TW201011421A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

Provided are a liquid crystal aligning agent with good whitening and printing performance which generates no aggregate that causes an uneven gap in a liquid crystal panel during printing while maintaining the good electric property of a polyimide alignment film, and a liquid crystal alignment film and a liquid crystal display element which are obtained by using the same. The liquid crystal aligning agent is characterized by containing a resin component containing polyimide obtained by imidizing a polyamic acid obtained by a reaction between a diamine component and a tetracarboxylic dianhydride, and a solvent component containing a pyrrolidone compound composed of N-ethyl-pirrolidone or N-cyclohexyl-2-pyrrolidone, and the liquid crystal alignment film and the liquid crystal display element are obtained by using the same.

Description

[Technical Field] The present invention relates to a liquid crystal alignment treatment agent used for a liquid crystal display element, a liquid crystal alignment film using the same, and a liquid crystal display element. % [Previous technique] The liquid crystal display element is a structure in which a liquid crystal molecule which is formed by liquid crystal molecules on a substrate is held by a film, and is responsive to a liquid crystal molecule which is aligned in a certain direction by a liquid crystal alignment film. Display component. In the liquid crystal alignment film, the surface of the polyimide film which is generally formed on the substrate with the electrode is produced by applying a pressure to the surface by rubbing or a nylon cloth, and performing a so-called "friction treatment". In addition, the alignment film for VA (abbreviation of Vertical Alignment) which is not subjected to the rubbing treatment, and the light alignment film which imparts anisotropy to the surface of the film by irradiation of the polarized light UV to align the liquid crystal is also attracting attention. As a means for forming a polyimide film on a substrate with an electrode, there is a method in which a solution of a polyimide precursor such as polyglycine is used as a coating film, and imidization is performed on a substrate. A method of using a solution containing a polyimine which has been previously imidized. Among them, the method using a solution containing a polyimine is such that even if it is baked at a lower temperature than *, it may form a reverse side of a polyimide film having good characteristics as a liquid crystal alignment film, and the film strength is formed. It is low, and it is easy to cause a problem of damage to the film surface or peeling of the film by the rubbing treatment. Damage or peeling of the surface of the liquid crystal alignment film is an important cause of display failure when it is used as a liquid crystal display element. Further, the ratio of polyimine to polyamine is higher than that of -5,011,114,21, and the solubility in an organic solvent is generally poor. Therefore, when imidization is performed in advance, it may be difficult to form a uniform coating film, and it is often used. Since the solvent of the liquid crystal alignment treatment agent is insolubilized, there is a problem that it cannot be contained in the liquid crystal alignment treatment agent. Therefore, the solubility of the polyimine contained in the liquid crystal alignment treatment agent is also important. Further, when a liquid crystal alignment agent containing polyimine is used, when printing is performed on a substrate, it is easy to cause whitening of the varnish containing the polyimine by moisture absorption, or agglutination due to drying of the varnish on the printing plate. The problem of things. In the above-mentioned problem, a liquid crystal alignment treatment agent containing a diamine component having a specific structure which is excellent in the friction resistance of the liquid crystal alignment film and the solubility of the polyimine is proposed (see, for example, Patent Document 1). Further, as a method of suppressing the whitening phenomenon of the varnish containing a polyimine, it has been proposed to use N-vinylpyrrolidone or N-cyclohexylpyrrolidone in 50% or more of the solvent (see, for example, Patent Document 2). However, liquid crystal alignment treatment agents for suppressing agglomeration due to varnish drying have not been proposed so far.

The dried agglomerates of the varnish have characteristics that are easily produced in the Q portion of the printing plate. Therefore, even if agglomerates are generated, they are not particularly problematic if they are not present in the pixels. However, in recent years, in order to realize high-speed response of the liquid crystal panel, the gap of the panel is narrowed. As a result, the interval between the two substrates constituting the liquid crystal cell is narrowed, so that it does not exist in the pixels in the past, that is, the above-mentioned aggregates which do not cause problems, and the cause of the unevenness of the panel gap is increasing. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] International Publication No. 2006/1 26555 (Patent Document 2) Japanese Patent Publication No. Hei 5-117587 It is known that the aggregate which is the cause of the unevenness of the gap of the panel can be produced irrespective of the whitening phenomenon caused by the moisture absorption of the varnish. φ In view of the above, the present invention provides a liquid crystal alignment which is excellent in whitening and printability and which does not cause unevenness of gaps in the liquid crystal panel during printing, in order to maintain good electrical characteristics of the polyimide film. The treatment agent is for the purpose. In addition, the liquid crystal alignment treatment agent is excellent in long-term storage stability in addition to properties such as whitening, printability, and agglomerates, and is excellent in friction resistance when the liquid crystal alignment film is used, and the liquid crystal has a high inclination angle and an alignment property. It is also a good liquid crystal alignment agent for the purpose. The present inventors intend to achieve the above object and carry out detailed research results to complete the present invention. That is, the present invention will be described below. A liquid crystal alignment treatment agent comprising a resin component and a solvent component, wherein the resin is obtained by imidization of a polyamido acid obtained by reacting a diamine component with a tetracarboxylic dianhydride. A resin component of an amine which is a solvent component of a pyrrolidone compound containing N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone. 2. The liquid crystal alignment treatment agent according to the above 1, wherein the pyrrolidone compound is N-ethyl-2-pyrrolidone, and the N-ethyl-2-pyrrolidone is 5 to 80% by mass of the solvent component. The liquid crystal alignment treatment agent according to the above 1, wherein the pyrrolidone compound is N-cyclohexyl-2·pyrrolidone, and the N-cyclohexyl-2-pyrrolidone is a solvent component of 5 to 40 mass. %. 4. The liquid crystal alignment treatment agent according to any one of the above 1 to 3, which contains a resin component of 1 to 10% by mass and a solvent component of 90 to 99% by mass.

The liquid crystal alignment treatment agent according to any one of the above 1 to 4, wherein the diamine component has a disubstituted amino group diaminobenzene substituted with an alkenyl group having 2 or 3 carbon atoms. (6) The liquid crystal alignment treatment agent according to the above 5, wherein the diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms is a diamine represented by the following formula [1]; 〕

7. The liquid crystal alignment treatment agent according to the above 6, wherein the diamine component further contains a diamine represented by the following formula;

