TW200925183A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

Providing a liquid crystal aligning agent which can form a liquid crystal aligning film has good durability to long period of thermal stress and a liquid display device whose display performance without deterioration even driven for a long time. The above liquid crystal aligning agent comprising at least one polymer selected from a group consisted by a polyamide acid formed by the reaction of a tetracarboxylic dianhydride and a diamine containing a compound represented by the following formula (A), and a polyimide formed by dehyaration closing ring of the polyamide acid. The above liquid crystal display device has a liquid crystal film formed by the above liquid crystal aligning agent.

Description

200925183 IX. 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 present invention relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having excellent heat resistance and a liquid crystal display element capable of suppressing display deterioration due to thermal stress and capable of being driven for a long period of time. [Prior Art] At present, as a liquid crystal display element, a ΤΝ-type liquid crystal display element having a so-called TN type (twisted nematic) 液晶 ^ liquid crystal cell is widely known, and a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is provided. As a substrate for a liquid crystal display element, two substrates are disposed opposite each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in a gap therebetween to form a unit cell of a sandwich structure, and a long axis of the liquid crystal molecules is from one piece The substrate is continuously twisted 90 degrees toward the other substrate. In addition, STN (Super Twisted Nematic) liquid crystal display elements, which have a higher contrast ratio than the ΤΝ-type liquid crystal display elements, and IPS (in-plane switching) type liquid crystal display elements with small viewing angle dependence have been developed, and IPS has been changed. The electrode structure ❹ improves the aperture ratio of the opening of the display element to improve the brightness of the FFS (Fringe Field Conversion) type liquid crystal display element, the VA (Vertical Alignment) type liquid crystal display element, and the viewing angle dependence is small, and the video picture has excellent high-speed response. OCB (optical compensation bending) type liquid crystal display element, etc. As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as polylysine, polyimine, polyamine, or polyester is known, and in particular, it is made of polyamic acid or polyimine. The liquid crystal alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, etc., and is used in many liquid crystal display elements 200925183 (see, for example, Patent Documents 1 to 3). A liquid crystal display element having a liquid crystal alignment film formed of these resin materials, in order to improve its performance so that it can be applied to a television set, is designed to have a durability of more than 10 years, and is compatible with the use of the liquid crystal display element of the prior art. Than 'requires a long-term drive that excels. If a conventionally known liquid crystal display element is continuously driven for a long period of time (for example, 1 000 hours or more), there is a problem that the contrast ratio of the element is lowered. This defect is considered to be caused by thermal stress caused by long-time driving, which causes thermal deterioration of the liquid crystal alignment film, and as a result, the voltage holding ratio of the liquid crystal is lowered. Therefore, it is required to display a liquid crystal alignment film having a stable voltage holding ratio and excellent heat resistance even when the liquid crystal display element is driven for a long period of time. However, a liquid crystal alignment agent capable of forming such a liquid crystal alignment film is not known. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2003-149648 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2003-107486 (Patent Document 4) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A liquid crystal alignment agent which is capable of forming a liquid crystal alignment film which is excellent in durability (heat resistance) which exhibits a stable voltage holding ratio for long-term thermal stress. Another object of the present invention is to provide a liquid crystal display element which does not deteriorate even when display performance 200925183 (especially contrast) even when driven for a long period of time. Other objects and advantages of the present invention will be apparent from the following description. According to the invention, the above object of the invention, the first, is achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of 2,3,5-tricarboxycyclopentane The polycarboxylic acid which is obtained by reacting a tetracarboxylic dianhydride of an acetic anhydride dianhydride with a diamine containing a compound represented by the following formula (A), and a polyimine which is obtained by dehydrating and ring-closing the polyamic acid.

The above object of the present invention 'second' is achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. According to the present invention, it is possible to form a liquid crystal alignment film which is excellent in heat resistance, i.e., a liquid crystal alignment film which does not deteriorate in liquid crystal alignment when a long-term thermal stress is applied. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be applied to various liquid crystal display elements. The liquid crystal display element of the present invention having such a liquid crystal alignment film does not deteriorate in display performance even when driven for a long period of time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, for example, for watches, portable game machines, word processors, notebook computers, car navigation systems, video cameras, PDAs, digital cameras, mobile phones, Display devices such as various monitors and liquid crystal televisions. [Embodiment] Hereinafter, the present invention will be described in detail. 200925183 The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and containing the above formula The polyamine acid obtained by the diamine reaction of the compound represented by (A) and the polyamidene obtained by dehydrating and ring-closing the polyamic acid are comprised. <Polyuric acid> The polyglycine which can be contained in the liquid crystal alignment agent of the present invention can be obtained by including tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and It is obtained by reacting a diamine of the compound represented by the above formula (A). [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. As the tetracarboxylic dianhydride, only 2,3,5-tricarboxycyclopentylacetic acid dianhydride may be used alone, or it may be used in combination with other tetracarboxylic dianhydride. Examples of the other tetracarboxylic dianhydride which can be used in the present invention include alicyclic tetracarboxylic acid phthalic anhydride other than 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and aliphatic tetracarboxylic acid II. Anhydride and aromatic tetracarboxylic dianhydride. Specific examples of the alicyclic tetracarboxylic dianhydride other than the above 2,3,5-tricarboxycyclopentyl acetic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl Tetracarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1,5- 200925183 diene-1,2,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxo Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarbonyl-2-carboxyl-norbornane-2:3,5 :6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&,4,5,9 hexahydro-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro- 5-ethyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-7-methyl-5-( Tetrahydrohydrogen-2,5-dioxo-3-furanyl)-naphthalene [1,2-indolyl]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro- 7-Ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3& 4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, 1 ,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]- Furan-1,3-diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydroindenyl)-3-methyl-3-cyclohexene-1,2 -dicarboxylic anhydride, ^bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane·2,4- Diketo-6-spiro-3'-(tetrahydrofuran-2',5'-dione), a compound represented by the following formula (Τ-ΐ) or (T-II), -10- 200925183 V (TI) y 0 J R2 R2 R4 R4 P y T—R3—V (T-II) ϊ ί where R1 and Each of R3 represents that 2® and R4 having an aromatic ring each represent a hydrogen atom or an alkyl group, and the presence thereof may be the same or different. Specific examples of the above aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid diphenylphosphonium tetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic acid dicarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride diphenyl decane tetracarboxylic dianhydride, 3,3', 4, 4'-Tetraphthalic anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3" diphenyl sulfide dianhydride, 4,4'-bis (3,4-di Carboxybenzene-anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropanol perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4, anhydride, Bis(phthalic acid) phenylphosphine oxide dianhydride, p- 3 phthalic acid dianhydride, m-phenylene-bis(triphenyl-o-bis(triphenylphthalate)-4,4' - Diphenyl ether dianhydride, valence organic group, R2 • each of R2 and R4, and examples thereof include dianhydride, 3,3', 4,4,-anhydride, 2,3,6,7 -naphthalene tetra, 3,3',4,4'-dimethyldecanetetracarboxylic acid didicarboxyphenoxy) carbyl)diphenylphosphonium di: dianhydride, 3,3',4,4'- 4'-biphenyltetracarboxylic acid diphenyl-bis(triphenyl) Phthalic anhydride) dianhydride, bis(triphenyl phthalate-11-200925183 formic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(deesterification), propylene glycol-double (dehydration partiality) Triglyceride), 1,4-butanediphthalate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), bis(anhydroelellitic acid ester), 2,2-double (4-hydroxyphenyl)propane-tricarboxylate), a water-based trimellitic acid-double (dehydrated 1,8-octanediol) represented by the following formulas (T-1) to (T-4) - Double (dehydration partial benzene compound, etc.).

