TW200948860A - Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Abstract

Provided is a liquid-crystal alignment material capable of giving a liquid-crystal alignment film which has a high voltage retention and which, even after having been exposed to a high-temperature atmosphere over long, is reduced in residual charge accumulated by direct-current voltage. Also provided is a liquid-crystal display element employing the liquid-crystal alignment film. The liquid-crystal alignment material comprises a copolymer obtained by reacting a diamine ingredient comprising at least one diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride. Diamine compound (A): at least one compound selected from the group consisting of compounds of the formulae [T1], [T2], and [T3], which are diamine compounds having a tertiary nitrogen atom. Diamine compound (B): a diamine compound having a carboxy group in the molecule. (Chemical formula 1) [T1] [T2] [T3] (In the formulae [T1] to [T3], W1 is a benzene ring or nitrogenous aromatic heterocycle; W2 is an aromatic group having 6 to 15 carbon atoms and having one or two benzene rings; W3 is C2-5 alkylene or biphenylene; W4 is cycloalkylene having 4 to 6 carbon atoms and substituted by a tertiary nitrogen atom; W5 is C2-5 alkylene; Z1 is amino substituted by two C1-6 aliphatic groups when W1 is a benzene ring, or Z1 is hydrogen or amino substituted by two C1-6 aliphatic groups when W1 is a nitrogenous aromatic heterocycle; Z2 is C1-5 alkyl or a benzene ring; and g is an integer of 0 or 1.)

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] At present, the liquid crystal alignment film of the liquid crystal display element mainly uses a liquid crystal alignment agent which is mainly composed of a solution of a polyfluorene imine or the like of polyφ lysine or a soluble polyimine (also referred to as a liquid crystal alignment agent). A liquid crystal alignment agent is a so-called polyimine-based liquid crystal alignment film which is applied onto a glass substrate and fired. The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, with the high refinement of the liquid crystal display element, the suppression of the contrast reduction of the liquid crystal display element or the reduction of the residual image development requires the voltage maintenance ratio to be increased in the liquid crystal alignment film to be used, or the residual charge is reduced when a DC voltage is applied. , and / or early mitigation of the residual Ο charge due to DC voltage characteristics have gradually become important. In the polyimine-based liquid crystal alignment film, as long as the time until the afterimage disappears due to the DC voltage is shortened, it is known to use a polyglycine other than the polyaminic acid or the phthalimide. A liquid crystal alignment agent of a tertiary amine having a specific structure (for example, refer to Patent Document 1), or a liquid crystal alignment agent using a soluble polyimine of a specific diamine having an acridine skeleton or the like as a raw material (for example, refer to Patent Document 2) ). In addition, as a result of shortening the time until the residual voltage due to the DC voltage is high and the voltage retention rate is high, it is known to use a very small amount of -5- except for polyacrylic acid or its ruthenium iodide polymer. 200948860 A liquid crystal alignment agent containing a compound having one carboxyl group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one compound of a tertiary amino group in the molecule (for example, see Patent Document 3). However, in recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements for such applications are more demanding than the remaining ones in comparison with display applications that have mainly displayed characters or still pictures. It is demanding and requires long-term use in an environment of excessively harsh use. Accordingly, the liquid crystal alignment film used also requires higher reliability than in the past, and the electrical characteristics of the liquid crystal alignment film not only require good initial characteristics, but also require, for example, long-term exposure even at high temperatures. Maintain good characteristics. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 8- No. Hei. No. Hei. . That is, the problem to be solved by the present invention is to provide a liquid crystal alignment of a liquid crystal alignment film which can obtain a high voltage holding ratio and which has only a small amount of residual electric charge accumulated by a DC voltage even when exposed to a high temperature for a long period of time. Agent. Further, the present invention provides a liquid crystal display element which is highly resistant to long-term use in a severe use environment. The inventors of the present invention have found in order to achieve the above objective, and have found a liquid crystal alignment agent which can achieve the object. The present invention is based on the result -6 - 200948860, which has the following features. (1) A liquid crystal alignment agent containing a copolymer obtained by reacting a diamine component of a diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride. Diamine compound (A): a compound of at least one selected from the group consisting of the formula [T1] 'Formula [T2] and the formula [T3] of a diamine compound having a tertiary nitrogen atom, a diamine compound (B): a diamine compound having a carboxyl group in the molecule, [Chemical Formula 1]

(In the formula [T1] to the formula [T3], 'Wi is a benzene ring or a nitrogen-containing aromatic hetero ring, and W2 is an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, W3 is a 2 to 5 carbon alkyl or biphenylene, w4 is a 4- to 6-membered cycloalkyl group which may be substituted by a 3 fluorene nitrogen atom, and W5 is a C 2 to 5 alkyl group, Z. In the case where Wi is a benzene ring, a disubstituted amine group having a carbon number of 1 to 6 which may be substituted by an aliphatic group, and a case where a nitrogen-containing aromatic heterocyclic ring is used may be a hydrogen atom or a carbon number. A disubstituted amino group substituted with an aliphatic group of 1 to 6, Z2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and g is an integer of 0 or 1. (2) The liquid crystal alignment agent according to the above (1), wherein the diamine compound (A) is a compound represented by the following formula [1] to formula [4]. 200948860

(Formula Π] to [4] where 'Al is a nitrogen-containing aromatic heterocyclic ring' A2 is an aromatic group having 6 to 15 carbon atoms' and having 1 to 2 benzene rings 'A3 is a carbon number 2 to 5 The alkyl group or the biphenylene group, A* is a group represented by the formula [4 a] or the formula [4b], As is a base group having a carbon number of 2 to 5, and Υ is an aliphatic group having 1 to 6 carbon atoms. The disubstituted amine group substituted by a group, Y2 is a phenyl or a benzene ring having a carbon number of 1 to 5, and k is an anthracene or an integer of 1). (3) The liquid crystal alignment agent according to the above (2), wherein the diamine compound (A) is a formula or a formula [2]. (4) The liquid crystal alignment agent according to the above (2), wherein A2 of the formula [3] is a benzene ring or the following formula [3a], [:3]

P -0 [3 a] (In the formula [3 a], P is a bond group selected from a single bond, -〇-, -NH-, a methyl group, and a fluorenyl group). The liquid crystal alignment agent according to the above (1) or (2), wherein the 'monoamine compound (A) is selected from the group consisting of the following formulas [5] to [18]. At least one diamine compound, [4] [5] [6] [7] [8]

[17] [18] 200948860 (in the formula [13], m and η are integers from 1 to 11 respectively] m + n is an integer from 2 to 12, and in the formula [15], j is an integer from 〇 to 3, In [18], h is an integer from 1 to 5.) (6) The liquid crystal alignment agent according to any one of the above (1), wherein the 'diamine compound (B) is a diamine compound represented by the following formula [19]. (fOOH)n i Cl 9] /Xi, Η/ ΝΗ2 (In the formula [19], Χι is an organic group having an aromatic ring of 6 to 30 carbon atoms, and η is an integer of 1 to 4). (7) The liquid crystal alignment agent according to the above (6), wherein the diamine compound (Β) is a diamine compound selected from the following formula [20] to formula [24].