[32] (In the above formula, k is not an integer from 1 to 20). 8. The liquid crystal alignment treatment agent according to the above 6, wherein the diamine represented by the formula [" contains 20 to 90 mol% in the total diamine component. -8 - 201011421 9. The liquid crystal alignment agent according to the above 8, wherein the diamine contains 5 to 40 mol% of the total diamine component, and is characterized by a liquid crystal alignment film. The liquid crystal alignment treatment agent according to any one of the above is obtained by firing a base cloth with an electrode. A liquid crystal display element characterized by having a liquid crystal alignment film loaded thereon. Φ The liquid crystal alignment treatment agent of the present invention can obtain an electrical property alignment film and can suppress the occurrence of agglomerates which become gaps in the liquid crystal panel during printing, so that a narrow gap crystal panel can be produced with good yield. A detailed description of the present invention is as follows. The liquid crystal alignment treatment agent of the present invention forms a treatment agent for a liquid crystal liquid crystal alignment film, which comprises a polyφ N-ethyl-2- which is obtained by imidating a polyamic acid obtained by reacting a dicarboxylic acid dianhydride. Pyrrolidone or N-cyclohexyl-2-pyrrolidone. The structure of the polyimine used is not particularly limited, and a diamine component and a tetracarboxylic dianhydride using a diamine group having a disubstituted amino group substituted with 2 or 3 alkenyl groups as a specific diamine are used. When the polyamidene obtained by imidization of the component is obtained by imidization, the solubility of the organic solvent is particularly preferable. [Diamine component] The diamine component used in the present invention (may be referred to as a liquid display having a high dependence on the liquid crystal unevenness which is well described in the description of the coating on the plate in the above paragraphs 32 to 9) The amine component of the element and the tetrakilylimine, and the carbon benzene (hereinafter referred to as the amine can be improved by the reaction) are not limited to the specific amine. The diamine may be one kind or used. The type of the plural kinds is not limited. Examples of the type of the diamine include an alicyclic diamine, an aromatic diamine, a heterocyclic diamine or an aliphatic diamine. Specific examples thereof are shown below. Examples of the cyclic diamine include fluorene, 4-diaminocyclohexanyl, diaminocyclohexane, 4,4,-diaminodicyclohexylmethyl, 4,4'-diamino group. - 3,3,-dimethyldicyclohexylamine, and isophorone diamine, etc. Examples of the aromatic diamines include fluorene-phenylenediamine and m-phenylenediamine. , p-phenylenediamine' 2,4-diaminotoluene, 2,5.diamine φ-methyltoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxy Benzene, 2,5-diamino-P- Xylyl, 1,3 -diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamine 1,2-diphenylethane, 4,4,-diamino-2,2'-dimethylbiphenylmethyl, 4,4'-diaminodiphenylmethane, 3,3 ,-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethyl, 4,4,-diamino-3,3'-dimethyldiphenyl, 2,2 '-Diamino symmetrical diphenyl phenanthrene, 4,4,-diamino symmetrical diphenyl styrene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenyl sulfide. 4,4,-diaminodiphenyl maple, 3,3,-diaminodiphenyl milling, 4,4'_ Aminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, anthracene, 3·bis(4-aminophenoxy)benzene, 1,4-bis(4-aminobenzene) Oxy)benzene, 3,5.bis(4-aminophenoxy)benzoic acid, 4,4,-bis(4-aminophenoxy)biphenylmethyl, 2,2-bis[(4) -aminophenoxy)methyl]propane, 2,2·bis[4-(4.aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl Propane, bis[4-(3-aminophenoxy)phenyl] ruthenium, bis[4·(4-aminophenoxy)phenyl]anthracene, 1,1_bis(4-aminobenzene) Base-10-201011421) cyclohexane, α,α'-bis(4-aminophenyl)-I,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4 -diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoguanidine, 1,3-diaminopurine, 1,6- Diamino hydrazine, 1,8-diamino hydrazine, 2,7-diamino hydrazine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2, 2 '-Dimethylbenzidine, 1,2-bis(4-aminophenylφ)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-amino group) Phenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl) Heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)anthracene Alkane, 1,3-bis(4-aminophenoxy) Alkane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy) Hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy) ) decane Φ, 1,1 〇 bis(4-aminophenoxy)decane 'bis(4-aminophenyl)propane-1,3-diester, bis(4-aminophenyl) Butane-1,4-diester, bis(4-aminophenyl)pentane-1,5-diester, bis(4-aminophenyl)hexane-1,6-diacid Ester, bis(4-aminophenyl)heptane-1,7-diester, bis(4-aminophenyl)octane-1,8-diester, bis(4-aminophenyl) ) decane-1,9-diester, bis(4-aminophenyl)decane-1,10-diester, 1,3-bis[4-(4-aminophenoxy)benzene Oxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy] Pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, -11 - 201011421 1,7-bis[4-(4-aminophenoxy)phenoxy Heptane, 1,8-bis[4-(4-amino) Oxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]decane, 1,1〇-bis[4-(4-aminophenoxy) Phenoxy) decane and the like. _ As an example of the heterocyclic diamine, 2,6-diaminopyridine,

2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole, 2, 4-Diamino-6-isopropyl-I,3,5.triazine, 2,5-bis(4-aminophenyl)_1,3,4-oxadiazole and the like. H. Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane. , i, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, anthracene, 9-diaminodecane, 1,10-diaminodecane, 1,3-Diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethyl Heptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like. In the present invention, as the diamine, in order to increase the solubility of the polyimine in an organic solvent, a diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms is used (hereinafter also referred to as It is preferred for a particular diamine). In particular, it is preferably a 2-propenyl group (hereinafter also referred to as allyl group) represented by the following formula [1]. A substituted disubstituted amino group-diaminobenzene is preferred. -12- 201011421 〔化3〕

m In the diamine represented by the formula [1], the position of each substituent on the benzene ring is not particularly limited, and it is preferred that the two amine group positions are meta or para. Preferred specific examples of the diamine are given below.

The above formula [2] is 2,4-diamino-N,N-diallylaniline, and the above formula [3] is 3,5·diamino-N,N-diallylaniline, the above formula [4] is 2,5-diamino-N,N-diallylaniline. The diaminobenzene is preferably at least one selected from the group consisting of the above [2], [3] and [4].

Among them, those in which the aforementioned diaminobenzene is 2,4-diamino-N,N-diallylaniline are particularly preferred. In the present invention, the diamine component which is a raw material of the polyimine may be one or more of a specific diamine or a combination of a specific diamine and another diamine. When a specific diamine is contained in the diamine component of the polyimine, the solubility of the polyimine in an organic solvent is improved. Further, the problem of damage to the film surface or peeling of the film when the coating film is subjected to rubbing treatment can be improved. The content of the specific diamine in the diamine component is preferably 20 mol% (m〇〇% or more, preferably 40 mol% or more, particularly preferably 50 mol% or more. The specific diamine in the diamine component The higher the content ratio, the higher the effect of the damage or film peeling on the surface of the alignment film from 13 to 201011421 during the rubbing treatment. Moreover, the solubility of the obtained polyimine in the organic solvent is also improved. The amine component may be only a specific diamine, but when a diamine other than a specific diamine is used, it is preferable to impart other characteristics necessary for the liquid crystal alignment film. Therefore, the content of the specific diamine is 90 mol% or less. It is preferred to use the specific diamine and 4-aminobenzylamine, 3-aminobenzylamine, or 4-aminophenethylamine to dissolve the solubility of the polyimine in an organic solvent. A liquid crystal alignment treatment agent which is improved and which has excellent liquid crystal alignment property is particularly preferable. Among the diamine components of 4-aminobenzylamine, 3-aminobenzylamine, or 4-aminophenethylamine The preferred content is 1 〇 mol%~5 0 mol. /. Also, to increase the pretilt angle of the liquid crystal, A diamine having a specific substituent is used. As a substituent which can increase the pretilt angle of the liquid crystal, a long-chain alkyl group, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic group, and a substituent thereof are combined. The steroid skeleton or the like is preferably a specific example of the following diamine having a substituent, but is not limited thereto. In the structure shown below, j represents 5 to 20, preferably 9 to 17. An integer, k represents an integer from 1 to 20', preferably from 4 to 15. 201011421

(CH^CHa (CH2)kCH3 (CH^CHs 0(CH2)kCH3 NH2 o=c OtCH^CHa [6] [7] {8] [9] [10] tm -15- 201011421

-16- 201011421

[21] [22] [23]

[24] [25] [26]

-17- [281201011421 [化8]

[32] [29] [30] [31] Among the above diamines, the diamines of the formulae [5] and [32] are preferred because of their excellent liquid crystal alignment properties. The diamine of the formula [1 2]~[1 9] can be used for 〇CB (Optically Compensated -18- 201011421) because it can greatly improve the tilt performance.