-12- 200925183

In the synthesis of the poly-proline which is contained in the liquid crystal alignment agent of the present invention, the other tetracarboxylic dianhydride used may be selected from 2,3,5-tricarboxycyclopentylacetic acid. Pyromellitic tetracarboxylic dianhydride other than anhydride and pyromellitic dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride in aromatic tetracarboxylic dianhydride (hereinafter also At least one of a group consisting of pyromellitic dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride collectively referred to as "specific aromatic tetracarboxylic dianhydride" is capable of From the standpoint of good liquid crystal alignment, it is more preferable to contain a 1,3-dimethyl-1,2,3,4- selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid phthalic anhydride, 1,2,3,4-cyclopentane Tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5-(2, 5-dioxotetrahydroindenyl)_3_methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1 , 2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorborn -2:3,5:6-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(four Hydrogen-2,5-dioxo-3-indolyl)-naphthalene [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2 ,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'·(tetrahydrofuran-2',5'-di And a compound represented by the following formula (T-5) to (T-7) in the compound represented by the above formula (T-I), and a compound represented by the above formula (T-II); At least one tetracarboxylic dianhydride in the group consisting of the compound represented by T-8), pyromellitic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride, -14-200925183

Further preferably, it contains a compound selected from the group consisting of 1,2,3,4·cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5 -(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, l,3,3a,4,5,9b-six Hydrogen-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, cis-3,7-dibutyl Cyclooctane-1,5-diene©-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-di Anhydride, 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2- c]-furan-1,3-diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione At least one tetracarboxylic dianhydride in the group consisting of the compound represented by the above formula (T to 5), pyromellitic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride More preferably, it contains a compound selected from the group consisting of 1,2,3,4-tetracarboxylic dianhydride, 1,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, pyromellitic acid-15- 200925183 dianhydride and 2,2',3,3 At least one of tetracarboxylic dianhydrides of the group consisting of '-biphenyltetracarboxylic dianhydrides. When the tetracarboxylic dianhydride contains an alicyclic tetracarboxylic dianhydride and a tetracarboxylic dianhydride other than the specific aromatic tetracarboxylic dianhydride, 'as an alicyclic tetracarboxylic dianhydride and a specific aromatic tetracarboxylic acid II Preferred tetracarboxylic dianhydrides other than the anhydride include, for example, butane tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4. '-Diphenyl maple tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the like. The tetracarboxylic dianhydride used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention preferably contains 50 mol% or more, more preferably 80 mol% or more, based on the total tetracarboxylic dianhydride. , 3,5-tricarboxycyclopentyl acetic acid dianhydride. [Diamine] The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (A). A preferred specific example of the compound represented by the above formula (A) is, for example, 3,5-diaminobenzoic acid. As the diamine, the compound represented by the above formula (A) may be used alone, or the compound represented by the above formula (A) may be used in combination with another 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'-diaminodiphenylanthracene, 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)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1, 3,3-trimethylindan, 3,4'-diaminodi-16- 200925183 phenyl 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-hydroquinone, 2,7-diamine Indole, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxy-linked benzene, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 1,4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenyleneisopropylene)diphenylamine, 2,2 '-Bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bipedyl-2,2'-bis(trifluoromethyl) An aromatic diamine such as biphenyl or 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl or bis(4-aminophenyl)benzidine; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoglycol Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0''7]undecene dimethyldiamine, Aliphatic and alicyclic diamines such as 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2, 6-diaminopyridine 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-diamino-2,4-dihydroxy Pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-three tillage, 1,4-bis(3-aminopropyl) piperene, 2,4-diamino- 6-Isopropoxy-1,3,5-tri-trap, 2,4-diamino-6-methoxy-1,3,5-trin, 2,4-diamino-6-benzene Base-1,3,5-three tillage, 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-three tillage, -17- 200925183 4,6·diamino-2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazolidinediamine, 5,6-diamino-1,3-dimethyl Urethane, 3,1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl lactate, 3,8-di•6-phenylphenanthridine, 1, 4-diaminopiperidine, 3,6-diaminoacridine, bisphenylphenyl)phenylamine, 1-(3,5-diaminophenyl)-3-indenyl amber 醯 1-( 3,5-Diaminophenyl)-3-octadecyl succinylamine, the following formula (D-shown compound v P 〇νΰ° (in the formula (D-I), R5 is selected from pyridine 1, pyrimidine, three-plowed, piperidine arable group of monovalent nitrogen-containing ring structure X1 is a divalent organic group organic group), the compound represented by the following formula (a square π) '2,6- amino group ([Amine, I) and piperazine group table,

(D-II) ❹ (In the formula (D-II), each of X2 is a divalent group having a cyclic structure containing a nitrogen atom selected from the group consisting of azopyridine, pyrimidine, triple well, piperazine and veins. R6 is a divalent organic group, and each of a plurality of X2 groups may be different from each other) a diamine having two -amino groups in the molecule and a nitrogen atom other than the primary amine; the following formula (D-III) The monosubstituted phenylenediamine n is represented by the same base, and the group is -18-200925183 OR7-R8 (D-III) ^ nh2 (in the formula (D-III), R7 is selected from -◦-*, - a group of divalent organic groups consisting of C00-*, -0C0-*, -NHC0-*, -C0NH-*, and -C0-* (wherein the bond is bonded to R8), and R8 is selected from a monovalent organic group of a skeleton or a group in a group consisting of a steroid skeleton, a trifluoromethyl group, and a fluorine group; or an alkyl group having 6 to 30 carbon atoms; the following formula (D-IV) indicates ® Compounds such as diamine organooxanes R9 R9 H^N-^ CH^- Si —fo—Si.·)〆·CHy^- NHg R9 R® (D-1V) (in formula (D-IV) R9 each represents a hydrocarbon group having 1 to 12 carbon atoms, and each of the plurality of R9 may be the same or different. , p is an integer of 1 to 3, and q is an integer of 1 to 20); the following formula (D-1) to (D-5) each show a compound such as Q -19- 200925183