200948860 (in the formula [2 0], ml is an integer from 1 to 4, and in the formula [21], X2 is a single bond, -CH2·, -C2ί^4", _C(CH3)2, -CF2, -C( CF3)2_,-0_, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, OCH2-, -COO-, -OCO-, -CON(CH3) -, or _N(CH3)CO·, m2, m3, S!l is an integer from 〇 to 4, and m2 + m3 represents an integer from 1 to 4, and in the formula [22], m4 and m5 are 1 to 5, respectively. An integer, in the formula [23], 0 X3 is a linear or branched alkyl group having 1 to 5 carbon atoms, m6 is an integer of 1 to 5, and in the formula [24], X4 is a single bond, -CH2-, - C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -〇-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, m7 is an integer from 1 to 4. (8) The liquid crystal alignment agent according to the above (7), wherein, in the formula [20], ml is an integer of from 1 to 2. (9) The liquid crystal alignment agent according to (7) above, wherein, in the formula [21] ,, x2 is a single bond, -(:112-, -(:2114-, -(:((:113)2-) , -0-, -(:0-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, or -OCO-, m2, m3 are integers of 1 at the same time. 0) The liquid crystal alignment agent according to the above (7), wherein, in the formula [24], a single bond, -CH2-, -0-, -CO-, -ΝΗ-, -CONH-, -NHCO-, - A liquid crystal alignment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment agent of any one of the above-mentioned (1), wherein The content of the diamine compound (B) in the diamine component is -11 - 200948860, which is 0.01 to 99 moles per mole of the diamine compound (A) (12) as described above (1) to (11) above. The liquid crystal alignment agent according to any one of the above (1) to (12) above, wherein the solvent is contained in the liquid crystal alignment agent, and 5 to 80% by mass is a weak solvent. The liquid crystal alignment agent described above, wherein the copolymer in the liquid crystal alignment agent is a polyimine obtained by dehydration ring closure of polyamic acid. (14) A liquid crystal alignment film, The liquid crystal display device of the above (1), which is obtained by the liquid crystal alignment device of the above (14). The liquid crystal alignment treatment agent of the invention can be obtained by a relatively simple method, and the liquid crystal alignment agent of the invention can obtain a high voltage retention ratio, and even when exposed to a high temperature for a long time, only a small amount is accumulated due to a DC voltage. A liquid crystal alignment film having a residual charge. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has excellent reliability, and is highly suitable for use in a large-screen and high-definition liquid crystal television. BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a liquid crystal alignment agent containing a copolymer obtained by reacting a diamine component containing a diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride, using the liquid crystal alignment. A liquid crystal alignment film obtained by the agent and a liquid crystal display element having the liquid crystal alignment film. -12- 200948860 <Diamine component> Diamine compound (A) used in the present invention And a diamine compound having a nitrogen atom of the formula 3 represented by the formula [T1] to the formula [T3]. The nitrogen atom of the third stage in the present invention means that the three bonding bonds of the nitrogen atom are atoms other than the hydrogen atom. Preferably, it is a nitrogen atom bonded to a carbon atom. The nitrogen atom of the diamine compound (A) used in the present invention has a function of hopping-site due to its conjugate structure. In the liquid crystal alignment film, the movement of charges can be promoted. Further, the above-mentioned three-stage nitrogen atom is bonded to the carboxyl group of the diamine compound (B) in its molecule via an electrostatic interaction forming a salt or a hydrogen bond, and causes a charge between the nitrogen atom of the third-order atom and the carboxyl group. Move. Therefore, the accumulated charge can be efficiently moved in the molecule and between molecules of the copolymer. In other words, when the liquid crystal alignment agent of the present invention is used as a liquid crystal alignment film, a liquid crystal having a high voltage holding ratio and having a residual charge accumulated by a DC voltage even when exposed to a high temperature for a long period of time can be obtained. Alignment film [diamine compound (A)] The diamine compound (A) used in the present invention is at least one selected from the group consisting of the following formula [T1], formula [T2], and formula [T3]. The compound is a diamine compound having a nitrogen atom of a 3-stage. -13- 200948860 [化9]

[Ding 1]

In the formula [T1] to the formula [T3], W! is a benzene ring or a nitrogen-containing aromatic heterocyclic ring 'W2 is an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W3 is carbon a number of 2 to 5 alkyl or phenyl, W4 is a ring alkyl group having 4 to 6 carbon atoms which may be substituted by a nitrogen atom of 3, and a alkyl group having 2 to 5 carbon atoms, Zi is When Wi is a benzene ring, it is a disubstituted amino group having 1 to 6 carbon atoms which may be substituted by an aliphatic group, and in the case of a nitrogen-containing aromatic heterocyclic ring, it may be a hydrogen atom or a fat having 1 to 6 carbon atoms. A disubstituted amino group substituted with a group, Z2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and g is an integer of 〇 or 1. Among the diamine compounds represented by the formula [T1] to the formula [T3], preferred compounds are, for example, the diamine compounds of the following formulas [1] to [4]. [化10] h2n

Cl]

[2] H2N'2, l)l/A3, N^-A2, NH2 [3] h2n

H2 [4] [4a] [4b] In the formula [4], A! is a nitrogen-containing aromatic heterocyclic ring, and A2 has 6 to 14-200948860 to 15 carbon atoms and has 1 to 2 The aromatic group 'A3 of the benzene ring is an alkylene group or a biphenylene group having a carbon number of 2 to 5, and a4 is a group represented by the formula [4a] or the formula [4b]. A5 is an alkylene group having 2 to 5 carbon atoms. Yi contains an aliphatic group having 2 to 12 carbon atoms of a nitrogen atom of 3, Y 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and k is an integer of 0 or 1. The oxime in the formula [1] is a nitrogen-containing aromatic heterocyclic ring, specifically, for example, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, and a pyridyl group. Oxazoline ring, oxazole ring, anthracene ring, thiadiazole ring, hydrazine ring, pyrazoline ring, three-till ring, pyrazolidine ring, triazole ring, piperidine ring, benzimidazole ring, benzimidazole Ring, thienoline ring, phenanthroline ring, anthracene ring, quinolino ring, benzothiazole ring, phenothiline ring, oxadiazole ring and acridine ring, more preferably pyrrole ring, imidazole ring, oxazole a ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, and more preferably a pyrrole ring, an imidazole ring, a oxacyclic ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline. ring. Specific Examples Examples are diamine compounds of the following formula [5] to formula π2].

[化11]

[5] [6] [7] [8]

200948860 The formula in the formula [2] is an aliphatic group, and a specific preferred amine compound. a lipid having a carbon number of 2 to 12 containing a nitrogen atom of 3, and a formula such as the following formula [丨3] or [14] [Chemical 12]

[13] A2 in the formula [3] is an aromatic group having a benzene ring, and A γ2 is an alkane of a carbon number of 1 to 5, and A2 in the formula [3] is more than [Chemical 13] 〇- [3a] Where p is the bonding group selected by the group. Preferred in the formula [3] is an amine compound.

3 is an alkylene group having a carbon number of 2 to 5 or a phenyl group or a benzene ring, and k is an integer of 1 or 1. It is preferably a stupid ring or a structure represented by the formula [3 a]. [3 a]

Single bond, _〇·, -NH-, methyl group, and guanamine, such as the following formula [15] to [17] bis -16 - 200948860 [Chem. 14]

H2 h2n

H2 In the formula [13], m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, and in the formula [15], j is an integer of 0 to 3. In the formula [4], A4 is a group represented by the formula [4a] or the formula [4b], and A5 is an alkylene group having 2 to 5 carbon atoms. A preferred embodiment of the formula [4] is a diamine compound of the following formula [18].

In the formula [18], h is an integer of 1 to 5. In the present invention, the diamine compound (A) may be used singly or in combination of plural kinds. [Diamine compound (B)] The diamine compound (B) used in the present invention has a diamine compound having a carboxyl group of -17-200948860 in its molecule. The specific structure thereof is not particularly limited, and is preferably a compound represented by the formula [2]. [化16] Ρη [19]

HgN' NH2 In the formula [19], X! is an organic group having an aromatic ring having 6 to 30 carbon atoms, and η is an integer of 1 to 4. The preferred structure of the formula [19] can be exemplified by the structures of the following formulas [20] to [24]. [Chem. 17]

2 CO〇H)mi

(CH2)m4CO〇H

(CH2)m5COOH [2 2] [2 0]

H2 In the formula [20], 'ml is an integer from 1 to 4' in the formula [21], χ2 is a single bond '-CH2-'-C2H4-'-C(CH3)2-. -CF2-^-C(CF3 ) 2- ' -Ο- ' -CO-, -ΝΗ-, -N(CH3)_, -CONH-, -NHCO-, _Ch2〇-, -OCH2- > -COO- ' -OCO- . -C 〇N(CH3)- - ^-N(CH3)CO-- m2 and m3 are integers from 〇 to 4, respectively, and m2+m3 represents an integer from 1 to 4 to -18-200948860, in the formula [22], m4 and M5 is an integer of 1 to 5, respectively, and in the formula [23], X3 is a linear or branched alkyl group having 1 to 5 carbon atoms, m6 is an integer of 1 to 5, and in the formula [24], X4 is a single bond, -CH2-, -C2H4·, -C(CH3)2-, -CF^- '-C(CF3)2-, -〇·, -CO-, -NH-, -N(CH3)-, -CONH -, -NHCO-, -CH2〇-, -OCH2-, -COO·, -OCO-, -CON(CH3)-, or -N(CH3)CO-, m7 is an integer from 1 to 4.