Bend) is used on an alignment film and an alignment film for VA (Vertical Alignment). In a preferred example, the diamine of the formula [5] or [32] contains 5 to 40 mol% of the diamine component in the alignment film of TN (Twisted Nematic) (pretilt 3 to 5°). Preferably, it is 10 to 30 mol%, and the diamine of the formula [12] to [19] contains 5 to 60 m of the diamine component in the alignment film (pretilt 10 to 90°) for OCB and VA. % is preferably 1 〇 to 40 mol%, but is not limited thereto. φ Among the above diamines, the diamine of the formula [3 2] has a high tilt angle, and when used in combination with the above specific diamine, it has excellent liquid crystal alignment even when the friction condition is weak. good. Further, the effect of the above diamine to increase the pretilt angle of the liquid crystal tends to be weak when the liquid crystal alignment agent contains a large amount of N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone, but the formula [ The diamine of 32] is not susceptible to these effects, and can be suitably used as a diamine component of the polyimine contained in the liquid crystal alignment treatment agent of the present invention. [Tetracarboxylic dianhydride component] In the present invention, the tetracarboxylic dianhydride component which is a raw material of the polyimine may be one type of tetracarboxylic dianhydride, or two or more types of tetracarboxylic dianhydride may be used. . However, even a polyimine having a high imidization ratio has an alicyclic ring from the viewpoint of easily obtaining a polyimide having a relatively high solubility and a voltage holding ratio which can increase the liquid crystal cell. A tetracarboxylic dianhydride of a structure or an aliphatic structure is preferred. -19- 201011421 As the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, 1,2,3,4·cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1 are mentioned. , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4- Tetrahydro-1-naphthalene succinic dianhydride, 1,2,3,4·butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid Anhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1, 5-diene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.0''5]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8 - two anhydrate, six rings [6·6·0·12'7·03,6·19,14.01(),13]hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 1, 1,12-dianhydride, etc. As the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, particularly, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4 is used. When tetrahydro-1-naphthalene succinic dianhydride or 1,2,3,4-butane tetracarboxylic dianhydride is obtained, an alignment film excellent in liquid crystal alignment property is particularly preferable. Further, in addition to the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure and the aromatic tetracarboxylic dianhydride, the liquid crystal alignment property can be improved, and the accumulated charge of the liquid crystal cell can be reduced. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyl. Tetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3 ',4-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxy 201011421 phenyl) maple di-anhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like. As an aromatic tetracarboxylic dianhydride, among them, pyromellitic dianhydride, 3,3,4,4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether Anhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride is particularly preferred. A tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, and an aromatic tetracarboxylic acid can be considered in consideration of a balance of solubility of a polyimine, alignment of a liquid crystal, a voltage holding ratio, and an accumulated charge. The ratio of the acid dianhydride to the former/the latter is preferably 90/10 to 50/50, preferably 80/20 to 60/40 ° [polyimine and its production method] The polyimine of the liquid crystal alignment agent of the invention is a polyimide which is imidized by polyamine which is obtained by reacting the above diamine component and a tetracarboxylic dianhydride component. Among them, polylysine can be obtained by mixing a tetracarboxylic dianhydride component and a di-φ amine component in an organic solvent and then reacting them. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, and stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and then directly adding a tetracarboxylic dianhydride component, Or a method of adding or dissolving in an organic solvent, or a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine Method of adding components interactively, etc. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of compounds, it is preferred to carry out the polymerization reaction in a state in which the plurality of components are mixed in advance, and the polymerization reaction may be carried out in an individual order from -21 to 201011421. The temperature at which the tetradecanoic dianhydride component and the diamine component are polymerized in an organic solvent is generally 〇 150 ° C, preferably 5 10 10 (TC, more preferably 10 to 80 ° C. The higher the temperature The polymerization reaction ends sooner, but when it is too high, a polymer having a high molecular weight cannot be obtained. Further, the polymerization reaction can be carried out at any concentration. When the concentration is too low, it is more difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the reaction is too high. The viscosity of the liquid is too high to be uniformly stirred, so the total concentration of the tetracarboxylic dianhydride component and the diamine component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. It is also possible to add an organic solvent after the concentration. The organic solvent used in the above reaction can dissolve only the produced polyamic acid, which is not particularly limited, but may be used for the liquid crystal alignment treatment agent. a component of N-ethyl-2-pyrrolidone or N. cyclohexyl-2-pyrrolidone, or another solvent. Specific examples thereof include N,N-dimethylformamide, N,N-dimethyl Ethylamine, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl飒, tetramethyl urea, pyridine, dimethyl mill, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethylimidazolidone, etc. These can be used alone or in combination. The solvent of the non-polyamine acid can be used in the above solvent in the range where the produced polyamic acid is not precipitated. Further, the water in the organic solvent hinders the polymerization reaction and becomes a polyamine produced by the hydrolysis. For the reason of the acid, the organic solvent is used as much as possible. The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polylysine is preferably 1: 0.8~1 at the molar ratio. : 1.2 is better, the closer the molar ratio is to 1:1, the closer the molecular weight of the obtained poly-proline is. The molecular weight of the poly-proline can be adjusted to adjust the polyimidation. Molecular weight of the quinone imine The molecular weight of the polyimine contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited, but is weight-averaged from the viewpoint of the strength of the coating film and the ease of handling as a liquid crystal alignment treatment agent. Molecular weight of 2,000 to 200,000 is preferred, preferably 5,000 5%. g The imidization of the polyplycosic acid obtained above is carried out in an organic solvent, and the mixture is stirred for 1 to 100 hours in the presence of an alkaline catalyst and an acid anhydride to dissolve. As the basic catalyst, pyridine, three may be mentioned. Ethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferred because it has a moderate basicity for carrying out the reaction. Further, as the acid anhydride, acetic anhydride, trimellitic anhydride, and pyromellitic anhydride may be mentioned. The purification of the obtained polyimine is also easier and preferable after the end of the imidization of acetic anhydride. As the organic solvent, the solvent used in the polymerization of the polylysine described above can be used. The imidization rate of the imine can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The amount of the inert catalyst at this time is 0.2 to 10 times that of the proline group having the poly-proline. The ear is preferred, preferably 0.5 to 5 times Mo. Further, the amount of the acid anhydride is preferably from 1 to 30 moles, more preferably from 1 to 10 moles, per mole of the amidinoic acid group of the polyglycolic acid. The reaction temperature is preferably -20 to 250 ° C, preferably 0 to 180 ° C. The imidization ratio of the polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited, but in view of electrical characteristics, it is preferably 40% or more, and 60% is required for higher voltage retention. The above is preferred, and more preferably 80% -23-201011421 or more. In the solution of the polyimine thus obtained, since the added catalyst or the like remains, the specific polyimine is recovered and washed, and the liquid crystal alignment treatment agent used in the present invention can be preferably used. The polyimine is recovered by adding the imidized solution to a weak solvent to be stirred, and filtering the polyimine. The weak solvent at this time may, for example, be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene or benzene. The recovery of the recovered polyimine can also be carried out by the weak solvent. The polyimine thus recovered and washed can be a powder at normal temperature or under reduced pressure under normal pressure or reduced pressure. [Liquid Crystal Alignment Treatment Agent] The liquid crystal alignment treatment agent of the present invention is obtained by using N-ethyl-2-pyrrolidinium or N-cyclohexyl-2-pyrrolidone as a solvent component when the polyimine is used as a resin component. Contains the solution. In the present invention, as a solvent component, it is necessary to use N·ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone, and when a pyrrolidone compound is used, for example, when N-methyl-2·pyrrolidone is used, as described later, As shown in the examples, there is a case where the coating film is whitened or the film thickness in the vicinity of the printing edge is uneven, and it is difficult to achieve the object of the present invention. The concentration of the solution constituting the liquid crystal alignment agent can be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed. However, the solvent component is preferably 9 to 99 parts by mass for 1 part by mass of the nonvolatile component such as a resin component. Good for 1 1.5 to 49 parts by mass. When the solvent component is more than 99 parts by mass, it is difficult to form a uniform and defect-free coating film from -24 to 201011421. When the amount is less than 9 parts by mass, the stability of the solution may deteriorate. The content of the solvent component in the liquid crystal alignment agent of the present invention is preferably from 90 to 99% by mass, preferably from 92 to 98 parts by mass, based on the total amount of the liquid crystal alignment treatment agent. The resin component in the liquid crystal alignment agent of the present invention may be a mixture of two or more kinds of polyimines having different structures. It can use polylysine or other species to the extent that it does not impair the electrical properties and does not reduce the preservation stability of the varnish, and does not cause agglomeration of the liquid crystal panel gap during printing. Resin. The amount of the resin to be used is preferably 0.05 to 7 parts by mass, more preferably 0.1 to 4 parts by mass, per part by mass of the polyamidene. In the liquid crystal alignment agent of the present invention, the content of the resin component is preferably from 1 to 10% by mass, preferably from 2 to 8% by mass based on the total of the liquid crystal alignment treatment agent. The solvent component in the liquid crystal