TW201005006A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The object of the present invention is to provide a liquid crystal display element, wherein is capable of forming a liquid crystal display element without reducing the voltage holding ratio even though applying thermal stress at long term, a liquid crystal alignment agent of a liquid crystal alignment film having high heat resistance, and the display quality does not reduce even though driving at long term. The solution of the present invention is to provide a liquid crystal alignment film, wherein said liquid crystal alignment agent comprising at least one polymer selected from the group consisting polyamic acid and polyimide, wherein in the molecule of the said polymer comprising at least one part of structure represented by following formula (A). The said liquid crystal display element has a liquid crystal alignment film forming from a liquid crystal alignment agent.

Description

201005006 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal display element capable of forming a liquid crystal alignment film which exhibits excellent heat resistance and a liquid crystal display element which does not deteriorate display quality for a long period of time. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) e liquid crystal cell is widely known, and a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided. As a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell of a sandwich structure, and the long axis of the liquid crystal molecules is directed from one substrate to the substrate. The other substrate is continuously twisted by 90 degrees. In addition, an STN (Super Twisted Nematic) liquid crystal display element capable of achieving a higher contrast ratio than a TN liquid crystal display element, an IPS (in-plane switching) type liquid crystal display element having a small viewing angle dependency, and an IPS type change have been developed. FFCB (Optical Compensated Bend) which is excellent in the FFS (Fringe Field Conversion) type liquid crystal display element which improves the aperture ratio of the display element portion to improve the luminance, and has excellent viewing angle dependence and high-speed response of the video picture. A liquid crystal display element and a VA (Vertical Alignment) type liquid crystal display element using nematic liquid crystal having negative dielectric anisotropy. As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as polyacrylic acid, polyamidiamine, polyamine, or polyester, particularly a liquid crystal made of polyamic acid or polyimine, is known. The alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, and the like, and is used in many liquid crystal display elements (see, for example, Patent Documents 1 to 3). The liquid crystal display element as described above requires a longer driving than before. For example, in recent years, liquid crystal televisions are required to maintain a good display state for a long period of time (for example, 10 years or more), and in particular, it is required to maintain a high voltage holding ratio even if thermal stress is applied due to long-term display driving. Performance (hereinafter also referred to as "heat resistance"). The resin material for a liquid crystal alignment film which has been known in the prior art is used for the purpose of improving heat resistance by using polyamidiamine or by using p-phenylenediamine as a monomer used in the preparation thereof. However, the use of such a strategy for the improvement of the heat resistance is limited, and the conventionally known resin material for a liquid crystal alignment film cannot satisfy the heat resistance required in the environment in which an increasingly severe liquid crystal display element is used. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-149. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The object of the present invention is to provide a liquid crystal alignment agent capable of forming a heat-resistant liquid crystal alignment film having a high thermal stress holding rate even if it is applied for a long period of time, and having a high heat resistance liquid crystal alignment film of 201005006, and a liquid crystal which does not deteriorate even if the display quality is driven for a long period of time. Display component. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above objects and advantages of the present invention, first, are achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and polyimine, wherein the polymer At least a part of the molecules have a structure represented by the following formula (A).

(A) The above object and advantages of the present invention, and secondly, achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which does not decrease even if a thermal stress voltage holding ratio is applied for a long period of time. The liquid crystal display element of the present invention having such a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention does not deteriorate in display quality 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, it can be applied to a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a PDA (personal digital assistant), Digital cameras, mobile phones, various monitors, LCD TVs, etc., ϋ-f· ccet are not installed. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polylysine and polyamidiamine 201005006, wherein the above polymer At least a part of the molecules have a structure represented by the above formula (A). Hereinafter, in the present specification, such a polymer is referred to as a "specific polymer." In the specific polymer, the structure represented by the above formula (A) may be present in the main chain of the polymer, or may be present in the side chain of the polymer, or in both the main chain and the side chain of the polymer. presence. The structure represented by the above formula (A) is preferably at least one selected from the group consisting of structural configurations represented by the following formulas (A-1) to (A-3).

(Ra in the formula (A-1) is a halogen atom, a cyano group, an isocyano group, -〇CN, -NCO, -SCN, -NCS or an azide group, and η is an integer of 0 to 3, each Expressed as a connection key;

Rb and R in the formulas (Α-2) and (Α-3). Each is independently a hydrogen atom, a halogen atom, a cyano group, an isocyano group, -〇CN, -NCO, -SCN, -NCS 201005006 or an azide group, each represented as a linkage). The content ratio of the structure represented by the above formula (A) in the polymer is preferably 2.0 x 10 -5 mol / g or more, more preferably Ι. ΟχΙΟ · 4 to 3.0 x l · 3 m / g, particularly preferably 2.0xl0·4 〜1·Οχ1〇·3 Moor/g. The polyamic acid having at least a part of the molecule having the structure represented by the above formula (A) can be obtained, for example, by reacting the following, that is, containing the structure represented by the above formula (A) and two carboxylic anhydrides. The tetracarboxylic dianhydride of the compound of the group is reacted with a diamine or a tetracarboxylic dianhydride is reacted with a diamine containing a compound having a structure represented by the above formula (Α) and two amine groups. The polyimine having at least a part of the molecule having the structure represented by the above formula (A) can be produced, for example, by dehydrating and blocking the polylysine obtained as described above. The specific polymer contained in the liquid crystal alignment agent of the present invention is preferably selected from the group consisting of reacting a tetracarboxylic dianhydride with a diamine containing a compound having the structure represented by the above formula (A) and two amine groups. At least one of the group consisting of polylysine and a polyamidene obtained by dehydration of the polyamic acid ring. <tetracarboxylic dianhydride> Examples of the tetracarboxylic dianhydride which is preferred for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention include alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic acid. A dianhydride and an aromatic tetracarboxylic dianhydride. Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutylidene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3· 201005006 dichloro-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-l,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclohexyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di-side oxygen Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5: 6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3 -furyl)-naphthoquinone [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro- 2,5-dioxa-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,913-hexahydro-5-ethyl- 5- (four -2,5-di-oxo-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-7- Methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-di Ketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c] -furan-1,3-dione, © 1,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxo-3-furan Base)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-5,8-dimethyl-5-(four Hydrogen-2,5-di-oxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuranyl)-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-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), the following formulas (T-I) and (T-II) Compounds, etc.; 201005006

(Τ-Ι)

(In the formulae (Τ-Ι) and (Τ-II), each of R1 and R3 is a divalent organic group having an aromatic ring, and each of R2 and R4 is a hydrogen atom or a plurality of R2 and R4 each The same, can also be different).

Specific examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride and the like. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3,4,4. '-Diphenyl milled tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3,,4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4,-tetraphenylnonane IV Carboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl succinic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3,,4, 4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4,-biphenyl tetraresic acid dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, pair Phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4' -diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane Anhydride, ethylene glycol-bis(hydrogen trimellitate), propylene glycol-bis(hydrogen trimellitate), i,4-butanediol-bis (dehydration partial-10-201005006 trimellitic acid ester), 1,6-hexanediol-bis(hydrogen trimellitate), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane- A compound represented by each of bis(hydrogen trimellitate) and the following formulas (T-1) to (T-4).

-11 - 201005006

-12- 201005006 These tetracarboxylic dianhydrides may be used alone or in combination of two or more. The tetracarboxylic dianhydride of the preferred polyamic acid for use in the synthesis of the liquid crystal alignment agent of the present invention preferably contains an alicyclic tetracarboxylic dianhydride, pyromellitic dianhydride and 2,2'. A tetracarboxylic dianhydride of at least one of the group consisting of 3,3'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride"). The specific tetracarboxylic dianhydride is preferably selected from the group consisting of 1,2,3,4·cyclobutane tetracarboxylic dianhydride and 1,3-dimethyl group from the viewpoint of exhibiting good liquid crystal alignment. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2 , 3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dihydrotetrahydro-3-furanyl)-3- Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxynorbornane- 2:3,5:6-dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxanoxy-3-yanoyl)-naphthalene [l ,2-c]-furan-1,3-dione, i,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3 -furyl)_naphthalene [1,2-(;]-furan-1,3-indanedion, 1,3,3 ugly, 4,5,91)-hexahydro-5,8-dimethyl_ 5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7- Alkene 2,3,5,6-tetracarboxylic acid , 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), represented by the above formula (T-I) a compound represented by the following formula (T-5) to (T-7), a compound represented by the following formula (T-8), and pyromellitic acid among the compounds represented by the above formula (τ-II); At least one of a group consisting of dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride, • 13-201005006

(Τ-5) σ-β)