=yNH2

O-(-c2h4)-o-^ ,

(D-4)

(y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1). These diamines may be used alone or in combination of two or more. Among them, preferred p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 -20- 200925183

Aminodiphenyl sulfide, i,5-diaminonaphthalene, 2,7-diaminopurine, 4,4,-diaminodiphenyl acid, 2,2-bis[4-(4-amine Phenyloxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2_ bis(4-aminophenyl)hexafluoropropane, 4,4,-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene) Aniline, cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), anthracene, 4_bis(4-aminophenoxy)benzene, 4,4, bis(4-aminobenzene) Oxy)biphenyl, a compound represented by the above formula (D -丨)~(D_5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, ^3,6-diaminopyridinium, a compound represented by the following formula (D-6) in the compound represented by the above formula (D-Ι), and a compound represented by the above formula (D_π) a compound represented by (D-7),

a compound represented by the above formula (D-III) and 1,3-bis(3-diaminopropyl)tetramethyldioxane in the compound represented by the above formula (d-IV), more preferably p-benzene Diamine. Among the compounds represented by the above formula (D-III), R7 is preferably -0-* or -COO-* in the above formula (d_in> (wherein a bond with "*·' is bonded to R8), and R8 is The compound having a monovalent organic group of a steroid skeleton is more preferably a compound represented by the following formula (D-8) to (D-16). -21- 200925183