alignment agent of the present invention may be only N-ethyl-2-pyrrolidone. However, it is preferred to contain other solvents in order to ensure or control the coating property to the reference substrate in order to improve the solubility of the resin component. On the other hand, in the case of N-cyclohexyl-2-pyrrolidone, the solubility of polyimine is inferior to that of N-ethyl-2-pyrrolidone, and therefore, from the viewpoint of long-term storage stability of the liquid crystal alignment treatment agent, It is preferable that the content is 40% by mass or less based on the entire solvent component, and the solvent may be contained as the other solvent component to ensure the solubility of the resin component. Examples of the solvent for ensuring the solubility of the resin component include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylhexene. Indoleamine, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl-25- 201011421 sub-milling, tetramethyl urea, dimethyl milling, hexamethyl argon, γ-butyrolactone, 1,3-two Methyl-imidazole and the like. Among them, hydrazine-methyl-2-pyrrolidone, 1,3-dimethylimidazolidone, and γ-butyrolactone are preferred because of their high solubility. Further, r-butyrolactone is suitable for use because it has an effect of suppressing whitening. The solvent used for controlling the applicability to the substrate is a solvent having a low surface tension. When the solvent component is moderately mixed with a solvent having a low surface tension, the uniformity of the coating film can be improved when the substrate is applied. Examples of the solvent having a low surface tension include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1-methoxy 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, diethylene glycol diethyl ether, propylene glycol Monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol '2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. Among them, butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether is particularly preferred from the viewpoint of coatability to the substrate. When the solvent component contains the above-mentioned other solvent, the amount of the oxime-ethyl-2-pyrrolidone or the oxime-cyclohexyl-2-pyrrolidone can be suppressed when the amount is 0.5 parts by mass or more based on 1 part by mass of the resin component. The effect of improving the generation of the aggregate is preferably 1 part by mass or more and 80 parts by weight or less, preferably 2 parts by mass or more and 70 parts by weight or less. In particular, oxime-ethyl-2-pyrrolidone is excellent in storage stability of varnish because it has excellent solubility in resin composition, and it is suitable for use because it is less likely to cause varnish whitening even if moisture absorption. In the present invention, the content of N-ethyl--26-201011421 2-pyrrolidone is preferably from 5 to 80% by mass based on the total of the solvent component, preferably from 10 to 70% by mass. On the other hand, the content of the N-cyclohexyl-2-pyrrolidone is preferably from 5 to 40% by mass based on the total of the solvent component, preferably from 10 to 30% by mass. In addition, as described above, it is preferable that N-ethyl-2-pyrrolidone is used as the solvent component of 40% by mass or less, from the viewpoint that the effect of the diamine which improves the pretilt angle of the liquid crystal is not weakened. In addition, when the amount of the solvent to ensure the solubility of the resin component is too large, the φ lacquer may be whitened or foreign matter may be generated during printing. Therefore, the content thereof is preferably 80% by mass or less, preferably 60% by mass of the solvent component. %the following. The solvent having a low surface tension can improve the coating property to the substrate. When the amount is too large, precipitation of the resin component occurs. Therefore, the content is preferably 60% by mass or less, preferably 50% by mass or less, based on the solvent component. . When a solvent which ensures the solubility of the resin component and a solvent having a low surface tension are used in combination, the solvent is preferably contained in an amount of 5 to 70% by mass, and the solvent having a low surface tension is used as a solvent to ensure solubility of the resin component. The preferred amount of the solvent which ensures the solubility of the resin component is from 1 to 45% by mass, and the solvent having a low surface tension is from 20 to 50% by mass. In the liquid crystal alignment treatment agent of the present invention, the solvent composition is 5 to 80% by mass, and the solvent for ensuring the solubility of the resin component is 5 to 70% by mass, which is low. The solvent of the surface tension is a mixed solvent of 10 to 60% by mass; the solvent of N-ethyl-2-pyrrolidone is 10 to 70% by mass, and the solvent for ensuring the solubility of the resin component is 1 〇 to 45% by mass, and has a low surface tension. The solvent is a mixed solvent of 20 to 50% by mass; the N-ethyl-2-pyrrolidone is 5 to 40% by mass, and the solubility of the resin component is ensured to be -27 to 201011421. The solvent is 5 to 70% by mass, and has a low surface tension. The solvent is a mixed solvent of 10 to 60% by mass: N-ethyl-2-pyrrolidone is 10 to 40% by mass, the solvent for ensuring the solubility of the resin component is 10 to 45% by mass, and the solvent having a low surface tension is 20 ~50% by mass of a mixed solvent; N-cyclohexyl-2-pyrrolidone is 5 to 40% by mass, a solvent for ensuring solubility of a resin component is 5 to 70% by mass, and a solvent having a low surface tension is 10 to 60% by mass. Mixed solvent; N-cyclohexyl-2-pyrrolidone is 10 The solvent having a solubility of the resin component of 40 to 4 mass% is 10 to 45 mass%, and the solvent having a low surface tension is 20 to 50 mass% of a mixed solvent. The liquid crystal alignment agent of the present invention may contain an additive for improving the film properties other than the above. Examples of the additive for improving the properties of the coating film include 3-aminopropylmethyldiethoxydecane, 3-phenylaminopropyltrimethoxydecane, and 3-aminopropyltriethoxydecane. A decane coupling agent such as (aminoethylaminomethyl) phenethyltrimethoxydecane. By the addition of these decane coupling agents, the adhesion to the coating film of the substrate can be further improved, but when added too much, the polyimine used in the present invention or the polymer compound used in the present invention can be agglomerated. the reason. Therefore, the content of the decane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per part by mass of the resin component used in the present invention. [Preparation method of liquid crystal alignment treatment agent] The preparation method of the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is present in a uniform state in the liquid crystal alignment treatment agent, and is not particularly limited to -28-201011421. An example of this is a method in which a powder of polyimine is dissolved in an organic solvent to form a polyimine solution, and an organic solvent is added to a desired concentration. In the dilution step, adjustment of the solvent composition for controlling the coating property to the substrate, addition of an additive for improving the coating film property, and the like can be performed. The solvent for dissolving the polyimide pigment powder may, for example, be N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone or the above solvent. It is preferred that the liquid crystal alignment treatment agent obtained above is filtered before being applied onto a substrate. % The liquid crystal alignment treatment agent of the present invention is applied to a substrate, and can be used as a coating film after drying and baking, and can be used as a liquid crystal alignment film for rubbing by rubbing the surface of the coating film. Further, it can be used as a liquid crystal alignment film for VA which is not rubbed or as a photo alignment film. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used, and an ITO electrode to be driven by a liquid crystal can be used. When the substrate is used, it is preferable from the viewpoint of simplification of the process. Further, in the reflective liquid crystal display device, an opaque substance such as a germanium wafer can be used only for the substrate on the chip side, and a material such as aluminum which can reflect light can be used as the electrode. Examples of the coating method of the liquid crystal alignment treatment agent include a spin coating method, a printing method, and an ink jet method. From the viewpoint of productivity, a quick-drying printing method is widely used in the industry, and the liquid crystal alignment treatment agent of the present invention is used. Also applicable. The drying step after the application of the liquid crystal alignment agent is not necessary, but it is preferable to include a drying step when the time from the application to the baking is not constant for each substrate or when the non-horse is baked after the application. This drying can be carried out by simply transferring the solvent to the extent that the shape of the coating film is not deformed by the substrate, and the drying means is not particularly limited to -29 to 201011421. Specific examples thereof include a method of drying on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes. The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of from 1 3 to 3 50 ° C, preferably 15 (TC to 300 ° C, more preferably 180 ° C to 2 50 °). C. When a proline group is present in the liquid crystal alignment treatment agent, the firing temperature can be changed from valeric acid to imine, but the liquid crystal alignment treatment agent of the present invention does not need to be 100% imidized. _ Coating after firing When the film thickness is too thick, it is disadvantageous in view of the power consuming surface of the liquid crystal display element. When the film thickness is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 10 to 200 nm, more preferably 50 to 100 nm. As the above-mentioned rubbing treatment of the coating film surface formed on the substrate, an existing friction device can be used. Examples of the material of the rubbing cloth at this time include cotton, enamel, nylon, etc. The liquid crystal display element of the present invention is as described above. After obtaining a substrate having a liquid crystal alignment film from the liquid crystal alignment agent of the present invention, a liquid crystal cell is produced by a known method as a liquid crystal display element. A liquid crystal cell is formed by a liquid crystal alignment film. Preferably, the substrate is sandwiched between 1 and 30 μm, more preferably 2~ The spacer of Ομιη is set to any angle of 0 to 270° in the direction of alignment treatment, and is fixed by a sealing agent around the inside, and the method of sealing after injecting liquid crystal is generally used. There is no particular limitation on the method of sealing the liquid crystal, and the reduction is exemplified. After pressing the liquid crystal cell, the vacuum method of injecting the liquid crystal, dropping the liquid crystal, and dropping the liquid crystal, etc. The liquid crystal display element thus obtained can be applied to a liquid crystal display element. 30-201011421, STN liquid crystal display element, TFT The liquid crystal display element and the 〇CB liquid crystal display element are further used for various types of display elements such as a horizontal electric field type liquid crystal display element and a VA liquid crystal display element. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the contents of the present invention. The abbreviations used in the examples and comparative examples are as follows. <tetracarboxylic dianhydride> CBDA: 1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