More preferably, it contains a 1,2,3,4-cyclobutanetetracarboxylic dianhydride, a base 1,2,3,4-cyclobutane tetracarboxylic dianhydride, a 2,3,5-tricarboxyl group. Cyclopentyl anhydride, 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexanedicarboxylic anhydride, 1,3,3&,4,5,91) - hexahydro-5-(tetrahydro-2,5-di-oxy)naphthalene [l,2-c]-furan-1,3-dione, cis-3,7-dibutylcyclohexane Alkene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxyl-9-2:3,5:6-dianhydride, 1,3,3&,4 ,5,91>-hexahydro-8-methyl-5-(tetrahydroxyloxy-3-furylnaphthalene [l,2-c]-furan-1,3-dione, 3-oxo [3· 2.1] octane-2,4·dione-6-spiro-3'-(tetrahydrofuran-2',5'-two-drawing (τ~5) compound, pyromellitic dianhydride and 2,2 a tetracarboxylic dianhydride of at least one of the group consisting of ',3,3' phthalic acid dianhydride, selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentanol, l,3,3a,4,5,9b-hexaamino-8-methyl-5-(tetrazo- 2,5-mono-anthranyl)-naphthalene [1,2-c ]-furan-1,3-dione and pyromellitic dianhydride structure, 3·diacetate diiso-1,2--3-furan-in-1,5-borneol-2,5- At least one of the above-mentioned 4-biphenyl fluorene-based acetoxy-3-furo-form group-14-201005006. As a preferred other four which can be used in combination with a specific tetracarboxylic dianhydride Examples of the phthalic acid dianhydride include butane tetracarboxylic dianhydride, 3,3', 4,4, benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl maple four. a carboxylic acid dianhydride, a 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. The tetracarboxylic dianhydride used for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention is preferably relative to all the tetracarboxylic acids. The dianhydride contains 60 mol% or more of the specific tetracarboxylic dianhydride as described above, and more preferably contains 80 mol% or more. © <Diamine> Preferred for synthesizing the liquid crystal alignment agent of the present invention The diamine of poly-proline is a diamine containing a compound having the structure represented by the above formula (A) and two amine groups (hereinafter referred to as "compound (A)"). As the compound (A), it is preferably A compound having a structure represented by the above formula (A-) and a compound having two amine groups (hereinafter referred to as "compound (A-!)"), a structure represented by the above formula (A-2), and two amines a compound of the group (hereinafter referred to as "the compound (A-2)") and a compound having the structure represented by the above formula (a-3) and two amine groups (hereinafter referred to as "compound (A-3)") At least one of the group formed. R + in the above formula (A-丨) is preferably a halogen atom, more preferably a fluorine atom. η is 〇 or 1», and Rb and R°' in the above formulae (a-2) and (A-3) are each preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a fluorine atom. The compound (A-1) may, for example, be a compound represented by the following formula (a-1 to 1), -15-201005006

(In the formula (A-1 - 1), Ra and n are respectively the same as defined in the above formula (A _1), and Ya is a single bond or an extended aryl group having 6 to 10 carbon atoms)" as the above formula (A) The aryl group having 6 to 10 carbon atoms of Ya in the group 1 to 1) may, for example, be a 1,4-phenylene group or a 1,5-naphthylene group. Specific examples of the compound represented by the above formula (A-1 -1) include, for example, 2,6-diamino group benzothiazole, 2,7-diaminobenzothiazole, and 2-(4-amino group). Phenyl)-6-aminobenzothiazole, 2-(4-aminophenyl)-7-aminobenzothiazole, and the like. Examples of the compound (A-2) and (A-3) include a compound represented by the following formulas (A-2-1) and (A-3-1), and the like.

(In the formulae (A - 2 - 1) and (a - 3 - 1), Rb and Rc are respectively the same as defined in the above formula (A-2) or (A-3), and Yb and Yc are each independently a single The bond or the aryl group having a carbon number of 6 to 1 Å). Examples of the Yb and Υ° in the above formula and (A-3-1) are an aryl group having 6 to 10 carbon atoms, and each of -16 to 201005006 can be exemplified by, for example, 1,4-phenylene group, 1,5. -naphthyl and the like. Specific examples of the compound represented by the above formula (A - 2_1) include, for example, 2,6-diaminobenzo[l,2-d:4,5-d']dithiazole, 2,6-double (4. Aminophenyl)benzo[l,2-d:4,5-d']dithiazole; and the specific example of the compound represented by the above formula (A-3 - 1), for example, 2, 6. Diaminobenzo[l,2-d:5,4-d']dithiazole, 2,6-bis(4-aminophenyl)benzo[1,2-(1:5,4 -(1']dithiazole, etc. As the diamine for synthesizing the preferred polyglycolic acid in the liquid crystal alignment agent of the present invention, only the compound (A) as described above may be used, or the compound ruthenium ( A) used in combination with other diamines. As other diamines which may be used herein, for example, an aromatic diamine, an aliphatic diamine, an alicyclic diamine, two primary amino groups in the molecule, and the primary amino group may be mentioned. a diamine or a monosubstituted phenylenediamine of a nitrogen atom other than

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,-diaminodiphenylethane, and 4,4. Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino Benzoquinone aniline, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4,-diaminobiphenyl, 5-amino group 1-(4'-aminophenyl)-l,3,3-trimethylindan, 6-amino-b (4'-aminophenyl)-1,3,3-trimethyl Indane, 3,4,-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4,-diaminobenzophenone, 4,4'-diaminodiphenyl Ketone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis(4-aminophenyl)hexafluoropropane, 2,2·bis[4-(4-aminophenoxy)phenyl] maple, U4_bis(4-aminophenoxy)benzene , 1,3- -17- 201005006 bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl) -10-hydroquinone, 2,7-diamino hydrazine, 9 ,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-di Aminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 2,2'-double [ 4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 , 4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-φ octafluorobiphenyl, bis(4-aminophenyl)benzidine, the following formula (D-1) ~(D-5) each represented by a compound, etc.

-18- 201005006 ❹ ΪΗ3 /CH3

(D, h2n- s-

NH2 (D-5) (y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 5); -19- 201005006 As the above aliphatic diamine, For example, 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, etc.; The diamine may, for example, be 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1. 02'7] eleven alkylene Dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, etc.; as the above molecule, having two primary amine groups and the first stage The diamine having an amine group as a nitrogen atom other than Φ may, for example, be 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine or 2,4-diaminopyrimidine. , 5,6-diamino-2,3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino- 1,3,5-triazole, 1,4-bis(3.aminopropyl) pipe trap, 2,4-amino-6-isopropoxy-1,3,5-diindole, 2 ,4-diamino-6-methoxy-1,3,5-three tillage, 2,4-di -6-phenyl-1,3,5-three tillage, 2,4-diamino-6-methyl-s-three tillage, 2,4-diamino-1,3,5-triazine , 4,6-diamino-2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-® diamine -1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinate lactate, 3,8 -diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 1-(3, 5-diaminophenyl)_3_mercaptosuccinimide, diaminophenyl)-3-octadecyl succinylamine, a compound represented by the following formula (D-z),

(In the formula (D-I), R5 is a monovalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple well, piperidine-20-201005006, and a bottom-bottom well, X1 a divalent organic group, R 6 is an alkyl group having 1 to 4 carbon atoms, and al is an integer of 0 to 3), a compound represented by the following formula (D - II), and the like.

(In the formula (D_II), R7 is a divalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine, and piperene, and each of X2 is divalent. The organic group may have the same or different X2 groups, each of which is an alkyl group having 1 to 4 carbon atoms, and each of a2 is an integer of 0 to 3); as the monosubstituted phenylenediamine, For example, a compound represented by the following formula (D - III), etc. (R11) a3 h2n

OR9—R10 (ηπ) I nh9 ❹ (In the formula (D - III), R9 is ·〇-, -COO-*, -OCO-*, -NHCO-*, -CONH-* (wherein the above, With a linkage to R1G) or -CO-, R1G is a backbone or group having a skeleton selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group. a valence organic group, or an alkyl group having 6 to 30 carbon atoms, and R11 is a carbon atom of 1~

The alkyl group of 4, a3 is an integer of 0 to 3), and the compound represented by the following formula (D-IV), etc., as the above-mentioned diaminoorganooxane, -21 -

201005006 r12 H2N-f-CH2 tfH. - ft^H2々NH2 R12 R12 (D-IV) (In the formula (D-IV), R12 is each a plurality of R1 2 having a carbon number of i~12, and may be the same or different, each of p 3 The integer 'q is an integer from 1 to 20). These diamines may be used alone or in combination. The benzene ring of the above aromatic diamine may be optionally substituted by one or two alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. Preferably, each of r6, r8 and R11 in the above formulae (D - II) and (D-III) is such that θ a2 and a3 are each preferably 〇 or 1, more preferably 〇. The steroid skeleton in R1C of the above formula (D-III) means a structure composed of a perhydrophenanthrene nucleus or a skeleton in which one or both of carbon-carbon bonds are double bonds. As the group of Ri 具有 having such a steroid skeleton, a group having 17 to 51 carbon atoms is preferable, and a group having 17 to 29 carbon atoms is more preferable. Specific examples of Ri(R) having such a steroid skeleton, such as cholest-3-yl, cholest-5-en-3-yl, cholest-24-ene-indole-5,24-diene- 3-yl, lanostan-3-yl and the like. Specific examples of the compound represented by the above formula (D - I) include, for example, a compound represented by the following formula (D-6); and the hydrocarbon group of (D-6) is independently 1 or more or two or more (D- I), 3 bases, a 1 , Cyclopentanol - The number of organic atoms of one or more valences is exemplified by 3-base, cholesteryl, and -22-201005006 can be listed as a specific example of the compound represented by the above formula (D_ Π). For example, a compound represented by the following formula (D-7); qn-^)^NH2 (1>7) Specific examples of the compound represented by the above formula (D-III) include, for example, the following formula (D). — 8)~(D-16) each represented by a compound or the like. ❹