-22- 200925183

The diamine used in the synthesis of the polyamic acid contained in the liquid crystal alignment agent of the present invention preferably contains the above formula (A) in an amount of 1 mol% or more, more preferably 1 mol% or more, based on the total of the diamine. compound of. Further, the diamine of the present invention used in the present invention preferably contains at least a compound selected from the group consisting of the compound represented by the above formula (D-III) and p-phenylenediamine in addition to the compound represented by the above formula (A). One. In this case, it is more preferable that the compound represented by the above formula (D-III) is contained in an amount of 1 to 50 mol% based on the entire diamine. Further, it is more preferable to contain 30 to 90 mol% of p-phenylenediamine relative to the entire diamine. [Synthesis of Poly-Proline] The poly-proline contained in the liquid crystal alignment agent of the present invention can be obtained by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride with the above formula - 23- 200925183 A compound represented by (A) is obtained by reacting a diamine. The ratio of use of the tetracarboxylic dianhydride to the diamine to be supplied to the polyaminic acid synthesis reaction is preferably from 0 to 2 equivalents per equivalent of the amine group of the diamine to the acid anhydride group of the tetracarboxylic dianhydride. More preferably, it is a ratio of 0.7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C, preferably from 1 to 72 hours, more preferably Carry out 3 to 48 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid, and may be exemplified by, for example, 1-methyl-2-pyrrolidone 'N,N-dimethylacetamide, N , N-dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy- An aprotic solvent such as a guanamine compound such as N,N-dimethylpropionamide, dimethyl hydrazine, butyrolactone, tetramethyl urea or hexamethylphosphonium triamine; m-methylphenol and dimethyl A phenolic compound such as phenol, phenol or halogenated phenol. The amount (α) of the organic solvent is usually preferably such that the total amount (/3) of the tetracarboxylic dianhydride and the diamine is from 0.1 to 30% by weight based on the total amount of the reaction solution (α + /3). Here, when the organic solvent is used in combination with the following non-solvent solvent, the amount (α) of the above organic solvent means the total amount of the organic solvent and the poor solvent. In the above organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons which are generally considered to be poor solvents of polyaminic acid may be used in combination in a range in which the produced polyaminic acid is not precipitated. , hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butane. Alcohol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl-24- 200925183 ethyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate Ester, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol Propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, L,2-dichloroethane, 1,4-dichlorobutyl Alkane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate , isoamyl ether, etc.When an organic solvent is used in combination with a poor solvent, the amount of the poor solvent can be appropriately set within a range in which the produced polyaminic acid is not precipitated, and is preferably 30% by weight or less based on the total amount of the solvent. Preferably, it is 20% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be supplied to the liquid crystal alignment agent as it is, or may be prepared by separating the polyamic acid contained in the reaction solution and supplying the liquid crystal alignment agent, or may be used to refine the separated polyamine acid. The liquid crystal alignment agent is then supplied. The separation of the polyamic acid can be carried out by adding the above-mentioned reaction solution to a large amount of poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. Further, the poly-proline can be purified by a method of re-dissolving the polyamine in an organic solvent once or several times and then precipitating it with a poor solvent or by evaporating under reduced pressure with an evaporator. -25-200925183 <Polyimide> The polyimine which may be contained in the liquid crystal alignment agent of the present invention can be obtained by dehydrating and ring-closing the polylysine as described above. The polyimine contained in the liquid crystal alignment agent of the present invention may be a complete ruthenium imide of a glycosidic acid structure in which the polyamic acid raw material has a dehydration ring closure, or a partial deuterated acid structure dehydration ring closure. A partial ruthenium imide of a proline structure and a quinone ring structure. The polyamidene contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 40 mol% or more, more preferably 80 mol% or more. By using a polyimine having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a shorter afterimage erasing time can be obtained. The above ruthenium iodide ratio means the total amount of the guanidine structure and the number of the quinone ring structure in the polyimine, and the ratio of the number of the quinone ring structure is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium imidization rate can be obtained by dissolving the polyimine in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) with tetramethyl decane as a reference substance at room temperature (for example, 25 ° C). 1H-NMR was measured, and the measurement result was obtained by the following formula U). Ruthenium amination rate (%) = (1 - AVA2xa ) xl00 (i) (In equation (1), A1 is the peak area originating from the NH proton near the chemical shift of 10 ppm, and A2 is the peak area derived from other protons. , α is the ratio of the number of other protons relative to one of the precursors of polyimine (polyproline). The dehydration ring closure of polylysine is preferably (i) by heating the polyglycolic acid -26-200925183 method, or (ii) by dissolving the polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst. Add as needed. The reaction temperature in the method of heating poly-proline in the above (i) is 50 to 200 ° C, more preferably 60 to 170 ° C. The reaction time is preferably from 3 to 5 hours. When the reaction temperature is less than 50 °C, it should not be sufficient. If the reaction temperature exceeds 200 °C, the molecular weight of the quinone imine will decrease. On the other hand, in the method of (ii) in the polyamic acid solution and the dehydration ring-closure catalyst, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used as the dehydrating agent. The dehydrating agent is preferably a ruthenium imidation ratio of 0.01 to 20 moles per 1 mole of the polyamic acid structure. Further, as the dehydration, for example, pyridine, trimethylpyridine, lutidine or a hydrazine can be used. However, it is not limited to these. The dehydration ring-closure catalysis is preferably 0.01 to 10 moles of the dehydrating agent, and the more the dehydration ring-closing catalyst is used, the higher the amount of dehydration. As the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of lysine can be used. The reaction temperature should preferably be 0 to 180 ° C, more preferably 10, preferably 1 to 8 hours, more preferably 3 to 5 hours. In the above method (ii), a solution containing a polyzyme is obtained as described above. The reaction solution can be supplied as it is to the liquid crystal alignment agent. The dehydrating agent can be removed from the reaction solution and the dehydration ring closure catalysis can be carried out. The progress of the process to the solution is preferably 1 to 8 hours, and the dehydration ring closure occurs to obtain the polyaddition dehydrating agent to be used. For example, the amount is based on the amount of the guanidine ring catalyst of valine acid, triethylamine, etc., in the ear. The above deamidation ratio is enumerated as a dehydration ring closure of ~10.5 °C. The preparation of the reaction of the anti-imine is also provided after the preparation of the liquid crystal alignment agent of -27-200925183, and the preparation of the liquid crystal alignment agent may be carried out after separating the polyimine, or the separated polyimine may be refined. The liquid crystal alignment agent is then supplied. The dehydrating agent and the dehydrated closed-loop catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the polyimine can be carried out in the same manner as the above-described separation and purification method of polylysine. - Terminal-modified polymer - The poly-proline or polyimine contained in the liquid crystal alignment agent of the present invention may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating performance and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminally modified polymer can be produced by adding a molecular weight modifier to a polymerization reaction system during the synthesis of polyamic acid. The molecular weight modifier may, for example, be a monobasic acid anhydride, a monoamine compound or a monoisocyanate compound. Examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic acid anhydride, n-tetradecyl succinic anhydride, and n-hexadecane. Succinic anhydride and the like. As the above monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and n- Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, orthopedic limbs, etc. The monoisocyanate compound may, for example, be phenyl isocyanate ortho-naphthyl ester or the like. The ratio of use of the molecular weight modifier is preferably less than or equal to 1 part by weight, more preferably 1 part by weight, based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride and the diamine used in the acid synthesis. the following. - solution viscosity - polylysine or polyimine prepared as above, preferably having a solution viscosity of 20 to 800 mPa's when formulated into a concentrated 10% by weight solution, having a temperature of 30 to 50 Q mPa.s Solution viscosity. The solution viscosity (mPa.s) of the above polymer is a 10% by weight polymer solution prepared using the polymer solvent, using E-type rotational viscosity ® 25. . The measured enthalpy. <Other Additives> The vertical alignment type liquid crystal alignment film of the present invention contains one of the group consisting of polyamidene as described above and polyhydrazide which is dehydrated and closed, as an essential component, and as needed It can also contain its points. As such other components, other polymers, adjuvants, etc. are mentioned, for example. The above other polymers may be used for the purpose of improving solution properties and electrical enthalpy. The other polymer is a polycarboxylic acid obtained by reacting a tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentyl dianhydride with a compound represented by the above formula (A) and making the polyfluorene The polymer other than the polyamine obtained by dehydration of the amine acid is, for example, a tetracarboxylic dianhydride containing no 2,3,5-tricarboxyacetic acid dianhydride and a compound represented by the above formula (A). Polylysine obtained by diamine reaction (hereinafter referred to as "other polyacid"), polyimine (hereinafter referred to as "other polyimine") obtained by dehydration of the polyamine, and polylysine Esters, polyesters, polyamines, polycondensation of 20 degrees is a better measure. The adhesive properties of the amine acetate ruthenium cyclopentane amide are called oxime -29- 200925183 An alkane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. Among them, other polyamines or other polyimines are preferred. The ratio of use of the other polymer to the total amount of the polymer (refers to the above tetracarboxylic dianhydride containing 2,3,5-tricarboxycyclopentylacetic acid dianhydride and the compound represented by the above formula (A) The polyamine acid obtained by the diamine reaction and the polyamidimide obtained by dehydrating and ring-closing the polyamic acid and the other polymer are the same, preferably 30% by weight or less, more preferably 20% by weight. %the following. © The above-mentioned adhesive additive can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the surface of the substrate. As such an adhesion aid, 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 listed. 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 ether, 2,2-dibromoneopentyl glycol diglycidyl ether, hydrazine, 3,5,6·four Glycidyl-2,4-hexanediol, ^1,1^,1^',1^-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl) Aminomethyl)cyclohexane, N,N,N',N'_tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidol Aminopropyltrimethoxylate, 3-(N,N-glycidyl)aminopropyltrimethoxydecane, and the like. The use ratio of the epoxy group as described above is preferably 40 parts by weight or less with respect to 100 parts by weight of the total amount of the polymer, more preferably ο.1 -30 to 200925183 to 30 parts by weight. The decane compound may, for example, be 3 -aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltriethoxylate. Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3 -ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecyl® propyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane-1,4, 7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-amine Propyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Triethoxy decane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like.