Preferably, in the formula [20], ml is an integer structure of 1 to 2, and in the formula [2 1 , X2 is a single bond, -CH2-, -C2H4·, -C(CH3)2-, -0- , -CO-, -NH-, -N(CH3)-, -CONH-...NHCO-, -COO-, or -OCO-, m2 and m3 are both an integer integer structure, in the formula [24], x

Is a single bond, -CH2-, -Ο-, -CO-, -NH-, -CONH-, .NiiCO integer -CH2O-, -OCH2-, -COO-, or -OCO-, m7 is 1 to structure. Among them, the structure represented by the formula [20] is the best. Specific examples are exemplified by the compounds of [35] to [35] of the formula [25].

[27] [2 8]

[3 3] H〇〇c

〇〇H -19- [31] 200948860 [Chem. 19]

H2

COOH

[34] ih2 In the formula [34], 'X5 is a single bond, -CH2-, -0-, -CO-, -NH-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO- , or -OCO-, in the formula [35], X6 is a single bond, -CH2-, -0-, -CO-, -NH·, -CONH-, -NHCO-, -CH20-, -〇CH2-, -COO-, or -OCO-. [Other diamine compound] In the present invention, other diamine compounds other than the diamine compound (A) and the diamine compound (B) may be used as a diamine component in a range which does not impair the effects of the present invention. Specifically, it is shown below. p-Toluenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl Base-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diamine Phenolic, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoisoxoxyl, 4,4'-diaminobiphenyl, 3 , 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4, 4'-Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4' -diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl-20- 200948860 methyl, 2,2'-diaminodiphenylmethane, 2,3' -diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2, 2'-Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis ( 4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diamino Diphenylamine, 3,3'-diamine φ-diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'- Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene , 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-di Amino naphthalene, 1,8-diaminonaphthalene, 2,5-diamidinonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1.2- double (4_ Phenyl) ethane, 1,2-bis(3-aminophenyl)ethane, 1.3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane , 1.4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, I,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3 - bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1 , 4-phenylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, -21 - 200948860 3,4'-[1 , 4-phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-stretch Phenylbis(methylene)]diphenylamine, 3,3'·[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminobenzene) Methane], 1,4-phenylene bis[(3-aminophenyl)methane], 1,3-phenylene bis[(4-aminophenyl)methane], 1,3-stretch Phenyl bis[(3-aminophenyl)methane], 1,4- Phenyl bis(4-aminobenzoate), :l,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoic acid) Ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)-p-phenylene Formate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, 1^^'-(1,4-phenylene) Bis(4-Aminobenzylamine), hydrazine, Ν'-(1,3-phenylene)bis(4-aminobenzylamine), hydrazine, Ν'- (1,4-phenylene) Bis(3-aminobenzamide), hydrazine, Ν'-(1,3-phenylene)bis(3-aminobenzylamine), hydrazine, Ν'-(4-aminophenyl) pair Benzoguanamine, hydrazine, Ν'-(3-aminophenyl)-p-xylyleneamine, hydrazine, Ν'-(4-aminophenyl)m-xylyleneamine, hydrazine, hydrazine - (3-Aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene , 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 '-bis(4-amino group Phenyl) hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2, 2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane , 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, I,4-bis(4-aminophenoxy)butane-22 - 200948860 Alkane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenyl)pentane, 1,5-bis(3-aminophenoxy) Pentane, 1,6-bis(4, oxalyl)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-phenoxy) heptane, 1, 7_bis(3-aminophenoxy)heptane, 4 amine, 8 - $(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy) & ^ Alkane, stupid (3-indolyl), 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminobenzene), 1,10-double (4-Aminophenoxy)decane, 1,10-bis(3-aminopentyl)decane, 1,11-bis(4-aminophenoxy)undecane, l, U, _ Aminophenoxy Undecane, 1,12-bis(4-aminophenoxy)decene, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexane, bis(4) -amino-3-methylcyclohexyl)methane, 1,3-diamine, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino约余!, 7. Diamino heptane, 1,8-diaminooctane, 1,9-diaminodecane,], 10, diaminodecane, 1,11.diamine Further, it may be exemplified that the diamine has an alkyl group, a fluorine-containing oxime ring, an aliphatic ring, a heterocyclic ring, and the like, in the side chain of the diamine. Specifically, the diamine compound represented by the following formula [DA1] to formula [DA26] can be exemplified as the diamine of the large-sized base. [20] h2n

H2 h2n [DAI] [DA2] [DA3]

[DA4]

[DA 5] (In the formula [DAI] to the formula [DA5], Ri is a -23-200948860 alkyl group or a fluorine-containing alkyl group having a carbon number of 1 or more and 22 or less. [21] h2n

H2

(In the formula [DA6] to the formula [DA9], R2 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH2-, -Ο-, -CO- or -NH-, and R3 represents carbon number 1 or more and 22 or less alkyl groups or fluorine-containing alkyl groups). [化22]

H2N

[DA1 0] [DAI 1]

(In the formula [DA10] to the formula [DA11], R4 represents -0-, -OCH2-, -CH20-, -COOCH2- or -CH2OCO-, and R5 represents an alkyl group having 1 to 22 or more carbon atoms, an alkoxy group, Fluorinated alkyl or fluoroalkoxy). -24- 200948860 [Chem. 23]

(In the formula [DA12] to the formula [DA14], R6 represents -COO-, -OCO-, ❿-CONH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, -OCH2- or -CH2- R7 represents a hospital base, a hospitaloxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having a carbon number of 1 or more and 22 or less. [Chem. 24]

(In the formula [DA1 5] to the formula [DA1 6], R8 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, OCH2., -CH2- , -Ο- or -NH-, R9 represents fluorine, cyano, trifluoromethyl, nitro, azo, methylidene, ethyl hydrazine, ethoxylated or hydroxy). -25- 200948860 [化25] h2n

:h3 [DAI 7] [DAI 8] h2n

[DAI 9] [DA20] [Chem. 26]

[化27]

H3 [DA2 5] [DA2 6] -26- 200948860 In addition, a diamine-based sand chamber represented by the following formula [DA27] can also be exemplified. [28] h2n—(CH2)3-