-23- 201005006

〇CO OCF coo—( h2n NH: (D-15)

Preferred polyplycosyl p-phenylenediamine, 4,4'-diamine 1,5-diaminonaphthalene, 2,7-bis[4-(4-aminophenoxy) 2 , 2-bis[4-(4-aminophenoxy) as the other diamine for synthesizing the liquid crystal alignment agent of the present invention, among which the above-mentioned preferred use is selected from the group consisting of diphenylmethane and 4,4'-diaminodiphenyl. Thioetherdiamine hydrazine, 4,4'-diaminodiphenyl ether, 2,2 phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, phenyl)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p--24- 201005006 phenylene diisopropylidene)diphenylamine, 4,4'- Phenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4,-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy) Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4 - a diaminopyridine, a 2,4-diaminopyrimidine, a 3,6-diamino acridine, a compound represented by the above formula (D-6), a compound represented by the above formula (D-7), and the above formula ( Compound represented by D-III) and 1,3-bis(3-diaminopropyl-propyl) At least one of the group consisting of _tetramethyldioxane. In the above formula (D-III), R9 is -0- or -COO-* (wherein the linkage is bonded to R1G), and R1() has The compound of the monovalent organic group of the steroid skeleton is particularly preferably a compound represented by the above formula (D-8) to (D-13). As the other diamine, it preferably contains a compound selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and bis[4-(4.amine) a diamine of at least one group consisting of a compound of the above formula (D - III), particularly preferably a p-phenylenediamine, a 4,4'-diamine At least one of the group consisting of stilbene-β-methane, 4,4′-diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl]anthracene and the above formula (D_) The diamine of the compound represented by III). The preferred diamine of the polyglycolic acid used in the synthesis of the liquid crystal alignment agent of the present invention preferably contains 1 mol% or more, more preferably 5 to 90 mol% relative to all diamines. Further preferably contains 1 〇 ~ 80 mol %, especially good containing 15 ~ 30 mol% of compound (a). The di-25-201005006 amine for use in synthesizing the preferred polyglycolic acid in the liquid crystal alignment agent of the present invention preferably contains 1 to 50 mol%, more preferably 5 to 30 mol%, based on the entire diamine. A compound represented by the formula (d _ III). The preferred polyamine of the polyglycolic acid used in the synthesis of the liquid crystal alignment agent of the present invention preferably contains 30 to 90 mol%, more preferably 40 to 80 mol%, based on the entire diamine. a group consisting of phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl] mill At least one of the groups. <Synthesis of Polylysine> © Preferred polyphthalic acid in the liquid crystal alignment agent of the present invention can be produced by reacting a tetracarboxylic dianhydride as described above with a diamine containing the compound (A) Got it. The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group in the diamine, and the anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of 〇7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of -20 to 150 ° C, more preferably 0 to 10 ° C, preferably 1 to 72 β hours, more preferably Good 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 1-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and the like. Ν,Ν·Dimethylformamide, 3-butoxy-oxime, Ν·dimethylpropanamide, 3-methoxy-oxime, Ν-dimethylpropionate, 3-hexyloxy - anthraquinone compounds such as hydrazine, hydrazine, dimethyl propylamine, dimethyl sulfonium I, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; Phenolic compounds such as phenol, xylene, phenol, and halogenated phenol. The amount of the organic solvent (α), usually, -26-201005006 is preferably such that the total amount (β) of the tetracarboxylic dianhydride and the diamine is 0.1 to 30% by weight based on the total amount of the reaction solution (α + β). The amount. Further, when the organic solvent is used in combination with the poor solvent described below, the amount of the above organic solvent (〇〇 is understood to mean the total amount of the organic solvent and the poor solvent. In the above organic solvent, the produced polyamine is not formed. In the range of acid precipitation, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are generally considered to be poor solvents for poly-proline, may be used in combination as a specific solvent. Examples thereof include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol. Ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methoxy propyl Methyl ester, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, di-glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-Dichlorobutane, 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 use ratio of the poor solvent can be appropriately set within a range in which the produced polyamine acid is not precipitated. The total amount of the organic solvent and the poor solvent is preferably 30% by weight or less, more preferably 20% by weight or less. -27- 201005006 As described above, a reaction solution in which polylysine is dissolved is obtained. The solution may be directly supplied to the liquid crystal alignment agent to be prepared, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent for preparation, or the separated polyamic acid may be purified. Supply liquid crystal alignment agent to prepare. When polylysine is dehydrated When the ring is made into a polyimine, the reaction solution may be directly supplied to the dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated and supplied to the dehydration ring-closure reaction, or the separated polymer may be Φ. The proline acid is purified and then supplied to the dehydration ring-closure reaction. 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 then drying the precipitate under reduced pressure, or The organic solvent in the reaction solution is subjected to a method of distilling off under reduced pressure in an evaporator. Further, the polylysine is dissolved in an organic solvent and then precipitated with a poor solvent, or once or several times. Polyacetamide can be purified by a method of distilling off under reduced pressure in an evaporator. <Polyimine> The preferred polyimine 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 in the liquid crystal alignment agent of the present invention may be a complete ruthenium imide of a protonic acid structure in which the precursor polyamic acid has a dehydration ring closure, or a partial dehydration ring closure of only the proline structure. a partial ruthenium imide of a valeric acid structure and a quinone ring structure. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of -28 to 201005006 of 4 〇 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 better charge leakage property 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 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) based on tetramethyl decane. The substance 'at room temperature (for example, 25 ° C) The W-NMR was measured, and the measurement result was obtained by the following formula (1). Ruthenium amination rate (%) = (1 - A"A2x a )xl 00 (1) (In equation (1), A1 is the peak area originating from the NH matrix near the chemical shift of 10 ppm, and A2 is the source In the peak area of other protons, α is the proton of one sulfhydryl group in the precursor of polyimine (poly-proline), the ratio of the number of other protons.) The dehydration ring closure of poly-proline Preferably, (i) is carried out by heating the polyaminic acid method or (ii) by dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction time is preferably from 1 to 8 hours, more preferably from 3 to 3. 5 hours. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficient. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyimine will decrease. -29- 201005006 In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyaminic acid solution of the above (ii), As the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is determined according to the desired ruthenium imidation ratio, preferably 1 mol of the polyglycolic acid. The structure of the amine acid is 0.01 to 20 mol. 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 thereto. Preferably, the dehydrating agent is 0. 01~10 mol with respect to 1 mol. The more the dehydrating agent and the dehydrated ring-closing agent are used, the higher the niobium amination rate can be used. The organic solvent is exemplified as the organic solvent used for the synthesis of the polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. Preferably, it is 1 to 8 hours, more preferably 3 to 5 hours. The polyimine prepared in the above method (i) can be directly supplied to a liquid crystal alignment agent for modulation, or the obtained polyfluorene can also be obtained. The imine is refined and then supplied to the liquid crystal. Further, in the above method (ii), a reaction solution containing a polyimine is obtained, and the reaction solution may be directly supplied to a liquid crystal alignment agent for preparation, or may be dehydrated from the reaction solution. After the agent and the dehydration ring-closing catalyst are supplied to the liquid crystal alignment agent for preparation, the polyimine may be separated and supplied to the liquid crystal alignment agent for preparation, or the separated polyimine may be purified and then supplied to the liquid crystal alignment agent for preparation. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and for example, a method such as solvent replacement can be used. The separation and purification of the polyimine can be carried out in the same manner as described above for the separation and purification method of polyglycine. - 201005006 Operation. - Terminal-modified polymer - The poly-proline and the polyimine contained in the liquid crystal alignment agent of the present invention may each 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 carried out by adding a molecular weight modifier to a polymerization reaction system during the synthesis of polyamic acid. As the molecular weight modifier, a monoanhydride, a monoamine compound, a monoisocyanate compound or the like can be listed. As the above-mentioned monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the above monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine®, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid. - solution viscosity - polylysine and polyimine prepared as above, each preferably having a solution viscosity of 20 to 800 mP a. S when formulated into a solution having a concentration of 10% by weight, -31-201005006 Good with a solution viscosity of 30~500 mPas. The solution viscosity (mPa's) of the above polymer is a polymer solution having a concentration of 10% by weight prepared by using a good solvent of the polymer, and measured by an E-type rotational viscometer at 25 °C. <Other Additives> The liquid crystal alignment agent of the present invention contains the specific polymer as described above as an essential component, and may further contain other components as necessary. As such other components, for example, other polymers, an adhesion enhancer, and the like can be given. φ The above other polymers can be used for improving solution properties and electrical properties. The other polymer is a polymer other than the specific polymer, and for example, a polyglycine prepared by reacting a tetracarboxylic dianhydride with a diamine containing no compound (A) (hereinafter referred to as "other poly" "Proline" "), a polyimine (hereinafter referred to as "other polyimine") obtained by dehydration of the poly-proline, a polyphthalamide, a polyester, a polyamide, a polypeptone Oxylkane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. Among them, other poly-proline or other polyimine are preferred. The use ratio of the other polymer is preferably 90% by weight or less, and more preferably 85% by weight or less based on the total amount of the polymer (refer to the total amount of the specific polymer and the other polymer, the same applies hereinafter). The above-mentioned adhesiveness enhancer can be used for the purpose of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. As such a binder 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 - 32-201005006 may be mentioned as the above epoxy group compound. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-phenylene Methylamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, ^:^',:^'-tetraglycidyl-4,4'-diaminodiphenyl Methane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, © 3-(anthracene, 二glycidyl)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-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl® methyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3·ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane 1,4,7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-amine Propyl triethoxy-33- 201005006 decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine Alkyl, 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 〇. 2 parts by weight, based on 100 parts by weight of the total amount of the polymer. The liquid crystal alignment agent of the present invention is preferably prepared by dissolving a specific polymer as described above and other additives optionally blended as needed 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·butylide, N,N-dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene Alcohol ether acetate, diglyme, di-glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, 3-butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-indole, hydrazine-dimethylpropanamide, 3-hexyloxy-indole, hydrazine-dimethyl propyl Amidoxime 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 Torr. The range of % by weight. That is, the liquid crystal alignment agent of the present invention is coated on the surface of the substrate as described below, preferably by heating to form a coating film as a liquid crystal alignment film, which will cause the coating when the solid content concentration is less than 1% by weight. The thickness of the film is 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 adhesion of the liquid crystal alignment agent The increase in properties leads to poor coating properties. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to 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 particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the viscosity of the solution falls within the range of 12 to 50 mPai. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the 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 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal ruthenium alignment agent of the present invention as described above. Preferred working modes of the liquid crystal display device of the present invention include a TN type, a VA type, and an IPS type. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). For step (1), the substrate used differs depending on the desired mode of operation. Steps (2) and (3) are common to various operation modes. (1) First, a coating film is formed on a substrate by applying a liquid crystal alignment agent of the present invention on a substrate and then heating the coated surface. -35- 201005006 (1 ~ 丨) 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, roll coating, or spin In the coating method or the inkjet printing method, the liquid crystal alignment agent of the present invention is applied to each of the surfaces on which the transparent conductive film is formed to form a coating film. 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. Plastic transparent substrate such as olefin). As the transparent conductive film provided on one side of the substrate, a transparent film made of tin oxide (Sn02), a NESA film (registered trademark of PPG, USA), an indium oxide-tin oxide (ln203-Sn02), or the like can be used to form a transparent pattern. The 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 a transparent conductive film is formed, 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 a compound or the like ® After applying a liquid crystal alignment agent to such a substrate, preheating (prebaking) is preferably performed for the purpose of preventing liquid sagging or the like. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 1 ° C. The prebaking time is preferably from 0.25 to 10 minutes, more preferably from 0.5 to 5 minutes. After prebaking, in order to completely remove the solvent in the film and when the polymer contained in the liquid crystal alignment agent has a proline structure, it is subjected to a retanning (post-baking) step for the purpose of thermally imidating it. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, and -36 to 201005006 is preferably 10 to 100 minutes. The thickness of the coating film thus formed is preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm. (1 - 2) On the other hand, when manufacturing an IPS type liquid crystal display element, it is preferable to use an offset printing method, a roll coating method, a spin coating method or an inkjet printing method, and a transparent conductive film having a comb-tooth pattern is provided. Applying the liquid crystal alignment agent of the present invention to the conductive film forming surface of the substrate and the opposite substrate on which the conductive film is not provided, and then preferably heating each coated surface (prebaking and post-baking) to form a coating film. . At this time, the material of the substrate and the transparent conductive film to be used, the method of forming the transparent conductive film pattern, the pre-treatment of the substrate, the pre-baking and post-baking conditions after coating, the film thickness of the formed coating film, and the above ( 1 - 1) Same. 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 a liquid crystal alignment film by removing an organic solvent after coating, when the liquid crystal alignment agent of the present invention contains When the polymer is polylysine or a polyimine having a quinone ring structure and a guanine structure in the same state as β, it may be subjected to a dehydration ring-closure reaction by further heating after forming a coating film to form a further hydrazine. The imidized coating film. (2) The coating film formed as described above may be used as a liquid crystal alignment film for a VA liquid crystal display element as it is, or the coating film surface may be optionally subjected to the following polishing treatment. When the coating film formed as described above is used as a liquid crystal alignment film for a ruthenium type or IPS type liquid crystal display element, liquid crystal alignment is produced by polishing the surface of the coating film to produce alignment energy of liquid crystal molecules on the film of -37-201005006. membrane. The polishing treatment can be carried out by rubbing the surface of the coating film in a predetermined direction with a roll of a cloth made of a fiber such as nylon, rayon, or cotton. In addition, the liquid crystal alignment film formed as described above is, for example, Patent Document 4 (Japan) A process of irradiating a part of a liquid crystal alignment film with ultraviolet rays and changing a pretilt angle of a partial region of the liquid crystal alignment film, as shown in Japanese Laid-Open Patent Publication No. Hei 6-281-93, Or, after forming a resist film on a part of the surface of the liquid crystal alignment film, which is shown in the patent document 6 (JP-A-H05-107544), the resist film is removed in a direction different from the previous polishing process to remove the resist film. The treatment makes the liquid crystal alignment film have different liquid crystal alignment energy in each region, and can improve the field of view performance of the obtained liquid crystal display device. (3) A pair of substrates on which the liquid crystal alignment film was formed as described above was fabricated, and the two substrates were placed oppositely through the gap (cell gap) so that the polishing direction of the liquid crystal alignment film was perpendicular or antiparallel to each other. The peripheral portions of the two substrates are bonded together with a sealant, and a liquid crystal is injected into the interstitial space surrounded by the surface of the substrate and the sealant, and the injection hole is sealed to form a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell so that the polarizing direction thereof coincides with 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 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 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-38-201005006 Liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal liquid crystal, etc. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added under the trade names "C-15" and "CB-15" (manufactured by Merck). A chiral agent for sale, a ferroelectric liquid crystal such as a nonyloxybenzylidene-p-amino-2-methylbutyl cinnamate, or the like is used. The polarizer to be bonded to the outer surface of the liquid crystal may be a polarizer formed by stretching a polyvinyl alcohol and absorbing iodine to absorb iodine, and a polarizing film called a "ruthenium film" is sandwiched between the cellulose acetate protective film, or A polarizer made of the enamel itself. The liquid crystal display element of the present invention produced as described above has an advantage that the display performance does not deteriorate even if it is continuously driven for a long period of time as compared with the conventionally known liquid crystal display element, and specifically, for example, liquid crystal is not considered to occur. The backlight film is thermally deteriorated to cause backlight leakage or the like which causes a poor alignment of the liquid crystal. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. Further, the solution viscosity of the polymer in the synthesis example was measured by a Ε-type viscometer at 25 °C. <Synthesis of Compound (A)> Synthesis Example 1 (Synthesis of 2,6-diaminobenzothiazole) Synthetic starting material 2-Amino-6-nitrobenzoxazole was directly used in Tokyo Chemical Industry Co., Ltd. The product. 