p-PDA : p_phenylenediamine DDM: 4,4'-diaminodiphenylmethane BAPP : 1,5-bis(4-aminophenoxy)pentane C12DAB : 4-dodecane Methoxy-1,3-diaminobenzene-31 - 201011421 C14DAB: 4-tetradecyloxy-1,3-diaminobenzene C18DAB: 4-octadecyloxy-1,3 -di Aminobenzene PCBA-PDA: 4-(t-4 -pentylcyclohexyl)benzamide 2.2,4·-phenylenediamine (1 〇)

3-ΑΒΑ : 3-aminobenzylamine <organic solvent> NMP : Ν-methyl-2-pyrrolidone NEP : Ν-ethyl-2-pyrrolidone NCP: Ν-cyclohexyl-2-pyrrolidone yBL : Γ-buty vinegar

DMI : 1,3-dimethylimidazolidone Q BC : butyl cellosolve DPM : dipropylene glycol monomethyl ether EC : ethyl carbitol < determination of molecular weight > The molecular weight of polyimine is 'this poly The imine was measured by a GPC (normal temperature gel permeation chromatography) apparatus. The number average molecular weight and the weight average molecular weight in terms of polyethylene glycol and polyethylene oxide were calculated. -32- 201011421 GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: made by Shodex (inline of KD803, KD805)

Column temperature: 50 °C Dissolved solution · N,N-dimethylformamide (as additive, lithium bromide _ hydrate (LiBr.H2〇) is 30mmol/L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) is l〇mi/L) Flow rate: 1.0 mL/min. Measured wire for standard sample: TSK standard polyethylene oxide manufactured by Tosoh Co., Ltd. (weight average molecular weight about 900,000, 1 50,000, 1 〇〇, 〇〇〇, 3 0,000), and polyethylene glycol (weight average molecular weight of about 12,000, 4,000, 1, 〇〇〇) manufactured by Polymer Laboratories. <Measurement of imidization ratio> The imidization ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube, and 3% crude dimethyl sulfite (# DMSO-d6 '〇.〇5% TMS mixture) 〇.53 mL was added to completely dissolve it. This solution was measured for proton NMR at 500 MHz by a NMR measuring instrument (JNM-ECA500) manufactured by JEOL Ltd. The imidization ratio is determined by using a proton obtained from a structure having no change before and after imidization as a reference proton, and a proton of the proton is used to calculate a ruthenium and a proton of an NH group derived from a valeric acid present near 9.5 to 10.0 ppm. The peak product is obtained by the following formula. Imidization rate (%) = ( 1 -α · x/y ) X 1 00 -33- 201011421 In the above formula, X is the proton peak product 値 from the NH group of proline, and y is the peak total of the reference proton値, α is the ratio of the number of protons of the proline to the reference proton of one ruthenium matrix in the case of polyproline (0% imidization). (Synthesis Example 1) As a tetracarboxylic dianhydride component, CBDA 13.53 g (0.0 6 9 mol ) 'PMDA 6.54 g (0.030 mol) was used, and as a diamine component, 2,4-DAA 6.10 g (0.03 0 mol ) and 3 were used. - ABA 4.89 g (0.040 mol), C14DAB 9.62 g (0.030 mol), and NMP 162.7 g were reacted at 23 ° C for 24 hours to obtain a polyaminic acid solution. To 142.8 g of the polyamic acid solution, 3.2 g of NMP 3 3 was added and diluted, and 21.5 g of acetic anhydride and 9.2 g of pyridine were added thereto, and the mixture was reacted at 50 ° C for 3 hours to imidize. After the reaction solution was cooled to room temperature, it was put into 1.8 L of methanol to recover the precipitated solid matter. Further, the solid matter was washed several times with methanol, and then dried under reduced pressure at a temperature of °C to obtain a white powder of polyimine (SPI). The polyimine had a number average molecular weight of 13,472 and a weight average molecular weight of 35,859. Further, the imidization ratio was 89% (Synthesis Example 2) 131.3 g of rBL was added to 17.9 g of the polyimine obtained in the same manner as in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the 201041021, the polyimine is completely dissolved. (Synthesis Example 3) 1.6 g of the polyimine obtained in the same manner as in Synthesis Example 1 was added to NEP 1 4.4 g, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. φ (Synthesis Example 4) 14.4 g of NMP was added to 1.6 g of the polyimine obtained in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyamidene was completely dissolved. (Synthesis Example 5) 8 g of t*BL and 6.4 g of NCP were added to 1.6 g of the polyamidene obtained in Synthesis Example 1, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine is completely dissolved. (Synthesis Example 6) As a tetracarboxylic dianhydride component, CBDA 13.53 g (0.069 mol) > PMDA 6.54 g (0.030 mol) was used, and as a diamine component, 2,4-DAA 7.12 g (0.035 mol) and 3 were used. -ABA 4.89g (0.040mol),