Si—(CH2)3—nh2 ch3 [DA2 7] (in the formula [DA27], m is an integer from i to i〇). Other diamine compounds may be used singly or in combination of two or more kinds depending on the characteristics of liquid crystal alignment, voltage maintenance characteristics, and accumulated electric charge when used as a liquid crystal alignment film. &lt;tetracarboxylic dianhydride&gt; The tetracarboxylic dianhydride used in the present invention may be at least one compound of φ among tetracarboxylic dianhydrides, and specific examples thereof are as follows. For example, 'pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 154,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-fluorene tetracarboxylic dianhydride, 3,3,4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, Bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1' 1,3 , 3,3-hexafluoro-2,2-bis(3,4-dimercaptophenyl)propyl, bis(3,4-dicarboxyphenyl)dimethylnonane, double (3, deducted two - 27- 200948860 Carboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4 , 4'-diphenyltricarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 1,3-diphenyl-i, 2,3,4-cyclobutane tetracarboxylate Acid dianhydride, oxydiphenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2 , 3,4-cyclobutanine tetradecanoic acid dianhydride, iota, 2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4- Dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-trimethylcyclopentyl acetic acid dianhydride, 3,4-disyl-i,2,3,4-tetrahydro-1-naphthalene Acidic dianhydride, bicyclo [3.3.0] xinyuan-2,4,6,8-tetraresidic acid dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylate Acid dianhydride, bicyclo[4,4,0]decane _ 2,4,7,9-tetrapic acid dianhydride, bicyclo[4,4,0] brothel _2,4,8,10-tetraquinone Acid dianhydride, tricyclo[6.3.0.0&lt;2,6&gt;]~[--alkane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-dibutyltetradecanoic acid Dihydride, 4-(2,5-dioxotetrahydrofuran_3_yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2] Oct-7-ene-2,3,5'6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-di Carboxylic dianhydride, tetracyclo[6,2,1,1,0,2,7]indole-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxygalbornane _ 2: 3,5: 6-dicarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride Wait. Among them, the use of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1.2.3.4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dihydride, 1.2.3.4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, iota, 2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dihydride, 1,3-dimethyl-l,2,3,4-cyclobutanetetra-28- 200948860 carboxylic acid dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2 , 3,4,5_tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic acid di-hepatic, 2,3,5-trimethylcyclopentyl acetic acid dianhydride, 3, 4-Dicarboxy-12,3,4-tetrahydronaphthalene succinic dianhydride, bicyclo [3.3.0] xinyuan-2,4,6,8-tetradecanoic dianhydride, bicyclo[4,3,0] Decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane _ 2.4.7.9- tetraresidic acid dianhydride, bicyclo[4,4,0]decane_2 , 4,8,10-tetracarboxylic acid di-hepatic, bicyclo[6·3·0·0&lt;2,6&gt;] eleventh hospital-3,5,9,11-tetrahydro acid dianhydride, hydrazine 1, 2,3,4-butanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-didecanoic acid Di野, bicyclo[2,2,2]oct-7-discriminate _ 2,3,5' 6 -tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3_A Benzyl-3-cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo[6,2,nojj]癸_ 4,5,9,10-tetracarboxylic dianhydride, 3,5,6-three Carboxyl norbornane-2:3,5:6-dicarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 12,4,5-cyclohexanetetracarboxylic acid Preferably, the tetracarboxylic dianhydride of at least one compound selected from the group consisting of anhydrides is preferred. More preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, iota, 2,3,4-cyclopentane pentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane Carboxylic dianhydride, 3,4-didecyl-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, bicyclo[3.3.0]octane-2,4, 6,8-tetracarboxylic dianhydride, bicyclo[4,3,0] brothel _ 2.4.7.9- tetracarboxylic dianhydride, bicyclo[4,4,0]nonane-2' 4,7,9- Tetracarboxylic dianhydride, bicyclo[4,4,0]indole-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6·3.〇·〇&lt;2,6&gt;]10— Alkane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butylene tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1 , 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5 - (2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2_ -29- 200948860 dicarboxylic dianhydride, tetracyclo[6,2,1,1,0, 2,7]癸-4,5,9,1〇-tetracarboxylic dianhydride, 3,5,6-tricarboxy-norbornane-2: 3,5:6-dicarboxylic dianhydride, 1,2 At least one selected from the group consisting of 4,5-cyclohexanetetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used singly or in combination of two or more depending on the liquid crystal alignment property, voltage retention property, and accumulated electric charge when the liquid crystal alignment film is used. <Copolymer> The copolymer used in the present invention is polyglycine and polyimine. The polyamic acid is a polyamic acid obtained by reacting a diamine component ' containing a diamine compound (A) and a diamine compound (B) with a tetracarboxylic dianhydride. The polyimine of the present invention is a polyimine obtained by subjecting the polyamic acid to dehydration ring closure. Any of the polyamic acid and the polyimine is suitable as a copolymer of a liquid crystal alignment agent. The higher the content of the diamine compound (A) in the diamine component, the higher the voltage holding ratio, and after exposure to a high temperature for a long period of time, there is little residual charge accumulated by the DC voltage. Further, the diamine compound (B) has an effect of further improving the aforementioned effects. The content of the diamine compound (B) in the diamine component is preferably from 1 to 99 moles per gram of the amine compound (A). More preferably from 0.1 to 50 moles, the optimum is from 5 to 20 moles, and particularly preferably from 0.5 to 10 moles. The present invention can be used as a diamine component by using a diamine compound (A) or a diamine compound -30-200948860 other than the diamine compound (B) without impairing the effects of the present invention. The amount of the other diamine compound used at this time is preferably from 1 to 1 mol with respect to 1 mol of the diamine compound (A), more preferably from 0.1 to 5 mol. [Method for Producing Copolymer] The polylysine used in the present invention can be obtained by a known polymerization method. In general, for example, a method in which a tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine component is relatively easy to carry out in an organic solvent, and it is preferred that no by-products are produced. The organic solvent to be used at this time may be any solvent which can dissolve the produced polyamic acid. The following is a specific illustration thereof. Examples are hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, Tetramethyl urea, pyridine, dimethyl milling, hexamethylarylene, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl hydrazine Ketone 'methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve 'ethyl cellulolytic, methyl cellosolve acetate, ethyl cellosolve B Acid ester, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetic acid Ester, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene di-31 - 200948860 alcohol monopropyl ether, dipropylene glycol monoacetate Monopropyl ether, 3-methyl-3-methoxybutyl B Acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether , diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, carbonic acid Propylene ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3 - butyl methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used singly or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used in the above solvent without being precipitated in the range in which the produced polyaminic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, it is preferred that the organic solvent be dried as much as possible. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, for example, a solution obtained by stirring or dissolving a diamine component in an organic solvent, and directly adding a tetracarboxylic dianhydride, or making it a method of dispersing or dissolving in an organic solvent; and conversely adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent; and simultaneously adding tetracarboxylic dianhydride and two Any of these methods may be used as the method of the amine component. Further, when the tetracarboxylic dianhydride or the diamine component is composed of a plurality of kinds of compounds, the reaction may be carried out in a state of being mixed beforehand, or may be reacted in a sequence of -32 to 200948860, and the individual reaction may be carried out. The low molecular weight body is mixed and reacted into a high molecular weight body. The polymerization reaction of the polyamide can be selected from -20 ° C to 15 (any temperature of TC, but preferably in the range of -5 ° C to l ° ° C. In addition, the reaction can be arbitrary At the concentration, it is difficult to obtain a high molecular weight copolymer because the concentration is too low. When the concentration is too high, the viscosity of the reaction liquid is too high, so that uniform stirring becomes difficult, so the reaction of the tetracarboxylic dianhydride with the diamine component is dissolved. The total concentration in the φ liquid is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is further added. In the synthesis reaction of poly-proline The molar content of the diamine component is preferably from 0.8 to 1.2 with respect to 1 mole of the tetracarboxylic dianhydride. The closer the molar ratio is to 1.0, the molecular weight of the formed polyamine can be increased. The polyimine used in the present invention is a polyimine obtained by subjecting the above polyamic acid to dehydration ring closure, which can be used as a polymer for producing a liquid crystal alignment film. ◎ In the polyimine used in the present invention, The dehydration ring closure ratio of the proline group (the imidization ratio) is not necessarily 100%, depending on the use. The purpose of making the arbitrarily adjusted. The method for imidizing the polyruthenium imidate is exemplified by the heat-imidization of the solution of the poly-proline acid directly, and the catalyst added to the solution of the poly-proline The temperature at which the hydrazine imidization in the polyamic acid solution is from 100 ° C to 40 ° C, preferably from 120 ° C to 250, and preferably the hydrazine imidization reaction - 33- 200948860 The water produced is excluded from the system. The catalyst of imide can be imidized by adding a basic catalyst and an acid anhydride to the solution of poly-proline, and preferably at -20 to 250 °C. It is carried out by stirring at a temperature of 180 ° C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 of the amidate group. Up to 5 〇 moles, preferably 3 to 30 moles. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., among them, The pyridine is preferred because it can maintain a moderate basicity to allow the reaction to proceed. The acid anhydride can be exemplified by acetic anhydride, trimellitic anhydride, benzene tetracarboxylic anhydride, etc., wherein the reaction is terminated if an acid anhydride is used. The subsequent purification becomes easier and preferable. The imidization ratio of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. Among the polyimine used in the present invention, The dehydration ring closure ratio (protonation rate) of the proline group is not necessarily 1%, and can be adjusted arbitrarily according to the purpose or purpose. The optimum is more than 50%. From polyglycine or polyimine When the reaction solution recovers the poly-proline or polyimine produced, the reaction solution can be poured into a weak solvent to form a precipitate. The weak solvent used for the precipitation can be exemplified by methanol, acetone, hexane, butyl cellosolve. , heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. Pour into a weak solvent and the polymer of the Shen Dian is recovered by filtration and can be used under normal pressure or reduced pressure. , dry at room temperature or heat. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. The weak solvent at this time is exemplified by, for example, an alcohol, a ketone, a hydrocarbon, etc., and if three or more kinds of weak solvents selected from the group are used, it is preferable because the purification efficiency can be further improved. The molecular weight of the poly-proline and the polyimine contained in the liquid crystal alignment agent of the present invention is determined by GPC in consideration of the strength of the coating film obtained therefrom and the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the (gel permeation chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 S 1 50,000 ° 0 &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film. The coating liquid is composed of a resin component which forms a resin film and an organic solvent which dissolves the resin component. In the present invention, the resin component is a resin component containing a copolymer of at least one selected from the group consisting of polylysine and polyimine used in the present invention. In this case, the content of the resin component in the coating liquid is from 1% by mass to 20% by mass, preferably from 2% by mass to 10% by mass. In the present invention, the above-mentioned resin components may be all of the copolymers used in the present invention, or those in which the other polymers are mixed in the copolymer of the present invention. At this time, the content of the other polymer in the resin component is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass%. The other polymer, for example, a polyamine or a polyamine obtained by using a diamine compound (A) and a diamine other than the diamine compound (B) as a diamine component reactive with a tetracarboxylic dianhydride component醯imine and so on. The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve the organic solvent of the above resin component. Specifically, for example, -35-200948860 is listed below. For example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, 2-pyrrolidone, Ν-ethyl pyrrolidone, Ν-vinyl pyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl milling, hexamethyl argon, γ-butyrolactone, 1,3 - Dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate Ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents may be used in combination of two or more kinds. When the polyimine is dissolved in an organic solvent, it can be heat-treated for the purpose of promoting the dissolution of the polyimide. When the heating temperature is too high, the molecular weight of the polyimine will be lowered. Therefore, the temperature is preferably from 30 to 100 ° C. The liquid crystal alignment agent of the present invention may contain other components than the above. The solvent or compound which can improve the uniformity of the film thickness or the surface smoothness when the liquid crystal alignment agent is applied, and the compound which improves the adhesion between the liquid crystal alignment film and the substrate can be exemplified. Examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness are as follows. Examples are, for example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Kikabi alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol , propylene glycol monoacetate, propylene glycol monomethyl ether, -36- 200948860 propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol II Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol single Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, B Isobutyl butyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone oxime, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane ,positive Alkane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 -methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, butyoxy-2-propanol, 1 -phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-ethyl a solvent having a low surface tension such as an acid ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate Wait. Among these solvents, butyl cellosolve, propylene glycol monomethyl ether, and ethyl lactate are preferred. These weak solvents may be used singly or in combination of plural kinds. When the solvent is as described above, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total of the solvent contained in the liquid crystal alignment agent. -37-200948860 The compound which improves the uniformity after film or the surface smoothness is exemplified by a fluorine-based surfactant, a ruthenium-based surfactant, a nonionic surfactant, and the like. More specifically, for example, F TOP EF301, EF3 03, EF352 (manufactured by TOKEMU PRODUCT), MEGAFAX F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M), ASAHIGUARD AG710, SURFLON S-382 'SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactants is preferably from 1 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, per part by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate are the functional decane-containing compound or the epoxy group-containing compound shown below. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N - (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecyl propyl triethylidene triamine, N-trimethoxydecyl propyl triethylidene triamine, trimethoxy decyl _1, 4, 7 - triazadecane, 1 -triethoxydecyl-14,7-triazadecane, 9-trimethoxydecyl- 3,6-diazepine acetate, 9_ Triethoxy-38- 200948860-based alkyl-3,6-diazaindolyl acetate, N-benzyl-3-aminomethoxydecane, N-benzyl-3-aminopropyl three Ethoxy decane, &gt; 3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethane, N-bis(oxyethyl)-3-aminopropyltrimethyl Oxydecane Ethyl ethyl-3-aminopropyl triethoxy decane, ethylene glycol dioleate, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, New φ diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol glyceryl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-glyceryl -2,4-hexanediol, ^:^', ^['-tetraglycidyl-m-diamine, 1,3-bis(indole, Ν-diglycidylamine 碁methyl) ring N, When N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane or the like is used to improve the adhesion to a substrate, the resin component contained in the liquid crystal alignment agent is 100. The parts by mass are preferably 3 parts by mass, more preferably 1 to 20 parts by mass. If the amount used is less than 〇, the effect of improving the adhesion cannot be expected. If it is more than 30, the alignment of the liquid crystal may be deteriorated. In the liquid crystal alignment agent of the present invention, in addition to the above, a dielectric or a conductive material may be added for the purpose of changing the dielectric constant or the conductive electrical property of the liquid crystal alignment film within a range that does not impair the effect. Further, a crosslinkable compound which increases the hardness of the film or the purpose of the film as a liquid crystal alignment film may be added. &lt;Liquid crystal alignment film, liquid crystal display element&gt; Propyltriphenyl-oxyindole, N-bis-glycidyl ether, tripentanediol di-condensed tetra-xylene xylene hexane, and the amount of ruthenium relative to 0.1 to 0" mass The quality of the present invention and the nature of the hair, etc. -39-200948860 The liquid crystal alignment agent of the present invention is applied to a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, or in vertical alignment use or the like. It can be used as a liquid crystal alignment film by alignment treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate which forms an ITO electrode or the like which is useful for driving the liquid crystal. Further, it is also possible to use an opaque material such as a tantalum wafer which is a single-sided substrate of the reflective liquid crystal display element, and a material such as aluminum which can reflect light can be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of screen printing, lithography, flexographic printing, ink jet printing or the like. As for other coating methods, there are dip coating, roll coating, slit coating, spin coating, etc., and these may be used depending on the purpose. The liquid crystal alignment agent is applied to the substrate and fired, and is heated at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate to evaporate the solvent to form a coating film. When the thickness of the coating film formed after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. If the thickness is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to l〇〇nm. When the liquid crystal is aligned horizontally or obliquely, the film after firing is treated by rubbing or polarized ultraviolet rays. The liquid crystal display element of the present invention is a substrate to which a liquid crystal alignment film is attached from the liquid crystal alignment agent of the present invention, and a liquid crystal cell is produced by a known method, and is used as a liquid crystal display element. For example, in the case of liquid crystal cell fabrication, one of the crystal-aligned films prepared to be formed with liquid - 40,488,480, and the substrate is disposed on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface becomes the inner side. In the method, another substrate is bonded, a liquid crystal is injected under reduced pressure, and the method is applied, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and packaged. The thickness of the separator at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm. As described above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. [Embodiment] [Embodiment] The present invention will be described in more detail below by way of examples and comparative examples, but the description of the present invention is not limited by the examples. The following are abbreviations and structural formulae for the compounds used in the examples. 〇(tetracarboxylic dianhydride) CBDA: 1,2,3,4•cyclobutane tetraresin dianhydride BODA:bicyclo[3,3,0 Octane-2,4,6,8-tetracarboxylic dianhydride [Chemical 29]