97.6 g (0.50 mol) of 2-amino-6-nitrobenzothiazole was dissolved in 3000 ml of ethanol, and 5 wt% of palladium/carbon 90 g was added, and the mixture was stirred at 70 ° C under a nitrogen-39-201005006 environment. hour. Then, 153 ml of hydrazine monohydrate was added, and the reaction was carried out by carrying the sample under reflux for 6 hours under a nitrogen stream. After completion of the reaction, palladium on carbon was removed by filtration through Celite, and the solvent was removed from the filtrate. The obtained solid was sufficiently washed with distilled water and then dried to give the object 2,6-diaminobenzothiazole 44.88 (54.0%). This synthesis operation was repeated in accordance with the above synthetic scheme to ensure the amount of 2,6-diaminobenzoxazole necessary for the synthesis of the following polymer. <Synthesis of Specific Polymer> Φ Synthesis Example 2 (Synthesis 1 of Polyimine) 1 , 3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) And l,3,3a,4,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]- Furan-1,3-dione 160g (0.50 mole) 'p-phenylenediamine as a diamine 84g (0.78 moles), 2,6-diaminobenzothiazole 16.5g (0.1 moles), 2, 2- bis(trifluoromethyl)-4,4-diaminobiphenyl 32g (0.10 mole) and 3,6-bis(4-aminobenzylideneoxy) bilirubin 6.4g (0.010 Mo The ear) and the aniline 2_8g (0.03 mole) as a monoamine were dissolved in 1200 g of N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C for 9 hours to obtain a polyglycine-containing solution. A small amount of the obtained polylysine solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 58 mPa·s. Then, 24 〇 Qg of NMP was added to the polylysine solution prepared above, and 400 g of pyridine and 410 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone (by the solvent replacement operation, pyridine and acetic anhydride used in the dehydration ring closure reaction of #-40-201005006 were removed to the outside of the system. The same as below]' was then concentrated to obtain about 3700 g of a solution containing 10% by weight of polyimine (PI-1) having a ruthenium iodide ratio of about 95%. The solution viscosity of the polyimine solution was 69 mPa's. Synthesis Example 3 (Synthesis 2 of Polyimine) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and 1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2·c]-furan-l,3-dione 160g ( 0.50 mole Φ ear) 'p-phenylenediamine as diamine 94g (0.87 mole), 2,6-diaminobenzothiazole 16.5g (〇.l mole), 1,3-bis(3-amine Propyl) tetramethyldioxane 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy)cholane 9.6g (0.015 moles), and as a monoamine Aniline 2.8 g (0.030 mol) was dissolved in 960 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 60 mP a·s ° © and then added to the obtained poly-proline solution. 2700 g of NMP was further added with 400 g of pyridine and 410 g of acetic anhydride, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 3 800 g of a polyimine containing 10% by weight of ruthenium iodide (about 88%). A solution of PI-2). The solution viscosity of the polyimine solution was 55 mP a·s. Synthesis Example 4 (Synthesis 3 of Polyimine) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride - 41 - 201005006 110 g (0·50 mol) and 1,3 , 3a, 4, 5, 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-one oxy-3-furanfuran-, 3_dione 16 〇g (〇5〇 Mohr) 'p-phenylenediamine as a diamine 94g (〇87 mole), 2 6-diaminobenzophthalene 16.5g (〇.i mol bis(3_aminopropyl)tetramethyl Dioxane 25g (0.10 mol) and 4_(4,_trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate 35g (〇〇8〇莫耳) And 2.8 g (0.030 mol) of aniline as a monoamine dissolved in 1271 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyglycolate solution was taken. NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 60 mPa·s. Then, 2500 g of NMP was added to the obtained poly-proline solution, and 400 g of pyridine and 410 g of acetic acid were further added. Anhydride, at 11 〇. (: 4 hours dehydration ring closure reaction. After dehydration ring closure reaction, by the solvent in the system The new γ-butyrolactone is subjected to solvent displacement and then concentrated to obtain about 3800 g of a solution containing 10% by weight of a polyimine (P1-3) having a ruthenium iodide ratio of about 96%. The viscosity of the solution was 55 mPa·s. Synthesis Example 5 (Synthesis of Polyimide 4) 110 g (0-50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride. 43 g (0.40 mol) of p-phenylenediamine as diamine, 16.5 g (0.1 mol) of 2,6-diaminobenzothiazole, and 3-(3,5-diaminobenzylideneoxy) cholesta 52 g (0.10 mol) of decane was dissolved in 830 g of NMP, and reacted at 60 ° for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added, and NMP was added to form a polypeptone. A solution having an amine acid concentration of 20% by weight, and a measured solution viscosity of 2200 mPa·s. -42 - 201005006 Then, adding 1,500 g of NMP to the obtained polyaminic acid solution, and further adding 40 g of pyridine and 51 g of acetic anhydride, 11 (4 hours of dehydration ring closure reaction under TC. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent, and then concentrated to obtain about 2700 g of 7% by weight. A solution of polyimine (PI-4) having a rate of about 50%. The solution viscosity of the polyimine solution is 30 mPai. Synthesis Example 6 (synthesis of polyimine) 5 will be used as tetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride © ll〇g (〇.5〇莫耳), p-phenylenediamine as diamine 49g (0.45mol), 2,6-diamino Benzothiazole 16.5 g (0.1 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 26 g (0.05 mol) were dissolved in 750 g of NMP for 6 hours at 6 (TC) The reaction was carried out to obtain a solution containing poly-proline. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution having a polyglycine concentration of 20% by weight, and measure the viscosity of the solution to 220 0 mP a·s » Then, add to the obtained poly-proline solution 1 800 g of NMP was further added with 40 g of pyridine and 51 g of acetic anhydride, and a dehydration β ring closure reaction was carried out for 4 hours under lure. After the dehydration ring closure reaction, a solvent of the system was replaced with a new hydrazine to obtain a solution of about 2,500 g of a polyimine (PI-5) containing 7 wt% of a ruthenium iodide ratio of about 50%. The solution viscosity of the polyimine solution was 50 mPa-s. Synthesis Example 7 (Synthesis 6 of Polyimine) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and p-phenylenediamine as a diamine 38 g (035 mol), 2,6-diaminobenzothiazole 16.5 g (0.1 mol), 4,4,-diaminodiphenylmethane•43-201005006 20g (0_l mole) and 3-( 3,5-Diaminobenzimidyloxy)cholestane 26 g (〇〇5 mol) was dissolved in 810 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was added, NMP was added to prepare a solution having a polyglycine concentration of 7% by weight, and the measured solution viscosity was 65 mPa·s. Then, 1 900 g of the obtained polyaminic acid solution was added. NMP was further added with 80 g of pyridine and 1 g of acetic anhydride, and a dehydration ring-closure reaction was carried out for 4 hours at U0 °C. After the dehydration ring closure reaction, a solvent of the system was replaced with a new ® NMP to obtain about 1 400 g of a solution containing 15% by weight of polyimine (PI-6) having a ruthenium iodide ratio of about 80%. A small amount of the solution of the brewed imine was added, and NMP was added to prepare a solution having a polyamidene concentration of 1% by weight, and the measured solution viscosity was 90 mPa*s. Synthesis Example 8 (Synthesis of Polyiminide 7) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, p-phenylenediamine as diamine 43 g (0.40 mol) and 2,6-diaminobenzothiazole 16.5 g (0.1 mol) were dissolved in l800 g of NMP, and the reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a mash having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 70 mPa*S. Then, 1800 g of NMP was added to the obtained polyamic acid solution, and 80 g of pyridine and 100 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 1200 g of a polyimine (15-7) containing 15% by weight of a ruthenium iodide ratio of about 89%. )The solution. Take less -44 - 201005006 The amount of the polyimine solution, add γ-butyrolactone, and prepare a solution with a concentration of 10% by weight of polyimine. The viscosity of the solution is determined to be 15〇111]?&.3. Synthesis Example 9 (Synthesis of Polyimine 8) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride 1658 (0.75 mol) and 1,3,33,4,5 as tetracarboxylic dianhydride , 91) _ hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene-furan, 3-dione 78g (0.25 mol) as diamine P-phenylenediamine 32g (0.30 mol), 2,6-diaminobenzothiazole 16.5 g (0.1 mol), 4,4'-diaminodiphenyl ether 80 g (0.4 mol) and {{4-(4-Aminophenoxy)phenyl}indole 85g (0.20 mol) was dissolved in 2600 g of NMP, and reacted at 6 (TC for 6 hours to obtain a polyglycine-containing solution. The obtained polyaminic acid solution was added with NMP to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 400 m P a · s ° . Then, 1 was added to the obtained poly-proline solution. 800 g of NMP, further adding 395 g of pyridine and 310 g of acetic anhydride, and performing a dehydration ring-closure reaction at llOt for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new β γ-butyrolactone solvent, followed by concentration. About 1 3 50 0g of polyethylenimine containing 15% by weight of hydrazine imidization rate of about 85% (P A solution of I - 8). A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the measured solution viscosity was 90 mPa·s. 10 (Synthesis of Polyimine 9) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride 11 〇g (0.50 mol) as 2,6-di of diamine Aminobenzothiazole 82-5 g (0.5 mol) is dissolved in 1800 g of NMP, and reacted at 60 ° C for 6 hours -45 - 201005006 to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution is obtained. NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 65 mPa_s. Then, 1800 g of NMP was added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride were added. 1 4 hours dehydration ring closure reaction at 10 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 1100 g of 15% by weight hydrazine imidization rate. A solution of about 83% polyimine (PI-9). Take a small amount of the polyimine solution and add γ-butyrolactone to form a polypeptone. A solution having an amine concentration of 10% by weight, the measured solution viscosity was 70 mP a·s. Synthesis Example 11 (synthesis of polyiminamide 10) 2,3,5-tricarboxycyclopentane as tetracarboxylic dianhydride Acetate dianhydride 11 (^ (0.50 mol), p-phenylenediamine 328 (0.30 mol) as diamine, 16.5 g (0.1 mol), 2,2' of 2,6-diaminobenzothiazole - bis(trifluoromethyl)benzene 16g (0.05 0 mole) and 4,4'-diaminodiphenylmethane 11g (〇, 〇50 mole) dissolved in 2000g NMP, carried out at 60 ° C The reaction was carried out for 6 hours to obtain a solution containing poly-proline. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution having a polyglycine concentration of 10% by weight, and measure the viscosity of the solution to 480 mPa·s °. Then, add 1800 g of NMP to the obtained poly-proline solution. Further, 126 g of pyridine and 163 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 is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 130% (containing 15% by weight of a polyamidiamine having a ruthenium iodide ratio of about 88%). ΡΙ - 1〇) solution. Take -46- 201005006 a small amount of the polyimine solution 'add γ-butyrolactone, and prepare a solution with a concentration of 10% by weight of polyimine. The solution viscosity is 35 mPa. s. <Synthesis of Other Polymers> Synthesis Example 12 (Synthesis of Other Polylysine 1) Pyromellitic dianhydride as a tetracarboxylic dianhydride 11 〇g (〇.50 mol) and 1,2 , 3,4·cyclobutane tetracarboxylic dianhydride 98 g (0.50 mol), as a diamine 4,4-diaminodiphenyl ether 200 g (l_0 mol) dissolved in 230 g NMP and 2010 g γ - In the mixed solvent of butyrolactone, the reaction was carried out for 3 hours at 401, and then 1,350 g of γ-butyrolactone was added to obtain about 3500 g of a solution containing 1% by weight of polyglycine (PA-1). The solution viscosity of the polyaminic acid solution is 2 〇〇mPa's. Synthesis Example 13 (Synthesis 2 of other polylysine) 1,2,3,4-cyclobutanetetracarboxylic acid as tetracarboxylic dianhydride Dianhydride 98g (0,50 moles) and pyromellitic dianhydride 11〇g (〇5〇莫耳), as a diamine 4'4'-aminodiphenylmethane 2〇〇g (1 〇mol) is dissolved in a mixed solvent consisting of 23〇gNMP and 210 〇g butyrolactone, and 3 hours at 40 〇C