The use ratio of the functional decane compound as described above is preferably 2 parts by weight or less, more preferably 0.01 to 0.2 parts by weight, based on the total amount of the 100 parts by weight of the polymer. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention is preferably at least one selected from the group consisting of polylysine and polyimine as described above, and other additives optionally blended as needed. It is composed of an organic solvent. As the organic solvent which can be used as the liquid crystal alignment agent of the present invention, it can be listed as -31-200925183, for example, N-methyl-2-pyrrolidone, τ-butyrolactone, r-butylide, n, N-di Methylformamide, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropyl Methyl ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol Dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, two Glycol monoethyl ether acetate, 3 -butoxy-indole, hydrazine-dimethylpropanolamine, 3-methoxy-hydrazine, hydrazine-dimethylpropanamide, 3·hexyloxy-hydrazine , Ν-dimethylpropanamide and the like. In the liquid crystal alignment agent, the solid content concentration (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范围 The range of weight %. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below, preferably by heating to form a coating film as a liquid crystal alignment film, and 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 content concentration exceeds 10% by weight, 'the thickness of the coating film is too thick to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased. , resulting in poor coating performance. A more preferable solid content concentration range ' differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, the solid content concentration is preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, the solid content concentration is preferably in the range of 3 to 9 % by weight, so that the viscosity of the solution falls within the range of 12 to 50 mPa_s. When the ink jet method is employed, it is more preferable to make the solid content concentration in the range of 1 to 5 wt%, so that the solution viscosity can be in the range of 3 to 15 mPa, s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇C to 200 ° C, more preferably 20 ° C to 60 ° c ° <liquid crystal display element> The liquid crystal display element of the present invention has the above The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. © As a preferred mode of operation of the liquid crystal display element of the present invention, a TN type, a VA type or an IPS type can be cited. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). The substrate to be used in the step (1)', the preferred coating method of the liquid crystal alignment agent, and the heating temperature after the application of the liquid crystal alignment agent differ depending on the desired operation mode, and the steps (2) and (3) are various. Common in working methods. (1) First, a coating film is formed on a substrate by applying the liquid crystal alignment agent of the present invention to a substrate and heating the coated surface. (1 _ 1) When manufacturing a TN type or VA type liquid crystal display element, two substrates each having a patterned transparent conductive film are used as a pair, preferably by offset printing, spin coating or ink jet printing. The liquid crystal alignment agent of the present invention is applied to each of the surfaces on which the transparent conductive film is formed, and then the coating film is formed by heating each of the coated surfaces. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether mill, polycarbonate, poly (aliphatic ring) can be used. A transparent substrate made of plastic such as a olefin-33-200925183 hydrocarbon. As the transparent film provided on one side of the substrate, a NESA film (US PPG registered trademark) made of tin oxide (Sn〇2), an ITO film made of indium oxide-tin oxide (In2〇3- Sn〇2), or the like can be used. The pattern of the transparent conductive film can be obtained by, for example, a method of forming a pattern by photolithography after forming a non-graphic transparent conductive film, or a method of using a mask having a desired pattern when forming a transparent film, or the like. In order to further improve the adhesion between the substrate surface and the transparent conductive coating film, it is also possible to apply a functional decane compound or a functional titanium compound to the coating film to be formed on the surface of the substrate during the application of the liquid agent. Pre-processing. The heating temperature after application of the liquid crystal alignment agent is preferably from 30 to 300 ° C, from 40 to 250 ° C, and the heating time is preferably from 1 to 60 minutes, more preferably from 30 minutes. The thickness of the formed coating film is preferably 0.001 to i; zm, more preferably 0_005 to 〇_5//m. (1-2) On the other hand, when manufacturing an IPS type liquid crystal display element, a pick-up roll coating method, a spin coating method, or an inkjet printing method, a conductive film of a substrate provided with a transparent conductive film forming a bar pattern The liquid surface agent of the present invention is applied to one surface of the forming surface and the opposite substrate on which the conductive film is not formed, and then the respective coated surfaces are heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the method of forming the transparent conductive pattern, and the pretreatment of the substrate and the heating temperature after the application of the (1_1) phase liquid crystal alignment agent are preferably 80 to 3001: 120 ~250C 'heating time is preferably 1~60 minutes, more preferably 30 minutes conductive paper note, the shape of the crystal guide film and the surface material is better 10~ better for the better tooth shape tangible crystal distribution film division . More preferably, 10~-34-200925183 The preferred thickness of the formed coating film is the same as (1 - 1) above. In any of the above (1 to 1) and (1 to 2), the liquid crystal alignment agent of the present invention forms a coating film as an alignment film by removing an organic solvent after coating, in the liquid crystal alignment agent of the present invention. When the polymer contained is polyamic acid or a polyimine having a quinone ring structure and a guanidine structure, it may be further subjected to dehydration ring closure by further heating after forming a coating film to form a further yam. Aminated 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 coating film is caused to generate alignment energy of the liquid crystal molecules to form a liquid crystal alignment film. Further, in the case of the VA type liquid crystal display element, the polishing process is not performed. In the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, the liquid crystal is shown in, for example, the patent document 4 (Japanese Laid-Open Patent Publication No. Hei 6-222366) or the patent document 5 (JP-A-H06-281937). A process in which a part of the alignment film is irradiated with ultraviolet rays to change the pretilt angle 一部分 of a portion of the liquid crystal alignment film, or is formed on a part of the surface of the liquid crystal alignment film as shown in Patent Document 6 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. After the protective film, the treatment for removing the protective film after the rubbing treatment is performed in a direction different from the previous polishing 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 pair of substrates on which the liquid crystal alignment film is formed as described above are placed opposite to each other through a gap (cell gap), so that the polishing direction of the liquid crystal alignment film of the two substrates is perpendicular or antiparallel, and the peripheral portions of the two substrates are bonded with a sealant. The liquid crystal gap is filled into the cell gap separated by the substrate-35-200925183 surface and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, a polarizing plate is attached to the outer surface of the liquid crystal cell so that the polarizing direction thereof is uniform or perpendicular to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff's-type liquid crystal, an azo-based liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane can be used. Liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals; and the trade names "C-1 5" and "CB-15" (manufactured by MERCK Corporation) A chiral agent sold; used for ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate or a ruthenium film formed by sandwiching a polarizing film called "H film" obtained by stretching the polyvinyl alcohol and simultaneously absorbing iodine, in a protective film of acetate. A polarizing plate made by itself. The liquid crystal display element of the present invention produced as described above has a display performance which does not deteriorate even when driven for a long period of time, as compared with the previously known liquid crystal display element. Specifically, it has the following advantages: it does not cause it to be considered to be due to The deterioration of the liquid crystal alignment film causes backlight leakage or the like due to poor alignment of the liquid crystal. [36] [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. Further, the 