-41 - 200948860 PCH7DAB : 1,3-Diamino-4-[ 4 · (4-heptylcyclohexyl)phenoxy]benzene DBA : 3,5-diaminobenzoic acid 2,4-DAA: 2 ,4-diamino-indole&gt;^-diallylaniline

Me-DADPA: N-methyl-4,4'-diaminodiphenylamine diamine (1): (refer to the following formula) Diamine (2): (refer to the following formula) [Chem. 30]

(Organic solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellulose &lt; molecular weight measurement&gt; The molecular weight of the polyimine in the synthesis example was a room temperature gel permeation chromatography method (manufactured by Showa Denko Co., Ltd.) GPC) device (GPC-101), Shodex company pipe column (KD-8 03, KD-805) for the following measurements -42- 200948860

Column temperature: 50 ° C Dissolution: N, N'-dimethylformamide (additive is lithium bromide monohydrate (LiBr · H20) is 30 mmol / L, phosphoric acid. Anhydrous crystal (〇 - phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is l〇ml / L) Flow rate: 1. Om 1 / min. Standard sample for the test line: TSK standard oxidized polyethylene (molecular weight 900,000, 150,000, 100,000, 30,000) made by Tosoh Corporation, 0 And polyethylene glycol (manufactured by Labo Co., Ltd. (molecular weight: about 12,000, 4,000 '1,000) ° &lt;Measurement of oxime imidization ratio> The ruthenium imidization ratio of polyimine in the synthesis example is as follows Generally measured. Add 20 mg of the polyimine powder to the NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd., Φ 5 ) to add 0.53 ml of deuterated dimethyl sub-mill (DMS0-d6 '0.05% TMS (four Methyl decane) Q mixture), and completely dissolved by ultrasonic waves. This solution was subjected to proton NMR of 500 mM of this solution using a NMR measuring instrument (JNW-ECA500) manufactured by Nippon Electric Corporation. The ruthenium imidization ratio is a peak estimation of the proton determined by using a proton derived from an unaltered structure before and after the imidization as a reference proton, and a proline derived from 9.5 to 1 〇. The estimation of the proton peak of the NH group is obtained by the following formula.醯imination rate (%) = (1 - α · x / y) xl 〇〇 In the above formula, x is the proton peak estimate derived from the NH group of the proline, y is the reference proton peak estimate 値, α It is the ratio of the number of the protons of a proton relative to the NH group of the proline in the case of poly-proline (the imidization ratio is -43 to 200948860 〇%). &lt;Synthesis Example 1 &gt; BODA ( 18.8 g, 75 mmol), M e - D A D P A (6 · 3 g,

3 Ommo 1 ) , DBA (6.1 g &gt; 40 mmol), and PCH7D AB (1 1.4 g, 30 mmol) were mixed in NMP (114.0 g), and reacted at 40 ° C for 3 hours, then CBDA (4.8 g, 25 mmol) and NMP (76.0 g) were reacted at 40 ° C for 12 hours to obtain a polyamine acid solution [A] having a resin content of 20% by mass. The polyamic acid solution had a number average molecular weight of 28,100 and an average weight molecular weight of 72,300. &lt;Synthesis Example 2&gt; In the polyamic acid solution [A] (80. Og) obtained in Synthesis Example 1, after adding NMP to 6% by mass, acetic anhydride (8.6 g) of a quinone imine catalyst was added, and Pyridine (6.7 g) was allowed to react at 80 ° C for 3 hours. The reaction solution was poured into methanol (990 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder [B]. The polyimine had a ruthenium iodide ratio of 53%, a number average molecular weight of 20,100, and a weight average molecular weight of 58,300. &lt;Synthesis Example 3&gt; BODA (1 8 · 8 g, 7 5 mm ο 1 ), Me - DADPA (6.3 g, 3 Ommol), DBA (6.1 g, 40 mmol), and PCH 7 DAB (1 1 · 4 g 200948860, 30 mmol) was mixed in NMP (1 14.0 g), and after reacting at 40 ° C for 3 hours, CBDA (4.8 g, 25 mmol) and NMP (76-0 g) were added and reacted at 40 ° C for 12 hours. A polyaminic acid solution was prepared. After the polyacrylic acid solution (80.0 g) was added to NMP and diluted to 6 mass%, acetic anhydride (17.2 g) and pyridine (13. 3 g) of a ruthenium imine catalyst were added, and the mixture was reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (1 040 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder [C]. The polyimine had a ruthenium iodide ratio of 81%, a number average molecular weight of 19,300, and an average weight molecular weight of 51,600. &lt;Synthesis Example 4&gt; BODA (9.4 g, 37 mmol), diamine (1) (5.9 g, 15 mmo 1 ), DBA (3-0 g, 20 mmol), and PCH7DAB (5.7 g, 15 mmol) in NMP (63.0) g) mixed, allowed to react at 80 ° C for 3 hours, then added CBDA (2.3 g, 12 mmol) and NMP (42.4 g), and reacted at 40 ° C for 12 hours to obtain a polyaminic acid solution. . After the polyaminic acid solution (5 〇.〇g) was added to NMP and diluted to 6 mass%, acetic anhydride (W.lg) ' and guanidine (3.9 g) of the quinone imine catalyst were added at 100 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder [D]. The polyimine had a hydrazine imidization ratio of 53%, a number average molecular weight of 21,200, and a weight average molecular weight of 60,400. -45- 200948860 &lt;Synthesis Example 5&gt; CBDA (9.7 g, 50 mmol) '2,4-DAA (2.0 g, 10 mmol), DBA (3.8 g, 25 mmol), and PCH7DAB (5.7 g, 15 mmol) in NMP ( The mixture was mixed in 85.0 g, and reacted at 23 ° C for 20 hours to prepare a polyaminic acid solution. After the polyproline solution (50.5 g) was added to NMP and diluted to 6 mass%, acetic anhydride (7.2 g) of ruthenium amide and pyridine (3.2 g) were added, and the mixture was reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (600 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 Torr to give a polyimine powder [E]. The polyimine had a hydrazine imidation ratio of 92%, a number average molecular weight of 1,800, and a weight average molecular weight of 46,400. &lt;Synthesis Example 6&gt; BODA (7.5 g, 30 mm ο 1 ), DBA (3.7 g, 24 mmol), diamine (2) (2.8 g, 4.0 mmol), and PCH 7 D AB (4 · 6 g) , I2.0mmol), mixed in NMP (49.2g), reacted at 80 ° C for 5 hours, then inject CBDA (1.9g, 10.Ommol) NMP (32.6g), react at 40 ° C 3 In hours, a polyaminic acid solution was prepared. After the polyaminic acid solution (50.0 g) was added to NMP and diluted to 6 mass%, acetic anhydride (5.0 g) of ruthenium amide was added, and pyridine (3.7 g) was added, and the reaction was carried out at 80 ° C for 2 hours. 45 minutes. The reaction solution was poured into methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol 200948860 and dried under reduced pressure at 100 ° C to obtain a polyimine powder [F]. The polyimine was imidized at a 50% yield average molecular weight of 20,800 and a weight average molecular weight of 60,200. &lt;Synthesis Example 7&gt; BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol), and PC Η 7 DAB (1 5 2 · 2 g, 400 mm ο 1 ) in NMP (φ 1290 g ) After mixing and reacting at 80 ° C for 5 hours, CBDA (38.8 g, 198 mmol) and NMP (320 g) were added and reacted at 40 ° C for 3 hours to obtain a polyaminic acid solution. After the polyaminic acid solution (600.2 g) was added to NMP and diluted to 6 mass%, acetic anhydride (63.9 g) of ruthenium amide catalyst and pyridine (49.6 g) were added, and the mixture was reacted at 80 ° C. hour. The reaction solution was poured into methanol (7700 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 10 ° C to obtain a polyimine powder [G]. The polyamidimide had a ruthenium iodide ratio of 57%, a number average molecular weight of 23,000, and a weight average molecular weight of 80,200. &lt;Synthesis Example 8&gt; The polyamic acid solution (1 〇 1.2 g) obtained in Synthesis Example 7 was added to NMP and diluted to 6 mass%, and then acetic anhydride (21.3 g) of ruthenium amide was added, and pyridine (16.5 g) was added. ) 'React at 90 ° C for 3 hours. The reaction solution was poured into methanol (1300 ml) to remove the resulting precipitate. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder [H]. -47- 200948860 The polyamidimide has an imidization ratio of 81%, a number average molecular weight of 20,400, and a weight average molecular weight of 63,000. &lt;Synthesis Example 9&gt; CBDA (7.8 g, 40 mmol), 2,4-D AA (4.9 g '24 mmol), and PCH7DAB (6.1 g, 16 mmol) were mixed in NMP (74.9 g) at 23 ° C The reaction was carried out for 20 hours to prepare a polyaminic acid solution. After the polyaminic acid solution (80.0 g) was added to NMP and diluted to 6 mass%, acetic anhydride (10 g. 4 g) of ruthenium imide catalyst, and pyridine (4.6 g) were added, and the reaction was carried out at 50 ° C. hour. The reaction solution was poured into methanol (100 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder [I]. The polyimine was imidized at a 97%' number average molecular weight of 18,300 and a weight average molecular weight of 44,200. 200948860 [Table l]