When D was reacted, 135 〇g γ-butyrolactone was added to obtain about 35 〇〇g of a solution containing 1 〇 by weight of poly-tantoic acid (PA-2). The solution viscosity of the polyamic acid solution was 1 2 5 mP a.s. Synthesis Example 14 (Synthesis 3 of Other Polylysine) 200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 22 as a diamine Dimethyl-44, diaminobiphenyl 21 〇g (1. oxime) was dissolved in a mixed solvent consisting of 370 g of NMP and 3300 g of γ·butyrolactone, and reacted at 4 (TC for 3 hours). A solution of about 3 500 g containing -47-201005006 with 10% by weight polyglycine (PA-3) was obtained. The solution viscosity of the polyaminic acid solution was 160 mPa's. Synthesis Example 15 (Other polylysines Synthesis 4) 196 g (0.9 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 19_6 g (0-1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as diamine 21.6 g (0.20 mol) of p-phenylenediamine and 80 g (0 8 mol) of 4,4'-diaminodiphenyl ether were dissolved in 24 g of NMP and reacted at 60 ° C for 4 hours. A solution containing about 10% by weight of polyglycine (PA-4) was obtained. The solution viscosity of the poly(A) acid solution was 200 mPa.s. Synthesis Example 16 (Synthesis of Other Polyimine) 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 110g (0.50 mole) And l,3,3a,4,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-sideoxy-3-furanyl)-naphthalene [l,2-c]- Iridium-i,3-dione 160g (0.50 mole), p-phenylenediamine as a diamine 95g (0.88 moles), 2,2-bis(trifluoromethyl)-4,4-amino group Biphenyl 32g (0.10 mol) and 3,6-bis(4-aminobenzyl methoxy) choline 6.4 g (0.010 mol), and aniline as a monoamine 2.8 g (0.03 mol) Dissolved in 1 200g of NMP, and reacted at 6 (rc for 9 hours) to obtain a solution containing poly-araminic acid. Take a small amount of the obtained polyamic acid solution, add NMP, and prepare a polyglycine concentration of 1% by weight. The solution has a measured solution viscosity of 58 mPa·s. Then, 2400 g of NMP is added to the obtained polyamic acid solution, 400 g of pyridine and 41 g of acetic anhydride are further added, and a dehydration ring-closing reaction is carried out for 4 hours at 11 〇〇c. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butane vinegar into the fr solvent and then concentrated to obtain about 37 〇〇g containing 10 -48-201005006% by weight 醯 imidization rate is about 95 a solution of % polyimine (PI-n). The solution of the polyimine solution is sticky The degree is 69 mPa·s. Synthesis Example 17 (Synthesis 2 of Other Polyimine) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and i, 3,3a,4,5,9b-hexahydro-8-methyl_5-(tetrahydro-2,5-one oxy-3-furanyl)-naphthalene [i,2-c]-furan-l , 3 -dione ^ (^ (0.50 mol), p-phenylenediamine as a diamine 94 g (〇_87 mol), iota, 3 -bis(3-aminopropyl)tetramethyldioxine 25g (0.10 moles) of alkane and 9.6g (〇.015 moles) of 3,6-bis(4-aminobenzylidene® methoxy)cholane, and octadecylamine 8.1g as monoamine (0.030 mol) was dissolved in 960 g of NMP and reacted at 60 ° C for 6 hours to give a solution containing poly-proline. A small amount of the obtained polyaminic acid solution 'supplemented with NMP' was added to a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 60 mPa·s. Then, 2700 g of NMP was added to the obtained polyaminic acid solution, and 400 g of pyridine and 41 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under ii〇-C. After the dehydration ring closure reaction, a solvent of the system is replaced with a new β-butyrolactone to obtain about 2300 g of a solution containing 15% by weight of a polyamidimide (pi-12) having a ruthenium iodide ratio of about 95%. . A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a concentration of 10% by weight of polyimine. The solution viscosity was 70 mPa·s. Synthesis Example 18 (Synthesis 3 of Other Polyimine) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and 1,3,3&,4 , 5 915_hexahydro-8-methyl_5_(tetrahydro-2,5-di-oxo-3-furanylnaphthalene [He].furan-indole, 3-diketone 16〇g (〇5〇莫- 49- 201005006 Ear) 'p-phenylenediamine as a diamine 88g (0.82 mol), U3-bis(3·aminopropyl)tetramethyldioxane 25g (0_10 mol) and 4-(4 , -Trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate 34 (0.080 mol)' and aniline as a monoamine 2.8 g (0-030 mol) dissolved in 1200 g NN1P The solution 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 NMP was added to prepare a solution having a polyalginic acid concentration of 10% by weight. The viscosity is 60 mPa·s. Then, 2500 g of NMP is added to the obtained polyamic acid solution, and 40 g of pyridine and 410 g of acetic anhydride are added thereto, and the dehydration ring-closure reaction is carried out for 4 hours at ll ° C. After replacing the solvent in the system with a new butyrolactone solvent Then, it was concentrated to obtain about 3600 g of a solution containing 10% by weight of polyimine (PI-13) having a ruthenium iodide ratio of about 96%. The solution viscosity of the solution of the polyimide solution was 55 mPa·s. Synthesis of other polyimines 4) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol), p-phenylenediamine as diamine 43 g (0.40 Mo The ear) and β 3_(3,5·diaminobenzylideneoxy)cholane 52g (0.10 mol) were dissolved in 83 0 g of NMP, and reacted at 60 ° C for 6 hours to obtain polydecylamine. A solution of acid. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution with a polyglycine concentration of 10% by weight, and measure the viscosity of the solution to 60 mPa*s. Then, to the obtained poly-proline solution 1900g of NMP was added, 4 〇g of pyridinium and 5ig acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours under litre. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP to obtain about 1100 g of 15 The weight % 醯 imidization rate is about -50 - 201005006 is a 50% solution of polyimine (PI - 14). Take a small amount of the polyimine solution, add NMP, formulated as a solution having a polyamidene concentration of 10% by weight, has a solution viscosity of 47 mPai. » Synthesis Example 20 (Synthesis of Other Polyimine 5) 2, 3, 5 as Tetracarboxylic Acid dianhydride - Tricarboxycyclopentyl acetic acid dianhydride 110 g (0.50 mol), p-phenylenediamine as a diamine 49 g (0.45 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 26 g (〇.〇5 mol) was dissolved in 750 g of NMP to carry out a reaction at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the viscosity of the solution was determined to be 58 mPa-s. Then, 1800 g of NMP was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out for 4 hours at U °C. After the dehydration ring closure reaction, a solution of about 1 000 g of a polyimine (PI-15) having a ruthenium iodide ratio of about 15% was obtained by solvent-replacement of the solvent in the system with new NMP. A small amount of the solution of the glycine imine was added, and NMP was added to prepare a solution having a polyamidene concentration of 1% by weight, and the viscosity of the solution was determined to be 85 mPai. Synthesis Example 21 (Synthesis 6 of other polyimine) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 11 (^ (0.50 mol)) as a tetracarboxylic dianhydride, as a diamine of benzene Diamine 388 (〇35 mol), 4,4,-diaminodiphenylmethane 20 g (0.1 mol) and 3-(3,5-diaminobenzylideneoxy) gallone 26 g (0.05 Mol) was dissolved in 800 g of NMP, and the reaction was carried out at 60 ° for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyamic acid solution was added to NMP to form a polyglycolic acid. 1 〇% by weight of solution -51 - 201005006, the measured solution viscosity is 60 mPa_s. Then, 1 800 g of NMP is added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride are added, and the reaction is carried out at 110 ° C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new NMP solvent to obtain about 105 Og of polyfluorene (15%) containing 15% by weight of ruthenium iodide. 6) Solution: A small amount of the polyimine solution was added, NMP was added, and a solution having a concentration of 10% by weight of polyimine was prepared, and the viscosity of the solution was determined to be 87 mPa*s. 2 (Synthesis of other polyimines 7) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 54 g of p-phenylenediamine as a diamine ( 0.50 mol) dissolved in 1 800 g of NMP, and reacted 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 NMP was added to prepare a polyglycine concentration. 10% by weight of the solution, the measured solution viscosity is 75 mPa·s 6 Then, 1 800 g of NMP is added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride are added, and the mixture is subjected to 1 1 (TC for 4 hours). Dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 140 g of polyfluorene containing 15% by weight of ruthenium iodide ratio of about 91%. A solution of imine (PI-17). Take a small amount of the polyimine solution, add γ-butyrolactone, and prepare a solution with a polyamidene concentration of 10% by weight. The measured solution viscosity is 150 mP a·s. Synthesis Example 23 (Synthesis of Other Polyimine 8) 2,3,5-Tricarboxycyclopentyl Acetate dianhydride as a tetracarboxylic dianhydride - 52 - 20 1005006 165g (0.75 mole) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3·furanyl)-naphthalene 1,2_c]_furan-1,3-dione 78g (0·25 mol) 'p-phenylenediamine as diamine 43g (0.40 mol), 4,4'-diaminodiphenyl ether 80g (〇.4mol) and bis{4-(4-aminophenoxy)phenyl}milled 85g (0.20 mole) dissolved in 2600g of NMP and reacted at 60 ° C for 6 hours to give polycondensation A solution of proline. A small amount of the obtained polyaminic acid solution was taken, and NMP' was added to prepare a solution having a polyglycine concentration of 丨〇% by weight, and the measured solution viscosity was 1 〇〇 mPa.s. Then, 1 800 g of NMP was added to the obtained polyamic acid solution, and 80 g of pyridine and i〇〇g acetic anhydride were further added thereto, and a dehydration ring-closing 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 γ-butyrolactone solvent, and then concentrated to obtain about 2700 g of a polyimine (PI-containing 15% by weight of a ruthenium iodide ratio of about 81%). 