3,5-diamino benzoic acid in the following synthesis example was directly used as a commercial product of Tokyo Chemical Co., Ltd. Further, the viscosity of the polymer solution in the synthesis example was measured by an E-type viscometer at 25 °C. Synthesis Example 1 (Synthesis Example 1 of Polyimine) ® 112 g (0.50 mol) and 1,3,3 & 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]T furan·1,3- Diketone 157g (0.50 mole) 'p-phenylenediamine as diamine 83g (0.78 moles), 3,5-diaminobenzoic acid 15.2g (0.10 moles), bisaminopropyltetramethyldifluorene 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy)cholestane i3g (0.020 moles) and 2.7g (0.030 moles) of aniline as a monoamine are dissolved in 9 60 g of N-methyl-2-pyrrolidone was allowed to react at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2.pyrrolidone was added to prepare a solution having a concentration of 10% by weight, and the solution viscosity was determined to be 4 8 mPa·s. Then, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 1 l ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new r-butyrolactone solvent (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system, the same below), and then - 37- 200925183 After concentration, about 2640 g of a solution containing 15% by weight of a polyamidimide (A-1) having a ruthenium iodide ratio of about 90% was obtained. A small amount of this solution was taken, and r-butyrolactone was added to prepare a solution having a concentration of 6.0% by weight, and the viscosity of the solution was determined to be 15 m P a · s. Synthesis Example 2 (Synthesis Example 2 of Polyimine) 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, p-phenylenediamine as a diamine 76 g (0.7 mol), 3,5·diamino benzoic acid 15 g (0.10 mol) and 105 g (0.20 mol) of the chemical compound represented by the above formula (D-10) were dissolved in 4500 g of N-methyl group. In 2-pyrrolidone, it was allowed to react at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polypyrene resin solution was taken and concentrated under reduced pressure to prepare a solution having a concentration of 丨〇% by weight, and the measured solution viscosity was 60 mPa·s. Then, 2700 g of N·methyl-2-thiazolinone was added to the obtained polyamic acid solution, and 396 g of pyridoxine and 409 g of acetic anhydride were further added at 110. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new r-butyrolactone solvent, and then concentrated to obtain about 2770 g containing 15% by weight of ruthenium amide. A solution of about 90% polyethylenimine (a - 2). Take a small amount of this solution, add r -butyrolactone, and prepare a solution with a concentration of 6. 〇% by weight. The measured solution viscosity is 16 mpa.s. Synthesis Example 3 (Synthesis Example 3 of Polyimine) A pair of diamines of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride (yttrium. 34 mol) Benzene diamine 19g (〇18 mole), 3,5_-amino benzoic acid 27g (0.18 mole) dissolved in i260g N-methyl-2-pyridin-38- 200925183 s-alkanone to make it at room temperature The reaction was carried out for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken and concentrated under reduced pressure to prepare a solution having a concentration of 10% by weight, and the viscosity of the solution was determined to be 80 mPa's. 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 g of acetic anhydride were further added, and the mixture was subjected to dehydration and ring closure at 110 ° C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with a new solvent of hydrazine-butyrolactone, and then concentrated to obtain 600 g of a polyimine containing 20% by weight of hydrazine imidization (about 85%). A-3) ® solution. A small amount of this solution was added, and r-butyrolactone was added to prepare a solution having a concentration of 6.0 wt%, and the measured solution viscosity was 22 mPa's. Synthesis Example 4 (Synthesis Example of Polyimine) 4) 224 g (l. mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, as a diamine p-phenylenediamine 76 g (0.7 mol), 3, 5-diaminobenzoic acid 15g (0.1 mole), 4,4'-diamino. Diphenylmethane_232 (0.1 mole) and 2,2'-trifluoromethyl-4,4'- The diaminobiphenyl 32 (0.1 mol) was dissolved in 27 OOg of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours to obtain a polyglycine-containing solution. The amine acid solution was concentrated under reduced pressure to prepare a solution having a concentration of 10% by weight, and the measured solution viscosity was 80 mPa's. Then, 2000 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 150 g was further added. Pyridine and 200 g of acetic anhydride were subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After dehydration ring closure reaction, the solvent in the system was replaced with a new r-butyrolactone solvent, and then concentrated to obtain -39-200925183 243 0g of a solution containing 15% by weight of polyamidiamine (A-4) having a ruthenium iodide ratio of about 85%. ' Take a small amount of this solution and add 7 · butyrolactone to prepare a solution having a concentration of 6.0% by weight. The measured solution viscosity was 20 mPa's. Synthesis Example 5 (Synthesis Example 5 of Polyimine) 66 g (0.29 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 3,5- as a diamine 50 g of diamino benzoic acid (0.33 mol) was dissolved in 12 60 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken and concentrated under reduced pressure to prepare a solution having a concentration of 10% by weight, and the viscosity of the solution was determined to be 55 mPa·s. Then, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and further, 16 16 g of pyridine and 90 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 1 hour under TC (dehydration ring closure reaction). The solvent in the system was replaced with a new r-butyrolactone solvent, and then concentrated to obtain about 9 76 g of a polyimine (A - 5) containing 15% by weight of a ruthenium iodide ratio of about 85%. A small amount of this solution was added to r·butyrolactone to prepare a solution having a concentration of 6.0% by weight, and the measured solution viscosity was 18 mPa·s. Synthesis Example 6 (Synthesis Example 1 of Other Polyimine) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 112 g (〇.5〇莫耳) and ^, ^/,, exo-hexahydro-methylpyrenetetrahydro- 〖^-Dioxo-3-furanyl)-naphthalene [i,2-c]·furan-1,3-dione 157g (0.50 mole)' p-phenylenediamine as diamine 94g (〇.88 Mohr), bisaminopropyltetramethyl-40- 200925183 bis-dioxane 25g (0.1 mol) and 3,6-bis(4-aminobenzylideneoxy)cholane 13g ( 0.020 mol), and 2.7 g of aniline as a monoamine (〇.〇30 mol) dissolved in 960 g In N-methyl-2-pyrrolidone, a solution containing poly-proline was obtained by reacting at 6 (TC for 6 hours). A small amount of the obtained polyaminic acid solution was taken and concentrated under reduced pressure to a concentration of 1 〇. % solution, the measured solution viscosity is 5 8 m P a · s. Add 2700g N-methyl-2-pyrrolidone to the obtained polyaminic acid solution, then add 396g pyridine and 409g acetic anhydride at 1 10 °C The dehydration ring closure reaction was carried out for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new r-butyrolactone solvent, and then concentrated to obtain about 2620 g containing 15% by weight of ruthenium amide. A solution of 95% polyimine (A-6). A small amount of this solution was added, and r-butyrolactone was added to prepare a solution having a concentration of 6.0% by weight, and the viscosity of the solution was determined to be 18 mPa·s. 7 (Synthesis Example 2 of Other Polyimine) ^ 73 g (0.33 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride as p-diphenyl compound Amine 3〇g (〇.28mol) and 36g (0.069 moles) of the diamine represented by formula (D-10) are dissolved in 5 60g of N-methyl-2-pyrrolidone, The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-methyl ketone was added to prepare a solution having a concentration of 10% by weight. The measured solution viscosity was 80 m P a. s. Then, 600 g of the obtained poly-proline solution was added with i300 g of N-methyl-2-lager's solution, and then 26 g of rhodium and 34 g of acetic anhydride were added. Hey. 〇下-41 - 200925183 Perform a 4-hour dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new r-butane solvent, and then concentrated to obtain 790 g of a polyimine (A-containing 10% by weight of ruthenium iodide ratio of about 92%). 7) solution. A small amount of this solution was taken, and butyrolactone was added to prepare a solution having a concentration of 6% by weight, and the viscosity of the solution was determined to be 30 mPa·s. Synthesis Example 8 (Synthesis Example 3 of Other Polyimine) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride 77 g (0.34 mol) and p-benzene as a diamine A diamine-containing solution was obtained by dissolving 38 g of diamine (0.36 mol) in 1260 g of N-methyl-2-pyrrolidone and allowing it to react at room temperature for 6 hours. A small amount of the obtained polyaminic acid solution was taken and concentrated under reduced pressure to prepare a solution having a concentration of 10% by weight, and the solution viscosity was determined to be 90 mPa·s. Then, 600 g of N · methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridoxine and 1 g of acetic anhydride were added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After dehydration ring closure reaction, through the system

