2500 g of N-methyl-2-pyrrolidone was added to the polyamine solution, and 80.2 g of pyridine and 1 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine having a 15% by weight hydrazine imidization ratio of about 50%. A — 16) solution. A small amount of this solution was taken, and N-methyl-2-pyrrolidone was added to prepare a polyimine concentration of 6.0% by weight. /. The solution was measured to have a viscosity of 22 mPa's. Synthesis Example 1 8 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 202 g (0.90 mol) and 1,3,3a,4,5,9b-hexahydro-8- Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione 32.0 g (0.10 mol) Diamine p-phenylenediamine 35g (0.33 mole), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2g (0.20 mole), 4,4,-Diaminodiphenylmethane 96g (0-425 mol) and 2,2'-trifluoromethyl-4,4,-diaminobiphenyl 16.0 g (0.050 mol) dissolved in 25 3 0 g of N-methyl-2·pyrrolidone was reacted at room temperature for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyamine solution was added, and N-methyl-2-pyrrolidone was added to dilute the solution into a polyglycine concentration of 1% by weight, and the solution viscosity was determined to be 56 mPa·s. Then, 2500 g of N-methyl-2-radosporin was added to the obtained polyamic acid solution, and 80.2 g of pyridine and i3 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under not. After the dehydration ring closure reaction, the solvent in the system -44 - 201015177 was solvent-substituted with a new hydrazine methyl 2-pyrrolidone, and then concentrated to obtain 2600 g of a polymer containing 15% by weight of a ruthenium iodide ratio of about 51%. A solution of quinone imine (A-17). A small amount of this solution was taken, and N_methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6 〇% by weight, and the solution viscosity was determined to be 2 1 mPa·s. Synthesis Example 9 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 202 g (0.90 mol) and 1,3,3a,4,5,9b-hexahydro-8- Methyl-5-(tetrahydro-2,5·dioxo-3-pyranyl)-naphthalene [l,2-c]-pyran-1,3-dione 320g (01() mole) And p-phenylenediamine as a diamine 35g (0.33 mole), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine 53.2g (0.20 mole) , 4,4,-diaminodiphenyl ether 85g (0.425 mol) and 2,2'-trifluoromethyl-4,4,-diaminobiphenyl 16.0 g (0-050 mol) are soluble In 2530 g of N-methyl-2-pyrrolidone, it was allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyamine solution was added and diluted with N-methyl-2-pyrrolidone to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 54 mPa-s. 2500 g of N-methyl-2-pyrrolidone was added to the amine acid solution, and 80.2 g of pyridine and 103 g of acetic anhydride were further added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent, and then concentrated to obtain 2600 g of a polyimine containing 15% by weight of ruthenium iodide (about 51%). A-18) solution. A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyamidene concentration of 6.0% by weight, and the measured solution viscosity was -45-201015177 degrees to 19 mPa, se Example 1 <Liquid alignment Preparation of the agent> The polyiminoimine (A-1)-containing solution prepared in the above Synthesis Example 1 in an amount equivalent to 20 parts by weight of the polyimine (A-1) is converted into a polyfluorene. The amine acid (B-1) is equivalent to 80 parts by weight of the polyglycine (B-1)-containing solution prepared in the above Synthesis Example 1 and mixed with 7·-butyrolactone: N-A The ratio of keto pyrrolidone:butyl cellosolve is 40:40:20 by weight, 7-butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve are added thereto, and 2 parts by weight are added thereto. The epoxy compound N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane of the adhesion enhancer was formulated into a solution having a solid content concentration of 3.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 1 /z m to prepare a liquid crystal alignment agent. <Production and Evaluation of Liquid Crystal Display Element> Using the liquid crystal alignment agent prepared above, a liquid crystal display element was produced and evaluated as follows. Further, the liquid crystal alignment agent of the present invention is preferably used for forming a liquid crystal alignment film of a horizontal electric field type liquid crystal display element, and the liquid crystal alignment property and the pretilt angle are changed to produce and evaluate the liquid crystal display element of the antiparallel alignment. (1) Liquid crystal display element and pretilt angle evaluation liquid crystal display element (reverse parallel alignment liquid crystal display element) was manufactured by a spin coater, and the above-mentioned liquid crystal was adjusted under the conditions of a rotation speed of 2000 rpm and a rotation time of 20 seconds. The alignment agent