18) solution. A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity was determined to be 95 mP a·s. Synthesis Example 24 (Synthesis of Other Polyimine 9) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, p-phenylenediamine as a diamine 43g (〇4〇莫耳), 2,2,_bis(difluoromethyl)benzene 16g (0.050 mol) and 4,4,-diaminodiphenylmethane 11g (0.050 mol) dissolved in 2600g NMP The reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the viscosity of the solution was determined to be 480 mPa*s. Then, 18 〇〇g of NMP was added to the obtained polyacrylic acid solution, and then -53-201005006 8 〇g of pyridine and 100 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at 11 °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 2500 g of a polyamidene containing 15% by weight of a ruthenium iodide ratio of about 88% (PI - 19) solution. A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity was determined to be 90 mPa_s. Example 1 <Preparation of Liquid Crystal Aligning Agent> φ The polyimine-containing amine (PI-2) obtained in the above Synthesis Example 3 in an amount equivalent to 20 parts by weight in terms of polyimine (PI-2) The solution is mixed with a polytyramine (PA-1)-containing solution prepared in the above Synthesis Example 12 in an amount equivalent to 80 parts by weight in terms of polyglycine (PA-1), to γ-butyl Lactone: Ν-methyl-2-pyrrolidone: butyl cellosolve ratio of 71: 17: 12 by weight, to which γ-butyrolactone, Ν-methyl-2-pyrrolidone and butyl cellosolve were added, and Adding 2 parts by weight of an epoxy compound Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane as an adhesion enhancer to a solid content of 3.5% by weight solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was used for evaluation as follows. <Manufacturing and Evaluation of Liquid Crystal Display Element> [Production of Liquid Crystal Display Element] (1) Application of Liquid Crystal Aligning Agent and Formation of Liquid Crystal Alignment Film Using a spin coater at a rotation speed of 2000 rpm and a rotation time of 20 seconds Next, the above-prepared liquid crystal alignment agent is applied onto a transparent conductive film of ITQ film provided on one surface of a glass substrate having a thickness of 1 mm -54 to 201005006, and prebaked on a hot plate at 8 ° C for 1 minute, and then After baking at 20 ° C for 1 hour, a coating film having a film thickness of 0.08 μη was formed. (2) Grinding treatment The above coating film was carried out under the conditions of a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a pile extrusion length of 0.4 mm, using a grinding machine equipped with a roller wound with a rayon cloth. The polishing treatment is performed to produce a liquid crystal alignment energy on the coating film to form a liquid crystal alignment film. © (3) Washing and drying of the substrate coated with the liquid crystal alignment film The substrate having the liquid crystal alignment film prepared above was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. . The same operation was repeated to produce two (a pair of) substrates having a liquid crystal alignment film. (4) Liquid crystal injection step, bonding and bonding of the polarizer, and then a ring of alumina balls having a diameter of 5.5 μm is applied to each of the outer edges of the pair of liquid crystal alignment films having the liquid crystal alignment film. After the oxy-resin adhesive, the liquid crystal alignment film surface is relatively heavily combined and pressed, and β is used to cure the adhesive. Next, a liquid crystal injection port is used to fill a liquid crystal injection port with a dielectric-curable anisotropic liquid crystal (manufactured by Merck, MLC-622 1). The film was sealed, and a polarizing plate was bonded to both surfaces of the substrate to produce a liquid crystal display element. [Evaluation of Liquid Crystal Display Element] (1) Evaluation of liquid crystal alignment property The liquid crystal display element manufactured above was observed with an optical microscope. In this case, when there is no light leakage, the liquid crystal alignment property is evaluated as "good". When it was confirmed that there was light leakage, the liquid crystal alignment property was evaluated as "poor". The liquid crystal alignment property of the liquid crystal display element was "good". (2) Evaluation of heat resistance (heat stress test) For the liquid crystal display element manufactured above, first, a voltage of 5 V was applied for a time span of 167 msec, the application time was 60 μsec, and then the voltage was released until after 167 msec. Voltage retention rate. The number 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 was determined. When the rate of change was less than 5%, the heat resistance was evaluated as "good", and the heat resistance was evaluated as "poor". The heat resistance of the liquid crystal display element was "good". (Examples 2 to 5) In the same manner as in Example 1, except that the polymer of the type ® shown in Table 1 shown in Table 1 was used, the liquid crystal alignment agent was prepared, and a liquid crystal display element was produced. Evaluation. The results are shown in Table 2. Example 6 <Preparation of Liquid Crystal Aligning Agent> The polyimidazole (PI - 4 ) prepared in the above Synthesis Example 5 in an amount equivalent to 100 parts by weight in terms of polyimine (PI-4) was used. a solution in which N-methyl-2-pyrrolidone and butyl cellosolve are added in a weight ratio of N-methyl-2-pyrrolidone:butyl cellosolve of 50:50, and 2 parts by weight are added thereto - 56- 201005006 The epoxy compound n, n, n', n'-tetraglycidyl-4,4'-diaminodiphenylmethane, which is a binder enhancer, is formulated to have a solid content concentration of 3.5% by weight. The solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size to prepare a liquid crystal alignment agent. <Production and Evaluation of Liquid Crystal Display Element> As a liquid crystal, a nematic liquid crystal (manufactured by Merck & Co. 'MLC-2038)' which exhibits a negative dielectric anisotropy is used and a manufacturing step of a liquid crystal display element In the same manner as in the first example, the liquid crystal display element was produced and evaluated for liquid crystal alignment and heat resistance. The results are shown in Table 2, except that the polishing treatment was carried out in the same manner as in Example 1. Examples 7 and 8 In the same manner as in Example 6, except that the polymer of the type shown in Table 1 shown in Table 1 was used, the liquid crystal alignment agent was separately prepared, and a liquid crystal display element was produced and evaluated. . The results are shown in Table 2. Example 9 <Preparation of Liquid Crystal Aligning Agent> ® Polyimine-containing amine (PI-7) obtained in Synthesis Example 8 in an amount equivalent to 100 parts by weight in terms of polyimine (PI-7) a solution to which 1 part by weight of an epoxy compound Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane and 0.75 by weight as a binder enhancer are added. a functional decane compound 3-[2-(3-trimethoxydecylpropylamino)ethylamino]propyl propionate, then a ratio of γ-butyrolactone:butyl cellosolve of 80:20 The weight ratio was added to γ-butyrolactone and butyl cellosolve to prepare a solution having a solid content concentration of 3.5% by weight. The solution was filtered through a filter having a pore size of Ιμπι to prepare a liquid crystal alignment agent of -57 to 201005006. <Production and Evaluation of Liquid Crystal Display Device> The liquid crystal display device is a nematic liquid crystal (manufactured by Merck & Co., MLC-2019) having a positive dielectric anisotropy, and is the same as in the first embodiment. The liquid crystal display element was produced and evaluated for liquid crystal alignment and heat resistance. The results are shown in Table 2. Example 1 0 and 1 1 In the same manner as in Example 9, except that the polymer of the type 〇 shown in Table 1 shown in Table 1 was used, respectively, a liquid crystal alignment agent was prepared to produce a liquid crystal display element. And evaluate. The results are shown in Table 2. Example 1 2 <Preparation of Liquid Crystal Aligning Agent> The polyimine-containing amine (PI - 10 ) prepared in the above Synthesis Example 11 in an amount equivalent to 40 parts by weight in terms of polyimine (P1-10) The solution is mixed with a polyglycine (PA-4)-containing solution prepared in the above Synthesis Example 15 in an amount equivalent to 60 parts by weight in terms of poly-proline (PA-4). Lactone: Ν-methyl-2-pyrrolidone: butyl cellosolve ratio of 40:40:20 by weight, to which γ-butyrolactone, Ν·methyl-2-pyrrolidone and butyl cellosolve are added. An additional 1 part by weight of an epoxy compound Ν, Ν, Ν, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane as a binder enhancer is added to a solid content concentration of 3.5% by weight solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was used for evaluation as follows. <Production and Evaluation of Liquid Crystal Display Element> -58-201005006 As a liquid crystal, a nematic liquid crystal (manufactured by Merck, MLC-2019) which exhibits positive dielectric anisotropy is used as a liquid crystal, and In the same manner as in Example 1, a liquid crystal display device was produced, and liquid crystal alignment properties and heat resistance were evaluated. The results are shown in Table 2. Comparative Examples 1 to 5 A liquid crystal display element was prepared and evaluated in the same manner as in Example i except that the polymer of the type shown in Table 1 shown in Table 1 was used. The results are shown in Table 2. Φ Comparative Examples 6 to 8 In the same manner as in Example 6, except that the polymer of the type shown in Table 1 shown in Table 1 was used, a liquid crystal alignment agent was prepared, and a liquid crystal display element was produced. Evaluation. The results are shown in Table 2. Comparative Examples 9 and 10 In the same manner as in Example 9, except that the polymer of the type shown in Table 1 shown in Table 1 was used, respectively, a liquid crystal alignment agent was prepared, and a liquid crystal display element was produced and carried out. Evaluation. The results are shown in Table 2. ® Comparative Example 1 1 A liquid crystal display element was produced by preparing a liquid crystal alignment agent in the same manner as in Example 12 except that the polymer of the type shown in Table 1 shown in Table 1 was used. Evaluation. The results are shown in Table 2. -59- 201005006 ❹ο £ 隐mg 隐(军最%) CS rj cs CN ΓΊ Μ 2 i (窜晕%) r-· 卜r- Ο Ο 〇ο r- r- ι> !- 〇Ο 〇j PQ (窜%%) ι«·Η iH Ο Ο Ο fH fH 〇〇〇S !〇SM to mg im $ __ Μ o Ο ooo ο ο ο 0.75 0.75 0.75 ο Ο oo Ο Ο 〇〇〇 0.75 0.75 Ο 1 1 1 1 幽 III MSPP MSPP MSPP I 1 1 1 I 1 1 1 1 MSPP MSPP I 松 4n § __ thtrtl 啊<N CN CS <S o Ο Ο Ο ο ο ο Ο (S CN CS <S Ο 〇 〇〇〇ο Ο m tips mm GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM <jn 趦狴mms __ tlmll full Ο ο ο ο Ο ο § 〇〇 ο ο m tltnll w PA-l PA-2 PA-3 PA-3 PA-3 I Yi III 1 PA-4 PA-l PA-2 PA-3 PA-3 PA-3 1 1 1 II PA-4 Nu K ϋ s ΦΜ 〇mi pit Ο ο Ο Ο Ο ο ο — o 〇〇〇Ο Ο ο κη Type PI-2 PI-2 PI-1 PI-2 PI-3 ΡΙ-4 ΡΙ-5 ΡΙ-6 ΡΙ -7 PI-8 PI-9 PI-10 PI-12 PI-12 PI-11 PI-12 PI-13 PI-14 PI-15 PI-16 PI-17 PI-18 PI-19 I Example 1 | Example 2 I Example 3 | Example 4 | Example 5 1 Example丨 丨 Example 7 丨 Example 8 丨 Example 9 1 Example 10 1 Example li Example I m 丨 Comparative Example 1 Comparative Example 2 丨 Comparative Example 3 | Comparative Example 4 Comparative Example 5 丨 Comparative Example 6 Comparative Example 7 Comparison Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 -09- 201005006 Reference Table 2 Liquid Crystal Display Element Liquid Crystal Liquid Crystal Alignment Heat Resistance Liquid Crystal Name Dielectric Anisotropy Example 1 6221 Positive Good Example 2 6221 Good and good Example 3 6221 just good good example 4 6221 positive good good example 5 6221 positive good good example 6 2038 negative good good example 7 2038 negative good good example 8 2038 negative good good example 9 2019 positive good implementation Example 10 2019 Positive good Example 11 2019 Positive good Example 12 2019 Positive good Good Comparative Example 1 6221 Positive good bad Comparative Example 2 6221 Positive good bad Comparative Example 3 6221 Positive good bad ratio Example 4 6221 Positive Good Defects Comparative Example 5 6221 Positive Good Defects Comparative Example 6 2038 Negative Good Defects Comparative Example 7 2038 Negative Good Defects Comparative Example 8 2038 Negative Good Defects Comparative Example 9 2019 Positive Good Defects Comparative Example 10 2019 Positive Good Defects Comparative Example 11 2019 It is good and bad. In addition, the "type" column and the solvent group of the adhesion enhancer in Table 1 are respectively referred to as the following meanings. -61 - 201005006 <Adhesion enhancer> Epoxy compound GAPM: 1^,:^,:^',:^'-tetraglycidyl-4,4'-diaminodiphenyltoluene function The decane compound MSPP: 3-[2-(3-trimethoxydecylpropylamino)ethylamino]methyl propionate <solvent composition> β BL : γ-butyrolactone NMP : Ν- Methyl-2-pyrrolidone BC : butyl cellosolve In addition, the contents described in the column of "liquid crystal name" in Table 2 have the following meanings. 6221 : MLC-6221 (trade name, manufactured by Merck) 2 03 8: MLC-203 8 (trade name, produced by Merck) 2019: MLC-2019 (trade name, produced by Merck) θ [Target] 4rrt No 0 [Main component symbol description] Sister" j\w -62-