The solvent of Q was replaced with a new 7-butyrolactone and concentrated to obtain 760 g of a solution containing 15% by weight of a polyamidimide (A-8) having a ruthenium iodide ratio of about 95%. A small amount of this solution was added, and r-butyrolactone was added to prepare a solution having a concentration of 6. 〇 by weight. The viscosity of the solution was determined to be 25 mPa·s. Synthesis Example 9 (Synthesis Example 4 of Other Polyimine) 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, and p-phenylene as a diamine Amine 87g (0.8 moles), 4,4,- -42- 200925183 diaminodiphenylmethane 23g (〇.l mole) and 2,2'-trifluoromethyl-4,4'-diamine 32 g of bisphenyl (0.1 mol) was dissolved in 2700 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 polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of 10% by weight, and the solution viscosity was determined to be 80 mPa·s. Then, 2000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 150 g of pyridine and 200 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 1 l ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new r-butyrolactone solvent, and then concentrated to obtain 2400 g of a polyimine (A) containing 15% by weight of a ruthenium iodide ratio of about 95%. - 9) solution. &gt; A small amount of this solution was added to add r-butyrolactone to prepare a solution having a concentration of 6.0% by weight, and the solution viscosity was determined to be 2 5 mP a · s. Synthesis Example 1 (Synthesis Example 5 of Other Polyimine) 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxogen) as tetradecanoic dianhydride 3-3-furyl)-naphthalene [1,2-c]-furan-1,3-dione 150 g (0.50 moule) 'p-phenylenediamine as diamine 43.2 g (0.40 mol) and 3 15.2 g (0.10 mol) of 5-diaminobenzoic acid was dissolved in 1220 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 polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a concentration of 10% by weight, and the solution viscosity was determined to be 90 mPa·s. Then, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 136 g of pyridine and 105 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 of -43-200925183 in the system was replaced with a new r-butyrolactone, and then concentrated to obtain 1380 g of a polyfluorene containing 15% by weight of ruthenium iodide of about 91%. A solution of the amine (A-10). A small amount of this solution was added, and γ-butyrolactone was added to prepare a solution having a concentration of 6.0% by weight. The viscosity of the solution was determined to be 25 mPa·s. Synthesis Example 11 (Synthesis Example 1 of Other Polylysine) 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and as a diamine 2,2'-Dimethyl-4,4'-diaminobiphenyl biphenyl 212g (l. oxime) dissolved in a mixture of 370g N-methyl-2-pyrrolidone and 3300g r-butyrolactone In a solvent, it was allowed to react at 40 ° C for 3 hours to obtain about 4200 g of a solution containing 1% by weight of poly-proline (B-1). The solution had a solution viscosity of 210 mPa.s. Synthesis Example 12 (Synthesis Example 2 of Other Polylysine) 2, g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and a perylene tetra Anhydride i96g (0.90 moles), and 159g (0.8 moles) of 4,4'-diaminodiphenyl ether as diamine^ and 21g (0.2 moles) of p-phenylenediamine are dissolved in 3600g of N-A In the base-2-pyrrolidone, it was reacted at 4 (TC for 4 hours) to obtain about 4000 g of a solution containing 10% by weight of polyglycine (B-2). The solution viscosity of the solution was 400 mPa.s. Example 1 &lt;Preparation of Liquid Crystal Aligning Agent&gt; The polyimine-containing (A-D-containing solution) prepared in Synthesis Example 1 was equivalent to 20 parts by weight in terms of polyimine (A-1). The amount of the polyglycine (B-1)-containing solution obtained in Synthesis Example 11 from -44 to 200925183 was mixed in an amount equivalent to 80 parts by weight in terms of poly-proline (B-1). The ratio of butyrolactone methyl-2·pyrrolidone:butyl cellosolve is 71:17:12 by weight, and r-butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve are added thereto, and then 2 is added. 5% by weight of epoxy compound as an adhesion aid Ν, Ν, Ν' , Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, 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 m. A liquid crystal alignment agent was prepared. The liquid crystal alignment agent was evaluated as follows. <Production and Evaluation of Liquid Crystal Display Element> '[Production of Liquid Crystal Display Element] A spin coater was used at a rotation speed of 2000 rpm and a rotation time of 20 The liquid crystal alignment agent prepared above was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm under the conditions of a second, and heated at 200 ° C for 1 hour to remove the solvent to form a film thickness of 〇. 〇 8 M m coating film. A grinding machine equipped with a roller wound with rayon cloth at a roller speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 0.4 mm. The coating film is subjected to a rubbing treatment to cause a liquid crystal alignment of the coating film to form a liquid crystal alignment film. The substrate having the liquid crystal alignment film is ultrasonically washed in ultrapure water for 1 minute, at 1 °°. Drying in C clean oven for 10 minutes 'Repeat the same operation to produce two ("pair" substrates having a liquid crystal alignment film. Then" on each of the outer edges of the pair of liquid crystal alignment films having a liquid crystal alignment film, a diameter of 5·5μπι of the alumina ball ring-45 - 200925183 After the oxygen resin adhesive, the liquid crystal alignment film surface is relatively recombined and pressed, and then the adhesive is cured. Then, the liquid crystal injection port is filled with dielectric between the substrates. After a nematic liquid crystal having a constant anisotropy (MLC-6221, manufactured by MERCK Co., Ltd.), the liquid crystal injection port was closed with an acrylic photocurable adhesive, and a polarizing plate was bonded to both outer surfaces of the substrate to produce a liquid crystal. Display component. [Evaluation of Liquid Crystal Display Element] (1) Evaluation of liquid crystal alignment property 0 The liquid crystal display element manufactured above was observed under crossed Nicols using a polarizing microscope. At this time, there was no light leakage, and liquid crystal alignment evaluation was performed. If it is "good" and it is confirmed that there is light leakage, the liquid crystal alignment property is evaluated as "poor". The liquid crystal alignment property of the liquid crystal display element was "good". (2) Evaluation of heat resistance (heat stress test) First, a voltage of 5 V was applied to the liquid crystal display element manufactured above for a time span of 167 milliseconds, and the voltage application time was 60 microseconds, and then eight measurements were released from the voltage. The voltage holding ratio after 167 milliseconds. The number 値 此时 at this time is taken as the initial voltage holding ratio (VHRbf). After the VHRBF was measured, the liquid crystal display element was placed in an oven at 100 ° C, and a thermal stress of 1 000 hours was applied. Then, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature, and then the voltage holding ratio VHRAF after the application of the thermal stress was measured. The rate of change of the voltage holding ratio before and after the application of the thermal stress is determined by the following formula (ii). When the rate of change is less than 3%, the heat resistance is evaluated as "good", and when it is 3% or more, the heat resistance is evaluated as "poor". . The heat resistance of the liquid crystal display element was "good". -46- 200925183 Rate of change (%) = vhrbf-vhraf vhrbp X 1 ο ο (i i) In addition, the voltage holding ratio was measured using "V H R _ 1 " manufactured by TOYO Corporation. Example 2 &lt;Preparation of Liquid Crystal Aligning Agent&gt; The polyimine-containing amine (Α-2) obtained in Synthesis Example 2 in an amount equivalent to 100 parts by weight of the polyiminoimine (Α-2) was measured. a solution of r-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve in a ratio of 4〇: 3〇: 2〇, to which is added butyl vinegar, N-methyl- 2-Dbiginone and butyl cellosolve' plus 2 parts by weight of epoxy compound as an adhesion aid Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodi The phenyl group 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 Ι/zm to prepare a liquid crystal alignment agent. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; In the first embodiment, a liquid crystal (manufactured by MERCK Co., Ltd., MLC-203 8) which exhibits a dielectric constant anisotropy of liquid crystal is used, and examples (1) A liquid crystal display element was produced in the same manner, and liquid crystal alignment properties and heat resistance were evaluated. The results are shown in Table 1. Example 3 &lt;Preparation of liquid crystal alignment agent&gt; The ruthenium-imidized polymer obtained in Synthesis Example 3 in an amount equivalent to 1 part by weight in terms of polyimine (A-2) was measured. a solution of α 3) to which 1 part by weight of an epoxy compound n, n, n, n, _ -47 - 200925183 tetraglycidyl-4,4'-diamino group is added as an adhesion aid Diphenylmethane and 0.75 parts by weight of functional decane compound 3-[2-(3-trimethoxydecylpropylamino)ethylamino] methyl propionate, followed by r-butyrolactone: butyl cellosolve The ratio of the agents was 90:10 by weight, and r-butyrolactone and butyl cellosolve were added to prepare a solution having a solid content concentration of 4% by weight. This solution was filtered through a filter having a pore size of lvm to prepare a liquid crystal alignment agent. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; ❹ Ο In the first embodiment, in addition to the nematic liquid crystal (MLC-20 19 manufactured by MERCK Co., Ltd.) which exhibits a positive dielectric enthalpy by dielectric anisotropy, In the same manner as in Example 1, a liquid crystal display element was produced, and liquid crystal alignment properties and heat resistance were evaluated. The results are shown in Table 1. (Examples 4 and 5) Each of the liquid crystal alignment agents was prepared in the same manner as in Example 3 except that the polymer was used in the amounts shown in Table 1 in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table 1. Comparative Example 1 A liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 except that the polymer of the type indicated in Table 1 was used in the amounts shown in Table 1. The results are shown in Table 1. Comparative Examples 2 and 5 Each of the liquid crystal alignment agents was prepared in the same manner as in Example 2 except that the polymer was used in the amounts shown in Table 1 in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table i. Comparative Example 3 and 4 - 48 - 200925183 A liquid crystal display element was produced in the same manner as in Example 3 except that the polymer was used in the amounts shown in Table 1 in the amounts shown in Table 1. Conduct an evaluation. The results are shown in Table 1.