was applied onto a transparent conductive film made of an IT0 film provided on one surface of a glass substrate having a thickness of 1 mm. The solvent was removed by heating at 2 〇〇-46 to 201015177 ° C for 1 hour to form a coating film having a film thickness of 0.08 μm. The coating film was polished by a sander equipped with a roller wound with a rayon cloth at a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. A liquid crystal alignment energy is generated on the coating film to form a liquid crystal alignment film. The substrate having the liquid crystal alignment film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. This series of operations was repeated to fabricate two (a pair of) substrates having a liquid crystal 〇 alignment film. Then, on each outer edge of the pair of liquid crystal alignment films having a liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5/zm is applied, and the liquid crystal alignment film is oppositely coated. Combine and press to harden the adhesive. Next, a liquid crystal injection port is used to fill a liquid crystal injection port with an acrylic light-curing adhesive after filling a substrate with a positive nematic liquid crystal (manufactured by Merck & Co., MLC-2019). A polarizing plate was bonded to both surfaces of the outer side of the substrate to produce a liquid crystal display element having an antiparallel alignment ©. (2) Evaluation of liquid crystal alignment property When the liquid crystal display element manufactured above was observed by an optical microscope, no light leakage was observed, and the liquid crystal alignment property was evaluated as "good", and light leakage was observed, and liquid crystal alignment evaluation was performed. In the case of "failed", the liquid crystal alignment property of the liquid crystal display element was "good" at this time. (3) Evaluation of pretilt angle For the liquid crystal display element manufactured above, the pretilt angle was measured by the Semen method at room temperature -47 - 201015177. When the enthalpy is less than 1.5 °, the pretilt angle is evaluated as "good", and when it is 1.5 or more, the pretilt angle is evaluated as "failed", and at this time, the pretilt angle 上述 of the liquid crystal display element is "good". (4) Production of liquid crystal display element (transverse-field type liquid crystal display element) for evaluation of after-image performance In the manufacture of the above-described antiparallel alignment liquid crystal display element, in addition to the pattern of two types of chrome comb-shaped transparent conductive film a glass substrate and a glass substrate not having a transparent conductive film as a pair, and coating the liquid crystal alignment agent on the transparent conductive film of the substrate having the comb-shaped transparent conductive film and the one surface of the other substrate, respectively The production of the liquid crystal display device of the above-described antiparallel alignment is performed in the same manner to produce a horizontal electric field type liquid crystal display element. A schematic view showing the configuration of the transparent electrode pattern on the glass substrate is shown in Fig. 1. The transverse electric field type liquid crystal produced as described above The transparent conductive film pattern of the two components of the display element is hereinafter referred to as "electrode A" and "electrode B" respectively. (5) Evaluation of afterimage performance ® The horizontal electric field type liquid crystal display element was fabricated, and a voltage of not applied to the electrode B was applied to the electrode B in an environment of 25 t and 1 atm, and a combined voltage of 3.5 V AC voltage and 5 V DC voltage was applied to the electrode A for 2 hours. Then, immediately to the electrode A and The electrode B was applied with an alternating voltage of 4 V. The time from the time when the alternating voltage of 4 V was applied to the two electrodes to the time when the electrode a and the electrode B had no difference in light transmittance was measured. When the time was less than 500 seconds, the residue was The image performance evaluation was "good". At this time, the afterimage performance of the above-described horizontal electric field type liquid crystal display element was "good". -48-.201015177 Examples 2 to 18 and Comparative Examples 1 to 1 8 except that only The polymer contained in the amount of the polymer contained in the amount shown in Table 1 was used in the same manner as in the above Example 1 except that a solution containing the polymer of the type shown in Table 1 was used as the polymer-containing solution. The liquid crystal display elements were prepared and evaluated, and the evaluation was carried out. The results are shown in Table 1.