Claims (1)

201005006 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of polyamic acid and polyimine, wherein at least a part of the molecules of the above polymer Has the following formula (A) The structure represented. 2. The liquid crystal alignment agent of claim 1, wherein the structure represented by the above formula (A) is selected from the group consisting of structures represented by the following formulas (A-1) to (A-3). At least one structure, (R")n Ra in the formula (A-1) is a halogen atom, a cyano group, an isocyano group, -OCN, -NCO, -SCN, -NCS or an azide group, and η is an integer of 0 to 3, each represented by a linkage; 1^ and Re in the formulas (Α-2) and (Α-3) are each independently hydrogen-63-201005006, halogen atom, amino group, isocyano group, -〇CN, -NC0, _SCN, -NCS Or an azide group, each represented as a linkage. 3. The liquid crystal alignment agent of claim 1 or 2 wherein the above polymerization product is at least one polymer selected from the group consisting of: the group consists of tetracarboxylic dianhydride and The polyamine acid obtained by reacting the diamine of the compound of the above formula (A) with the diamine of the compound of the two amine groups, and the polyimine obtained by dehydrating and ring-closing the polyamine. 4. The liquid crystal alignment agent of claim 3, wherein the compound having the structure represented by the above formula (A) 和 and the two amine groups is selected from the following formula (A-1- 1), (A-2) - 1) and at least one of the group consisting of the compounds represented by (A - 3 - 1), In the formula (A-1 to 1), "^ and η are respectively the same as defined in the above formula (A-1), and Ya is a single bond or an extended aryl group having 6 to 1 carbon atoms; -64 - 201005006 Rb and Rc in the formulae (A - 2 - 1) and (A - 3 - 1) are the same as defined in the above formula (A-2) or (A-3), respectively, Yb and γ. Each is independently a single bond or an extended aryl group having 6 to 1 carbon atoms. 5. The liquid crystal alignment agent according to claim 3, wherein the diamine further contains a compound represented by the following formula (D - in), h2n (D-III) ' In the formula (D-III), 'R9 is -0-, -COO-*'-OCO-*, -NHCO-*, -CONH·* or -CO-, of which, in the above, A linkage having "a linkage to RlG, R1 (> is a monovalent having a skeleton or group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trimethylmethoxyphenyl group, and a fluorophenyl group) The organic group 'or an alkyl group having 6 to 3 carbon atoms, Rii is a fluorenyl group having 1 to 4 carbon atoms, and a3 is an integer of 〇 to 3. 6. Liquid crystal alignment according to item 5 of the patent application And R9 in the above formula (D-III) is -〇· or -COO-*, wherein a linkage bond with "*," is linked to ® R10, and R1g is a monovalent organic group having a steroid skeleton 7. The liquid crystal alignment agent according to any one of claims 3 to 6, wherein the diamine further contains a selected from the group consisting of p-phenylenediamine, 4,4,-diaminodiphenyl-based, 4, 4 At least one of the group consisting of 'diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl] mill. 8. As claimed in any of claims 3 to 7. Liquid crystal alignment agent, wherein the tetracethopic acid dihepatic contains a tetracarboxylic acid selected from the group consisting of 12,34-cyclobutane tetracarboxylate Dihydride, 2,3,5-dicarboxycyclopentyl acetic acid dianhydride, 13,3&,45,9 hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3 -furanyl)-naphthalene [nc]-furan-i,3-dione-65-201005006, and at least one of the group consisting of pyromellitic dianhydride. 9. A liquid crystal display element characterized by having A liquid crystal alignment film formed of a liquid crystal alignment agent according to any one of claims 1 to 8. -66- 201005006 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❿