PCBA-PDA 1 0.1 9 g (0.025 mol) and NMP 1 6 9 · 1 g were reacted at 23 ° C for 24 hours to obtain a polyaminic acid solution. To 150 g of the polyamic acid solution, 350 g of NMP was added and diluted, and 21.74 g of -35-201011421 acetic anhydride and 9.27 g of pyridine were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours. The reaction solution was cooled to room temperature, and then poured into 1.86 L of methanol to recover a precipitated solid. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 10 ° C to obtain a white powder of polyimine (SPI). The polyimine had a number average molecular weight of 12,156 and a weight average molecular weight of 32,418. Further, the imidization ratio was 90%. (Synthesis Example 7) 35.2 g of r BL was added to 4.8 g of the polyimine obtained in the same manner as in Synthesis Example 6, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. (Synthesis Example 8) As a tetracarboxylic dianhydride component, TDA 15.01 g (0.05 mol) was used, and as a diamine component, p-PDA 4.87 g (0.045 mol), C18DAB 1.88 g (0.005 mol), and NMP 123.3 g were used. In, at 50. . A polyaminic acid solution was obtained after the next 24 hours of reaction. To the polyamic acid solution, N 50 3 50 g was added and diluted, and 51.0 g of acetic anhydride and 23.7 g of pyridine were added thereto, and the mixture was subjected to a reaction at 40 ° C for 3 hours to imidize it. After cooling the reaction solution to room temperature, it was poured into 1.7 L of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (201011421 SPI). The polyimine had a number average molecular weight of 9,273 and a weight average molecular weight of 18,815. Further, the imidization ratio was 84%. (Synthesis Example 9) 94.0 g of NEP was added to 6.0 g of the polymerized amine obtained in the same manner as in Synthesis Example 8, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. (Synthesis Example 1 〇) As a tetracarboxylic dianhydride component, CBDA 4.9 〇g (〇.〇25 mol )' PMDA 4.80 g (0.022 mol) was used, and as a diamine component, DDM 9.91 g (0.05 mol) &gt; NEP was used. In a mixed solvent of 55.5 g' yBL 55.5 g, the reaction was carried out for 5 hours at room temperature to obtain a polyaminic acid solution. The number average molecular weight of the polyamic acid was 11, 〇67, and the weight average molecular weight was 26,270 ° ❹ (Synthesis Example 1 1 ). NEP, BC was added to 50 g of the polyamidic acid solution obtained in Synthesis Example 10, and the mixture was adjusted to polyfluorene. The amine acid was 6 mass%, the NEP was 59 mass%, the γ-BL was 20 mass%, and the BC was 15 mass%. (Synthesis Example 1 2 ) As a tetracarboxylic dianhydride component, TDA 15.0 1 g (0.05 mol ) ' was used as a diamine component, and p-PDA 2.70 g (0.025 mol) ' 2,4- •37-201011421 DAA 3.05g was used. (0.0 1 5 mol ) 'PCBA-PDA 4.08g (O.Olmol), NMP 140.8g, obtained by reacting at 50 ° C for 24 hours to obtain a polyaminic acid solution. To the polyamic acid solution, 331 g of NMP was added and diluted, and 51.0 g of acetic anhydride and 23.7 g of pyridine were added thereto, and the mixture was reacted at 40 ° C for 3 hours to imidize. The reaction solution was cooled to room temperature, and then poured into 2.0 L of methanol to recover a precipitated solid. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (SPI). The polyimine had a number average molecular weight of 8,579 and a weight average molecular weight of 22,3 19 . Further, the imidization ratio was 87%. (Synthesis Example 1 3) 96.0 g of τ BL was added to 6.0 g of the polyimine obtained in the same manner as in Synthesis Example 12, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. (Synthesis Example 1 4) r BL and BC were added to 5 μg of the polyamidic acid solution obtained in Synthesis Example 10 to prepare a polyglycine of 6 mass% and γΒ of 59 mass%, and NEP was 20 mass%. BC is 15 mass%. (Synthesis Example 15) As a tetracarboxylic dianhydride component, CBDA 19.41 g (〇. 9 9 mol 201011421 ) was used, and as a diamine component, BAPP 5.73 g (0.02 mol) and 2,4-DAA 14.23 g (0.07) were used. Mol) &gt; PCBA-PDA 4.08g (O.Olmol) 'NMP 246.2g, 24 hours reaction at 23 ° C to obtain a poly-proline solution. 4 g of NMP 43 was added to the polyamic acid solution and diluted, and 25.8 g of acetic anhydride and ll. Og of pyridine were added thereto, and the mixture was subjected to a reaction at 35 ° C for 3 hours to imidize. φ The reaction solution was cooled to room temperature, and then poured into 2.7 L of methanol to recover a precipitated solid. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 10 ° C to obtain a white powder of polyimine (SPI). The polyimine had a number average molecular weight of 12,132 and a weight average molecular weight of 26,538. Further, the imidization ratio was 70%. (Synthesis Example 16) In 12.0 g of the polyimine obtained in the same manner as in Synthesis Example 15, 108.0 g of NEP was added thereto, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the end of the agitation, the polyimine was completely dissolved. (Synthesis Example 1 7) As a tetracarboxylic dianhydride component, 19.41 g (0.09 9 mol) of CBDA was used, and as a diamine component, 2,4-DAA 14.23 g (0.07 mol) and C12DAB 8.77 g (0.03 mol), NMP were used. In 169.7 g, a polyamine acid solution was obtained after 24 hours of reaction at 2 3 〇C. To the polyamic acid solution, 494.9 g of NMP was added and diluted, and -0.6-201011421 acetic anhydride 30.6 g and pyridine 13-lg were added, and the mixture was imidized at a temperature of 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 2.6 L of methanol, and the precipitated solid matter was collected. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (SPI). The polyimine had a number average molecular weight of 11,09 8 and a weight average molecular weight of 21,431. Further, the imidization ratio was 91%. (Synthesis Example 18) 14.6 g of NEP was added to 1.6 g of the polyimine obtained in the same manner as in Synthesis Example 17, and the mixture was stirred at a temperature of 5 (TC) for 24 hours. At the end of the stirring, the polyimine was completely dissolved. Example 1) After cooling 20.23 g of the solution obtained in the same manner as in Synthesis Example 2 to 23 ° C, 8.67 g of TBL, 4.93 g of NEP, and 14.78 g of BC were added, and the mixture was stirred at a temperature of 5 ° C for 20 hours. After that, it was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the obtained liquid crystal alignment treatment agent is shown in Table 1. <Evaluation of Voltage Retention Rate> For the above liquid crystal alignment treatment agent, liquid crystal cells were subjected to the following Evaluation of the voltage holding ratio. The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode for -40 to 201011421, and dried at 70 ° C for 7 seconds on a hot plate of TC. The hot plate was fired for 10 minutes to form a film having a film thickness of ι〇〇ηπι. The film surface was rubbed with a roll diameter of 12 mm, and the roll was rotated at 1000 rpm, and the roll was rotated at a speed of 50 mm/ Sec, the amount of impregnation is 〇.3mm, and the friction is obtained. A substrate with a liquid crystal alignment film is prepared. Two substrates are prepared, and a spacer of 6 μm is dispersed on the surface of the liquid crystal alignment film. The upper sealing substrate is bonded to the other substrate to bond the liquid crystal to the film surface. After the rubbing direction is straight, the sealing agent is hardened to produce a hollow cell. The liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) is injected into the hollow cell by a reduced pressure injection method, and the injection port is sealed to obtain a twist. In the liquid crystal cell, a voltage of 16.7 ms is applied at a temperature of 90 ° C, and a voltage of 16.67 ms is measured, and a voltage holding ratio at which the voltage can be maintained is calculated. A VHR-1 voltage retention rate measuring device manufactured by Toyo Denki Co., Ltd. was used. The evaluation results are shown in Table 2. &lt;Measurement of Tilt Angle&gt; The liquid crystal cell obtained by the same &lt;Production of Liquid Crystal Cell&gt; The tilt angle of the liquid crystal was measured. The measurement was performed using TBA107 manufactured by Autronic Co., Ltd. The measurement was carried out under the conditions of heating (23 t) and maintaining the liquid crystal cell at 60 ° C. The results are shown in Table 3. &lt;Weak friction Evaluation of liquid crystal alignment> In the above <Evaluation of Voltage Retention Rate>, the rubbing roller is changed to -41 - 201011421 0.2mm, and the rubbing direction is changed to 180° (anti-parallel), and the substrate is bonded under the same conditions. Liquid crystal cell. At this time, the presence or absence of the liquid crystal alignment of the liquid crystal cell was observed after the liquid crystal injection, and the following evaluation was performed. 〇: No flow alignment was observed. Δ: Flow alignment was slightly observed. X: Most strip flow alignments were observed. The evaluation results are shown in Table 3. &lt;Evaluation of Friction Resistance&gt; With respect to the above <Evaluation of Voltage Retention Rate>, the rubbing roller was rubbed to a condition of 0.5 mm to form a substrate with a liquid crystal alignment film. The surface of the liquid crystal alignment film was observed under a laser-microscope, and the following evaluation was carried out under visual observation. 〇: There is almost no slag or frictional damage. X: Slag is generated or there is a frictional injury. The evaluation results are not shown in Table 3. &lt;Evaluation of Drying Speed&gt; On the glass substrate (hereinafter referred to as Cr substrate) on which the liquid crystal alignment treatment agent was subjected to chromium vapor deposition (size l〇cm X 10 cm), spin coating was applied to the film thickness l〇 〇nm. Thereafter, at a temperature of 23 ° C and a humidity of 45%, the time from the completion of the spin coating to the uniform drying of the film was measured. The result is 3 40 seconds. -42 - 201011421 &lt;Evaluation of whitening characteristics&gt; The above liquid crystal alignment treatment agent was dropped into about 0.1 mL on each of the Cr substrates, and placed in an environment of a temperature of 23 ° C and a humidity of 45%. The microscope was observed every hour near the end of the droplet and near the center. Further, the vicinity of the end of the droplet was 100 times, and the vicinity of the center of the droplet was observed at a magnification of 50 times. When the agglomerates are seen at the end of the droplet and near the center within 6 hours, it is X, and even if it is not seen after 6 hours, it is 〇. The results are shown in Table 2. Φ &lt;Evaluation of Printing Unevenness&gt; Using an alignment film printer ("Angstromer" manufactured by Nippon Photo Printing Co., Ltd.) on a Cr substrate washed with the liquid crystal alignment agent and performing quick-drying printing (flow time 30 seconds) . After the first operation of the first time, the printing was started, and the printed substrate of the first film was used for observation. The printed substrate was placed on a hot plate at 80 ° C for 5 minutes to perform pseudo-drying of the film. The vicinity of the printed edge after the pseudo-drying was observed by an optical microscope ("Φ ECLIPSE ME600" manufactured by Nicon Corporation) at 50 times, and the film thickness was not caused by 不, and the generator was X. The results are shown in Table 2. &lt;Evaluation of foreign matter at the time of printing&gt; Printing was carried out using the same apparatus as described above. The printing press was stopped 1 minute after the implementation of 10 air transports, and the printing plate was dried. Thereafter, one Cr substrate was printed and fired in the same manner as described above. The fired substrate was observed near the printing edge by a confocal laser microscope ("VL2000" manufactured by Laser Dick Co., Ltd.), and no foreign matter of 3 μm or less was generated near the printing edge. -43- 201011421 Produced by X. The results are shown in Table 2. &lt;Evaluation of Preservation Stability&gt; The liquid crystal alignment treatment agent was kept at -2 ° C for 2 months, and the white turbidity in which no precipitation or varnish was produced was 〇, and the white turbidity of precipitation and varnish was x. (Example 2) 21.00 g of the solution obtained in the same manner as in Synthesis Example 2 was cooled to 23 ° C, and then rBL 3 - 87 g, NEP 10.21 g, and BC 15.32 g' were added and stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the obtained liquid crystal alignment treating agent is summarized in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. (Example 3) 18.77 g of the solution obtained in the same manner as in Synthesis Example 2 was cooled to 23 ° C, and then rBL 7.08 g, NCP 4.80 g, and BC 14.40 g were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the obtained liquid crystal alignment treating agent is summarized in Table 1. Using the liquid crystal alignment treatment agent, the voltage -44 - 201011421 retention rate, inclination angle, liquid crystal alignment, friction resistance, drying speed, whitening characteristics, uneven printing, foreign matter during printing, and storage stability were carried out in the same manner as in Example 1. Evaluation. The results are shown in Table 2 and Table 3. (Example 4) The solution I9.49 g obtained in the same manner as in Synthesis Example 2 was cooled to 23 ° C, and then rBL 3.28 g, NCP 9.60 g, and BC 14.40 g were added, and the mixture was stirred at a temperature of 50 ° C φ for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. 〇 (Example 5) After the solution obtained in the same manner as in Synthesis Example 3 was cooled to room temperature, 2.66 g of NEP and 8.00 g of BC were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. -45-201011421 (Example 6) After 20 g of the solution obtained in the same manner as in Synthesis Example 7, 8.8 g of r BL, 4.8 g of NEP, and 14.4 g of BC were added to the mixture for 20 hours. After the completion of the stirring, the liquid crystal alignment treatment agent is cooled. It is known that the liquid crystal alignment process is shown. The liquid crystal alignment treatment agent was used, and the retention ratio, the inclination angle, the liquid crystal alignment property, the friction resistance characteristics, the printing unevenness, the foreign matter at the time of printing, and the storage results are shown in Table 2 and Table 3. (Example 7) After 20 g of the solution obtained in the same manner as in Synthesis Example 7, 20 g of r BL, 14.4 g of NEP, and 9.6 g of BC were added thereto, followed by stirring for 20 hours. After the completion of the stirring, the liquid crystal alignment treatment agent is cooled. It is known that the liquid crystal alignment process is shown. The liquid crystal alignment treatment agent used in Example 1 and the retention ratio, the inclination angle, the liquid crystal alignment property, the friction resistance characteristics, the printing unevenness, the foreign matter at the time of printing, and the storage results are as described in Tables 2 and 3. (Example 8) The composition of the homogeneous agent was obtained after cooling to room temperature at 23 ° C at a temperature of 50 ° C. The evaluation of voltage Q, drying speed, and whiteness was carried out in the same manner as in Table 1. The temperature was cooled to room temperature. The composition of the homogeneous G agent was obtained at 23 °C at a temperature of 50 °C. The evaluation of voltage, drying speed and whiteness was carried out in the same manner as in Table 1. -46-201011421 20 g of the solution obtained in Synthesis Example 9 and 8 g of the solution obtained in Synthesis Example 11 were stirred at 23 ° C for 20 hours. After the completion of the stirring, a uniform liquid crystal alignment treatment agent is obtained. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. Φ (Example 9) 20 g of the solution obtained in Synthesis Example 13 and 8 g of the solution obtained in Synthesis Example 14 were stirred at 23 ° C for 20 hours. After the completion of the stirring, a uniform liquid crystal alignment treatment agent was obtained. The composition of the liquid crystal alignment treatment agent was as shown in Table 1. Using the liquid crystal alignment treatment agent, voltage holding ratio, tilt angle, liquid crystal alignment property, friction resistance, drying speed, white Φ characteristics, and the like were carried out in the same manner as in Example 1. Uneven printing, foreign matter during printing, and evaluation of preservation stability. The results are shown in Table 2 and Table 3. (Example 1 〇) After cooling 60 g of the solution obtained in the same manner as in Synthesis Example 16 to room temperature, 20 g of DM1 and 20 g of EC were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 t to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using the liquid crystal alignment treatment agent, the voltage-47-201011421 retention ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, uneven printing, foreign matter during printing, and storage stability were carried out in the same manner as in Example 1. Evaluation. The results are shown in Table 2 and Table 3. (Example 1 1) 60 g of the solution obtained in the same manner as in Synthesis Example 16 was cooled to room temperature, and then 10 g of NMP and 30 g of BC were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. (Example 1 2) The solution obtained in the same manner as in Synthesis Example 18 was cooled to room temperature. Then, 2.66 g of NEP and 8.0 g of BC were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. In the same manner as in Example 1, the liquid crystal alignment treatment agent was used to evaluate the voltage holding ratio, the inclination angle, the liquid crystal alignment property, the friction resistance, the drying speed, the whitening characteristics, the printing unevenness, the foreign matter at the time of printing, and the storage stability. The results are shown in Table 2 and Table 3. -48-201011421 (Comparative Example 1) The solution obtained in the same manner as in Synthesis Example 4 was cooled to 23. (: After adding 2.66 g of NMP and 8.00 g of BC, stirring was carried out for 20 hours at a temperature of 50 ° C. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the obtained liquid crystal alignment treatment agent was summarized. In the same manner as in Example 1, the liquid crystal alignment treatment agent was used to carry out voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, white Φ characteristics, uneven printing, foreign matter during printing, and preservation. Evaluation of the stability. The results are shown in Tables 2 and 3. Although no foreign matter was observed, whitening and uneven film thickness were observed. (Comparative Example 2) 19.49 g of the solution obtained in the same manner as in Synthesis Example 2 was cooled to After 23 ° C, 3.28 g of rBL, 9.60 g of NMP, and 14.40 g of BC were added, and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 23 ° C to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is as shown in Table 1. Using the liquid crystal alignment treatment agent, voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, and printing unevenness were performed in the same manner as in Example 1. Print Evaluation of foreign matter and preservation stability at the time of brushing. The results are shown in Tables 2 and 3. The whitening characteristics were good. No foreign matter was observed, but film thickness unevenness was observed. (Comparative Example 3) -49- 201011421