Synthesis Example Diamine Component [mmol: Tetracarboxylic Acid Component [mmol] Ruthenium Amination Rate (%) Diamine Compound (A) Diamidation (Β) Other Diamine 1 Polyamine Acid [A] Me-DADPA 301 DBA[40] PCH7DAB P〇l CBDA[25] BODA"751 - 2 Polyimine powder [B] Me-DADPA Γ301 DBA[40] PCH7DAB [301 CBDA[25] ΒΟΟΑΓ751 53 3 Polyimine powder [C] Me-DADPA Γ301 DBA[40] PCH7DAB 『301 CBDA[25] ΒΟΟΑΓ751 81 4 Polyimine powder [D] Diamine (1) Γ151 DBA[20] PCH7DAB Π51 CBDA[12] BODAP71 53 5 Polyimine Powder [E] 2,4-DAA Π〇1 DBAP5] PCH7DAB [151 CBDA[50] 92 6 Polyimine powder [F] Diamine (2) [41 DBA[24] PCH7DAB 『121 CBDA[10] BODAPOl 50 7 Polyimine powder [G] - DBA[400] PCH7DAB "4001 CBDA[198] BODA[60〇1 57 8 Polyimine powder [H] - DBA[400] PCH7DAB [4001 CBDA[198] BODA [60〇1 81 9 Polyimine powder [I] 2,4·ϋΑΑ Γ241 - PCH7DAB Γ161 CBDA[40] 97 In the table, "diamine compound (A)" and "diamine compound (B)" "-" in the column means the meaning of not using these diamine compounds [Liquid of the present invention Preparation and evaluation of crystal alignment agent] &lt;Example 1&gt; NMP (8.1 g) and BCS (16.0 g) were added to the polyamine acid solution [A] (1 0 · 1 g) obtained in Synthesis Example 1. After stirring at 25 ° C for 2 hours, a liquid crystal alignment agent [1 ] was obtained. The liquid crystal alignment agent did not exhibit turbidity or precipitation, etc. -49-200948860 Anomaly, and it was confirmed that the resin component was uniformly dissolved. [Production of Liquid Crystal Cell] The liquid crystal alignment agent π] obtained above was spin-coated on a glass substrate with a pole attached thereto, and dried on a hot plate at 80 ° C for 5 minutes, and then subjected to a hot air circulating oven for 1 hour. After baking, a film thickness liquid crystal alignment film is obtained. After preparing a 6 μm-sized distance aligner on the liquid crystal alignment film surface of the liquid crystal alignment film with the liquid crystal alignment film, the sealant was hardened to form an empty cell. The cell crystal was injected into a liquid crystal MLC-6608 (manufactured by Messen Co., Ltd.) using a reduced pressure injection method, and the injection port was closed to obtain a nematic liquid crystal cell. [Evaluation of Voltage Retention Rate] For the liquid crystal cell fabricated above, a voltage of 4 V was applied at a temperature of 80 ° C, after 16.67 ms, and after 1 667 ms: to determine the degree to which the voltage was maintained to calculate the voltage. The S measurement was measured by using the VHR-1 voltage holding ratio | by the Dongyang Technology Co., Ltd., and the measurement was performed under the conditions of Voltage: ±4 V, Pulse Width: 60 μδ Period : 16.67 ms or 1667 ms. The result ί is shown in Table 2. [Evaluation of residual charge] For the liquid crystal cell after the voltage holding ratio is measured, apply 3 0 /current voltage 5 · 8 Vpp and DC voltage 1 V, and measure DC voltage solution β ΙΤΟ electricity 2 1 0 ° C 1 0 0 nm, Print the empty crystal on it at 60ps: voltage, ; In addition, the voltage device (residual charge) generated in the cell of the liquid -50-200948860 after the intersection of the device and the film is described later. The results are shown in Table 3 below. [Evaluation after high-temperature standing] The liquid crystal cell after completion of the above measurement was placed in a constant temperature bath set at 60 ° C for 1 day, and the voltage holding ratio and residual charge were measured during the measurement period. The results are shown in Tables 2 and 3 below. ❹ &lt;Example 2&gt; NMP (24.4 g) was added to the polyimine powder [B] (5.0 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (12.3 g) and BCS (41.7 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [2]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [2], a ruthenium liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Example 3&gt; NMP (24.5 g) was added to the polyimine powder [C] (5.1 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (23.9 g) and BCS (30.0 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [3]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. -51 - 200948860 Using the obtained liquid crystal alignment agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Example 4&gt; NMP (25.0 g) was added to the polyimine powder [D] (5.0 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (20.1 g) and BCS (33.2 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [4]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Example 5&gt; NMP (24.5 g) was added to the polyimine powder [E] (4.9 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (29.0 g) and BCS (25.3 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [5]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. -52-200948860 &lt;Example 6&gt; NMP (25.0 g) was added to the polyimine powder [F] (5.0 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (11.5 g) and BCS (42.9 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [6]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [6], a liquid crystal cell was prepared in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Comparative Example 1 &gt; NMP (25.0 g) was added to the polyimine powder [G] (5.0 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (23.1 g) and BCS (28.5 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [7]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Comparative Example 2 &gt; NMP (25.0 g) was added to the polyimine powder [H] (5 · 1 g ) obtained in Synthesis Example 8 and stirred at 701: for 40 hours to be dissolved. To the solution, NMP (30.4 g) and BCS (23.3 g) were added, and after stirring at -53 to 200948860 at 25 ° C for 2 hours, a liquid crystal alignment agent [8] was obtained. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [8]', a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. &lt;Comparative Example 3 &gt; In the polyimine powder [I] (5.1 g) obtained in Synthesis Example 9, NMP (24.8 g) was added, and the mixture was stirred at 70 ° C for 40 hours to be dissolved. NMP (36.4 g) and BCS (17.3 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment agent [9]. The liquid crystal alignment agent did not exhibit an abnormal phenomenon such as turbidity or precipitation, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after high temperature standing were performed. The results are shown in Tables 2 and 3 below. Further, in Tables 2 and 3, the "-" of the imidization ratio means that the imidization ratio is not calculated. -54- 200948860 [Table 2] Liquid crystal alignment agent 醯 imidization rate (%) Voltage retention rate (%) Liquid crystal crystal 1 After the high entanglement 16.67 ms 1667 ms 16.67 ms 1667 ms Example 1 [1] - 96.9 56.8 96.7 56.5 Example 2 [2] 53 98.1 65.9 98.0 66.0 Example 3 [3] 81 98.0 66.7 98.0 66.7 Example 4 [4] 53 97.8 68.5 97.7 68.4 Example 5 [5] 92 97.9 69.0 97.9 68.9 Example Γ Γ 61 50 97.1 55.2 97.0 55.1 Comparative Example 1 [7] 57 97.8 64.5 97.5 64.3 Comparative Example 2 [8] 81 97.6 61.2 97.3 61.0 Comparative Example 3 "91 97 97.8 61.9 97.5 61.4 Liquid crystal alignment agent 醯 imidization ratio (%) Residual electricity 1 When the harsh (V) liquid crystal cell is produced at a high level, Example 1 [1] - 0.01 0.01 Example 2 [2] 53 0.02 0.03 Example 3 [3] 81 0.02 0.05 Example 4 [4] 53 0.03 0.06 Example 5 [5] 92 0.05 0.08 Example 6 [61 50 0.02 0.03 Comparative Example 1 [7] 57 0.15 0.25 Comparative Example 2 [8] 81 0.24 0.41 Comparative Example 3 Γ91 97 0.16 0.21 [Table 3] [Industrial Utilizing] The liquid crystal alignment agent of the present invention has a high voltage holding ratio and is small even after exposure to a high temperature for a long period of time. A liquid crystal alignment film which has a residual electric charge due to a DC voltage. Therefore, when the liquid crystal display element obtained by the method, that is, -55-200948860, can be used for a long period of time, it is possible to suppress a display failure such as burnt or display of a picture, so that it can become It has excellent reliability of the alignment agent, and is very suitable for large-screen and high-definition LCD TVs. As a result, it is very suitable for TN components, STN components, TFT liquid crystal components, and can be used for vertical alignment or horizontal alignment. The liquid crystal display element of (IPS), etc. The entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2008-014973, filed on Jan. Reveal the content.