-49- 201015177 Table 1

Liquid crystal alignment agent liquid crystal display element polymer polyimine polyacrylic acid liquid crystal pretilt image type amount (parts by weight 1 type ί parts by weight) Orientation (.) Performance Example 1 A- 1 20 B- 1 80 Good 1.1 (good) Good Example 2 A - 2 20 B - 1 80 Good 1.2 (Good) Good Example 3 A-3 20 B - -1 80 Good 1.1 (Good) Good Example 4 A-4 20 B -1 80 good 1_2 (good) good example 5 A-5 20 B- 1 80 good 1.1 (good) good example 6 A-6 20 B- 1 80 good 1.3 (good) good example 7 A-7 20 B- -1 80 good 1.4 (good) good example 8 A-8 20 B -1 80 good 1.2 (good) good example 9 A-9 20 B--1 80 good 1_3 (good) good example 10 A - 1 40 B -1 60 good 1_0 (good) good example 11 A-2 40 B- 1 60 good 1.1 (good) good example 12 A-3 40 B. -1 60 good 1.0 (good) good example 13 A- 4 40 B -1 60 good 1.1 (good) good example 14 A-5 40 B -1 60 good 1.0 (good) good example 15 A-6 40 B- 1 60 Good 1_2 (good) Good Example 16 A-7 40 B -1 60 Good 1.3 (Good) Good Example 17 A-8 40 B- 1 60 Good 1.1 (Good) Good Example 18 A-9 40 B-1 60 good 1_2 (good) good comparative example 1 A- 10 20 B- 1 80 good 1.7 (failed) good comparative example 2 A~ 11 20 B - 1 80 good 1.8 (failed) good comparative example 3 A - 12 20 B~1 80 Good 1.7 (failed) Good Comparative Example 4 A-13 20 B -1 80 Good 1_8 (failed) Good Comparative Example 5 A-14 24 B- 1 80 Good 1.7 (failed) Good Comparative Example 6 A— 15 20 B -1 80 Good 1_9 (failed) Good Comparative Example 7 A — 16 20 B -1 80 Good 2.0 (failed) Good Comparative Example 8 A — 17 20 B —1 80 Good 1.8 (failed) Good Comparative Example 9 A—18 20 B—1 80 Good 1.9 (failed) Good Comparative Example 10 A—10 40 B -1 60 Good 1.6 (failed) Good Comparative Example 11 A—11 40 B- 1 60 Good 1.7 (Failed) Good Comparative Example 12 A— 12 40 B -1 60 Good 1.6 (failed) Good Comparative Example 13 A— 13 40 B- 1 60 Good 1.7 (not compatible Good Comparative Example 14 A- 14 40 B -1 60 Good 1.6 (failed) Good Comparative Example 15 A - 15 40 B -1 60 Good 1.8 (failed) Good Comparative Example 16 A - 16 40 B -1 60 Good 1.9 (failed) Good Comparative Example 17 A—17 40 B -1 60 Good 1.7 (failed) Good Comparative Example 18 A— 18 40 B -1 60 Good 1.8 (failed) Good -50- 201015177 [Simple diagram 1 is a schematic view showing a configuration of two sets of transparent conductive film patterns included in a lateral electric field type liquid crystal display device produced for evaluation of afterimage performance in the examples and the comparative examples. [Main component symbol description] 〇 ❹

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Claims (1)

201015177 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a compound selected from the group consisting of a tetracarboxylic dianhydride and a compound having a structure represented by the following formula (A) and two amine groups. a polymer obtained by reacting a polyamine obtained by reacting a diamine with a polyamidene obtained by dehydration of the polyglycolic acid, and used for forming a liquid crystal alignment film, *——NN——* (A) ^ \_/ ❹ In the formula (A), it is expressed as a link key. 2. The liquid crystal alignment agent of claim 1, wherein the compound having the structure represented by the above formula (A) and the two amine groups is a compound represented by the following formula (A-1), / \ H2N-U- +-N^——UH—NH2 (A-1) \ /n In the formula (A_l), each U is a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenyl group, and a naphthyl group. And a cyclohexyl group, a pyrimidyl group or a triple well group, and η is an integer of 1 to 5, and the plurality of Us present may be the same or different. 3. The liquid crystal alignment agent of claim 1, wherein the diamine is further comprising at least one selected from the group consisting of a compound represented by the above formula (Α) and a compound having two amine groups. One. 4. The liquid crystal alignment agent of claim 3, wherein the diamine system further contains a compound represented by the following formula (D-II), -52- 201015177 R, H2N-fcH2)^-Si-(- R7 R7 I ' \ 〇-Sh R7 R7 CH2)^NH (D-Π) In the formula (D-II), the hydrocarbon groups of 'r7 each having a carbon number of i~I> may be the same, and the plurality of R7 may be the same. Differently, p is an integer of 1 to 3, and q is an integer of 1 to 20. 5. The liquid crystal alignment agent of claim 1, wherein the tetracarboxylic acid monoanhydride is selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, At least one of the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, pyromellitic dianhydride, and 4,4'-diphthalic dianhydride. 6. The liquid crystal alignment agent according to claim 2, further comprising a diamine selected from the group consisting of a tetracarboxylic dianhydride and a compound having no structure represented by the above formula (A) and two amine groups. A polymer of at least one of the group consisting of polylysine obtained by the reaction, Q, and polyimine obtained by dehydration of the polyglycolic acid. The liquid crystal alignment agent according to any one of claims 1 to 6, which is used for forming a liquid crystal alignment film of a horizontal electric field type liquid crystal display element. A liquid crystal alignment film comprising a liquid crystal alignment agent according to any one of the first to seventh aspects of the invention. -53-