19.49 g of the solution obtained in the same manner as in Synthesis Example 2 was cooled to 23 ° C, and then rBL 9.03 g, BC 9.13 g, and DPM 9.13 g' were added and stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the mixture was cooled to 231 to obtain a uniform liquid crystal alignment treatment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. Using this liquid crystal alignment treatment agent, evaluation of voltage holding ratio, inclination angle, liquid crystal alignment property, friction resistance, drying speed, whitening characteristics, printing unevenness, foreign matter at the time of printing, and storage stability were carried out in the same manner as in Example 1. The results are shown in Table 2 and Table 3. The whitening characteristics were good, but the film thickness was uneven, and foreign matter was also observed. (Example 1 3) The solution obtained in the same manner as in Synthesis Example 5 was cooled to room temperature, and then NCP 6.40 g and BC 9.60 g' were added and the mixture was stirred at a temperature of 50 ° C for 20 hours. After the completion of the stirring, the film was cooled to 23 ° C to obtain a uniform liquid crystal alignment agent. The composition of the liquid crystal alignment treatment agent is shown in Table 1. In the same manner as in Example 1, the liquid crystal alignment treatment agent was used to carry out evaluations of voltage retention, tilt angle, liquid crystal alignment, friction resistance, drying speed, and whitening characteristics 'printing unevenness, foreign matter at the time of printing' and storage stability. The results are shown in Table 2 and Table 3. -50- 201011421 [Table 1-1] Resin content of resin composition (% by mass) Imidization ratio (%) of resin in varnish Solvent composition (mass ratio) Tetracarboxylic dianhydride diamine Example 1 CBDA ( 69) PMDA(30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 5 89 yBL/NEP/BC =57.9/10.5/31.6 Example 2 CBDA(69) PMDA(30) 2, 4-DAA(30) 3-ABA(40) C14DAB(30) 5 89 yBL/NEP/BC =47.3/21.1/31.6 Example 3 CBDA(69) PMDA(30) 2,4-DAA(30) 3- ABA(40) C14DAB(30) 5 89 yBL/NCP/BC =57.9/10.5/31.6 Example 4 CBDA(69) PMDA(30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 5 89 yBL/NCP/BC = 47.3/21.1/31.6 Example 5 CBDA(69) PMDA(30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 6 89 NEP/B068.1/ 31.9 Example 6 CBDA (69) PMDA (30) 2,4-DAA (35) 3-ABA (40) PCBA-PDA (25) 5 90 yBL/NEP/BC = 57.9/10.5/31.6 Example 7 CBDA ( 69) PMDA(30) 2,4-DAA(35) 3-ABA(40) PCBA-PDA(25) 5 90 yBL/NEP/BC =47.4/31.6/21.1 Example 8 TDA(IOO) p-PDA( 90) C18DAB(10) 6 84 NEP/yBL/BC =70.2/17.0/12.8 CBDA(50) PMDA(44) DDM - Example 9 TDA(IOO) p-PDA(50) 2,4-DAA(35) PCBA-PDA(20) 6 87 yBL/NEP/BC =70.2 /17.0/12.8 CBDA(50) PMDA(44) DDM - -51 - 201011421 [Table 1-2] Resin composition Resin content (% by mass) The imidization ratio (%) of the resin in the varnish Solvent composition (mass ratio) Tetracarboxylic dianhydride diamine Example 10 CBDA (99) 2,4-DAA (70) BAPP (20) PCBA-PDA (IO) 6 70 NEP/DMI/EC = 57.4/21.3/21.3 Example 11 CBDA ( 99) 2,4-DAA(70) BAPP(20) PCBA-PDA(IO) 6 70 NEP/NMP/BC =57.4/10.6/31.9 Example Π CBDA(99) 2,4-DAA(70) C12DAB( 30) 6 91 NEP/B068.1/31.9 Comparative Example 1 CBDA(69) PMDA(30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 6 89 NEP/BC=68.1/31.9 Comparison Example 2 CBDA(69) PMDA(30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 5 89 yBL/NMP/BC =47.3/21.1/31.6 Comparative Example 3 CBDA(69) PMDA( 30) 2,4-DAA(30) 3-ABA(40) C14DAB(30) 5 89 yBL/BC/DPM =57.8/21.1/21.1 Example 13 CBDA(69) PMDA(30) 2,4-DAA( 30) 3-ABA(40) C14DAB(30) 5 89 yBL/NCP/BC =26.3/42.1/31.6 -52- 201011421

[Table 2] Example Voltage Retention Rate Drying Rate Preservation Stability Whitening Printability (%) (sec) Heterogeneous Material Example 1 94.82 340 〇〇〇〇 Example 2 94.84 410 〇〇〇〇 Example 3 96.01 1800 or more 〇〇〇〇Example 4 95.15 1800 or more 〇〇〇〇Example 5 93.43 1000 〇〇〇〇Example 6 93.01 355 〇〇〇〇Example 7 93.21 890 〇〇〇〇Example 8 92.80 1340 〇〇〇〇 Example 9 92.51 650 〇〇〇〇Example 10 93.05 970 〇〇〇〇Example 11 93.10 920 〇〇〇〇Example 12 95.93 1000 〇〇〇〇Comparative Example 1 94.09 800 〇XX 〇Comparative Example 2 94.48 340 〇 〇X 〇Comparative Example 3 95.33 190 〇〇XX Example 13 94.82 1800 or more X 〇〇〇-53- 201011421 [Table 3] Example of the liquid crystal alignment tilt angle in the friction resistance weak friction (.) 23 ° C 60 ° C Example 1 〇 △ 2.9 2.5 Example 2 〇Δ 2.8 2.4 Example 3 〇Δ 2.7 2.3 Example 4 〇Δ 2.8 2.4 Example 5 〇Δ 1.9 1.7 Example 6 〇 〇5.1 4.5 Example 7 〇〇 4.5 3.9 Example 8 X 〇 2.1 1.8 Example 9 〇〇 3.9 3.5 Example 10 〇〇 3.5 3.1 Example 11 〇〇 3.4 3.0 Example 12 〇 X 2.2 1.3 Comparative Example 1 〇 △ 2.2 1.7 Comparative Example 2 〇 Δ 2.5 2.0 Comparative Example 3 〇 Δ 3.5 2.9 Example 13 〇 Δ 2.1 1.8 Industrial Applicability The liquid crystal alignment treatment agent of the present invention has excellent voltage holding characteristics and does not become a liquid crystal panel during printing. Since the agglomerates are caused by unevenness of the gap, a liquid crystal panel having a narrow gap can be produced with good yield. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can be used as a highly reliable liquid crystal display device, a TN liquid crystal display device, an STN liquid crystal display device, a TFT liquid crystal display device, an OCB liquid crystal display device, and a lateral electric field type. A display element obtained by various methods such as a liquid crystal display element and a VA liquid crystal display element is used. The entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 201011421 2008- 1 46792, filed on Jun. 4, 2008, are hereby incorporated by reference.

-55-

Claims (1)

201011421 VII. Patent application scope: 1. A liquid crystal alignment treatment agent characterized by containing a resin component and a solvent component, and the resin is a polyamine acid imine obtained by reacting a diamine component with a tetracarboxylic dianhydride. The resin component of the polyimine obtained after the chemical component is a solvent component of a pyrrolidone compound containing N-ethyl-2-pyrrolidone or N-cyclohexyl-2-pyrrolidone. 2. The liquid crystal alignment treatment agent according to claim 1, wherein the pyrrolidinium compound is N-ethyl-2-pyrrolidone, and the N-ethyl-2-pyrroleone is a solvent component of 5 to 80 mass. %. 3. The liquid crystal alignment treatment agent according to claim 1, wherein the pyrrolidone compound is N-cyclohexyl-2-pyrrolidone, and the N-cyclohexyl-2-pyrrolidone is 5 to 40% by mass based on the solvent component. 4. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a resin component of 1 to 10% by mass and a solvent component of 90 to 99% by mass. 5. The liquid crystal@alignment treatment agent according to any one of claims 1 to 4, wherein the diamine component is a diamine having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms. Base benzene. 6. The liquid crystal alignment treatment agent of claim 5, wherein the diaminobenzene having a disubstituted amino group substituted with an alkenyl group having 2 or 3 carbon atoms is a diamine represented by the following formula [1]; -56- 201011421 〔化1〕 7- The liquid crystal alignment treatment agent of claim 6 wherein the diamine component further contains a diamine represented by the following formula [32]; (In the above formula, k represents an integer of 1 to 20). 8. The liquid crystal alignment treatment agent of claim 6, wherein the diamine represented by the formula [1] contains 〜90 mol% in the total diamine component. 9. The liquid crystal alignment treatment agent of claim 8, wherein the diamine represented by the formula [32] contains 5 to 40 mol% of the total diamine component. Φ 10. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment treatment agent according to any one of claims 1 to 9 on an electrode-attached substrate. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 10 of the patent application. -57- 201011421 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201011421 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None -4-