-56-

Claims (1)

200948860 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a copolymer obtained by reacting a diamine component of a diamine compound (A) and a diamine compound (B) with a tetrahydro acid dianhydride, Amine compound (A): a compound of at least one selected from the group consisting of the formula [T1], the formula [T2] and the formula [T3] of the diamine compound having a tertiary nitrogen atom, φ diamine compound (B): a diamine compound having a carboxyl group in the molecule, [Chemical Formula 1] [τι] [T2] H2N_〇^4^W4^^_n H2 [T3] (In the formula [T1] to the formula [T3], Wi is a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and W2 has 6 to 15 One carbon atom and having 1 to 2 aromatic groups of a benzene ring, W3 is an alkylene group or a biphenyl group having 2 to 5 carbon atoms, and W4 is a carbon atom 4 to 6 which may be substituted by a nitrogen atom of 3 a cycloalkyl group, W5 is an alkylene group having 2 to 5 carbon atoms, and Z1 is a disubstituted amino group having a carbon number of 1 to 6 which may be substituted by an aliphatic group in the case where Wi is a benzene ring, Wi is In the case of a nitrogen-containing aromatic heterocyclic ring, it is a disubstituted amino group which may be substituted by a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, Z2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and g is ruthenium or An integer of 1). 2. The liquid crystal alignment agent of the first aspect of the invention, wherein the diamine compound (A) is a compound represented by the following formula [1] to formula [4], -57- 200948860 [Chemical 2] /A ·) h2n [2] [3] [1] [4] [4a] [4b] (In the formula [1] to the formula [4], Ai is a nitrogen-containing aromatic heterocyclic ring 'A2 is an aromatic group having 6 to 15 carbon atoms' and having 1 to 2 benzene rings, and A3 is a carbon number 2 to An alkyl group or a biphenylene group, A4 is a group represented by the formula [4a] or the formula [4b], and A5 is an aliphatic group having a carbon number of 2 to 5 and an alkyl group having a carbon number of 1 to 6. Substituted disubstituted amine group, Y2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and k is an integer of 0 or 1. 3 _ The liquid crystal alignment agent of the second aspect of the patent application ' wherein the 'diamine compound (A) is of the formula [丨] or the formula [2]. 4. The liquid crystal alignment agent of claim 2, wherein A2 of the formula [3] is a benzene ring or the following formula [3a], [Chemical 3] [3a] (in the formula [3a], p is A bonding group selected from a single bond, -〇_, -NH-, methyl-methyl and aramidyl). -58-200948860 5. The liquid crystal alignment agent of claim 1 or 2, wherein the 'diamine compound (A) is at least one selected from the group consisting of the following formulas [5] to [is] Diamine compound, [Chemical 4] [Chemical 5] [13] [Chemical 6] [17] [18] -59- 200948860 (in [13], m and η are integers from 1 to 11, respectively, and m + n is an integer from 2 to 12 in the formula [15] where 'j is 〇 to 3 In the integer 'in the formula [18], 'h is an integer from 1 to 5). 6. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the diamine compound (B) is a diamine compound represented by the following formula [19], [19] (|〇OH) n /I, Η〆 NH2 (In the formula [19], Χ is an organic group having an aromatic ring of 6 to 30 carbon atoms, and η is an integer of 1 to 4). 7. The liquid crystal alignment agent of claim 6, wherein the diamine compound (Β) is a diamine compound selected from the following formula [20] to formula [24], [Chem. 8] Η2Ν-|· -j-(C〇〇H)in1 [2 0] ~ 60 - 200948860 (in the formula [2 0] 'ml is an integer from 1 to 4' in the formula [2丨], χ2 is a single bond, -(:112-, -.2114-, -€:(€:113 ) 2-, -〇?2-, -(:(.?3)2-,-0-, -CO-, -ΝΗ-, -N(CH3)-, -CONH-, -NHC〇-, _cH2 〇_, · OCH2-, -COO-, -OCO-, -CON(CH3)_, or -n(CH3)CO-, m2, m3 are integers from 〇 to 4, respectively, and m2 + m3 represents i to 4 In the formula [22], m4 and m5 are each an integer from 1 to 5, and in the formula [23], φ X3 is a linear or branched alkyl group having a carbon number of 1 to 5, and m6 is an integer of 1 to 5. In the formula [24], X4 is a single bond, _CH2-, -C2H4-, _C(CH3)2-, -cf2-, -c(cf3)2-, -o-, -co-, -nh-, -n(ch3)-, -conh-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)-' or -N(CH3)CO-,in7 is 1 8. The liquid crystal alignment agent of claim 7, wherein in the formula [20], ml is an integer of 1 to 2. 9. The liquid crystal alignment agent of claim 7 Where 'Formula 10 [2 1 ], X2 is a single bond, -CH2-, -C2H4-, -C(CH3)2-, -Ο-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO- Or -OCO-, m2, m3 are both an integer of 1. 10. In the liquid crystal alignment agent of the seventh aspect of the patent application, in the formula [24], X4 is a single bond, -CH2-, -〇-, - CO·, -NH-, -CONH· , -NHCO-, -CH20., _OCH2-, -COO-, or -OCO-, m7 is an integer from 1 to 2. 1 1. Patent application range 1 to 1 The liquid crystal alignment agent of any one of the items 0, wherein the content of the diamine compound (B) in the diamine component is phase -61 - 200948860, and 1 mole of the diamine compound (A) is 〇〇1 to 99. The liquid crystal alignment agent of any one of the liquid crystal alignment agents, wherein 5 to 80% by mass of the solvent contained in the liquid crystal alignment agent is a weak solvent. 1 3 · The liquid crystal alignment agent of any one of the inventions of the invention, wherein the copolymer in the liquid crystal alignment agent is a polyimine obtained by dehydration ring closure of polyamic acid. It is characterized in that the liquid crystal alignment agent of any one of claims 1 to 13 is used. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 14 of the patent application. -62- 200948860 IV. Designated representative drawings: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: no flaws 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: Chemical 1 (Chemical 1) -4-