-49- 200925183

Liquid crystal display heat resistance 1 Good, good, good, good, bad, n^ If poor, poor liquid crystal alignment, good I, good, good, good, good, good, good, good, good, good, liquid crystal, dielectric anisotropy, liquid crystal name, 6221 2038 2019 2019 2019 6221 2038 2019 2019 2038 Liquid crystal alignment agent solid content concentration (wt%) cn ρ pp V〇cn to p ρ v〇 adhesion aid functional decane compound parts by weight 〇〇0.75 0.75 v〇〇〇Ο 0.75 0.75 Ο Type 1 1 MSPP MSPP MSPP 1 1 MSPP MSPP 1 Epoxy compound parts by weight CS Cvl o Ο o CN o 〇C&lt;1 Sao tlmtl 郷GAPM : GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM Polymer Polyurethane Thunder Ο 〇 s 〇o 〇s 〇 species ώ I 1 csi PQ 1 PQ 1 1 cs ώ 1 polyimine _ by weight 丨Ο ψ—&lt; 〇1 &lt; 〇〇ψ -H 〇» _&lt; 0 1 &lt; o 〇1 1 &lt; Category &lt;C&lt;J&lt; CO &lt; inch &lt;&lt; VO &lt; O' &lt; oo &lt; 〇 &gt; A-10 Embodiment 1 Embodiment 2 Example 3 Example 4 Implementation Example 5 ratio Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 200925183 In addition, the "type, the abbreviation in the column" of the adhesion aid of Table 1 respectively represent the following definitions. The epoxy compound GAPM: N, N, N , N _tetraglycidyl-4,4 -monoamino-*benyl methane functional decane compound MSPP: 3-[2-(3·trimethoxy sand propylamino)ethylamine Methyl propionate and the description in the column of "Liquid crystal name" represent the following definitions. Ο 6221: MLC-6221 (product name, manufactured by MERCK) 2038: MLC-2038 (product name, manufactured by MERCK), 2019: MLC-2019 (trade name, manufactured by MERCK) [Simplified description of the drawing] None. [Description of main component symbols] and j\w 〇-51-

Claims (1)

200925183 X. Patent Application Range: 1. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The polycarboxylic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A) and a polyimine which is obtained by dehydrating and ring-closing the polyamic acid (A) The liquid crystal alignment agent of claim 1, wherein the diamine further contains a compound represented by the following formula (D-III), (D-III) In the formula (D-III), R7 is a group selected from -0-*, -COO-*, -OCO-*, -NHCO-*, -CONH-*, and -CO-* a divalent organic group (wherein a bond is bonded to R8), and R8 is a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethyl group, and a fluorine group A group or an alkyl group having 6 to 30 carbon atoms. 3. The liquid crystal alignment agent of claim 2, wherein R7 in the above formula (D - III) is -0-* or -COO-* (wherein the bond is bonded to R8), and R8 has 甾a monovalent organic group of a bulk skeleton. 4. The liquid crystal alignment agent of claim 1, wherein the diamine further contains p-phenylenediamine. -52- 200925183 5. The liquid crystal alignment agent as described in claim 1 of the invention is a polyimine. A liquid crystal alignment film comprising a liquid crystal alignment agent formed by the liquid crystal alignment agent according to any one of claims 1 to 5. 〇 〇 -53- 200925183 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: ΕΕ ΕΕ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: