TW200844139A - Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same - Google Patents

Abstract

Disclosed is a liquid crystal orientation treatment agent which enables to produce a liquid crystal orientation film having excellent rubbing resistance and a large liquid crystal pretilt angle and which can provide an excellent printing property even when the agent has a high imidization level. Also disclosed is a liquid crystal display element produced by using the liquid crystal orientation treatment agent. The liquid crystal orientation treatment agent comprises the following polyimides (A) and (B). Polyimide (A): a polyimide which is produced by the imidization of a polyamic acid produced by the reaction between a diamine component comprising a diamine represented by the formula (1) or a diamine component comprising a diamine represented by the formula (1) and at least one diamine selected from the group consisting of diamines respectively represented by the formulae (2), (3), (4) and (5) with a tetracarboxylic acid dianhydride.; Polyimide (B): a polyimide which is produced by the imidization of a polyamic acid produced by the reaction between a diamine component comprising diamines respectively represented by the formulae (1) and (6) or a diamine component comprising diamines respectively represented by the formulae (1) and (6) and at least one diamine selected from the group consisting of diamines respectively represented by the formulae (2), (3), (4) and (5) with a tetracarboxylic acid dianhydride.

Description

[Technical Field] The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film using the same, and a liquid crystal display element. In particular, the liquid crystal alignment film used for the liquid crystal display element produced by the rubbing treatment step uses a liquid crystal alignment film and a liquid crystal display element. [Prior Art] A liquid crystal display element is a structure in which liquid crystal molecules are sandwiched by a liquid crystal alignment film formed on a substrate, and a display element in which the liquid crystal molecules are responsive to a voltage is used. The liquid crystal alignment film has an important task of controlling the alignment direction and the pretilt angle of the liquid crystal molecules in an arbitrary state. The liquid crystal alignment film is usually produced by applying a pressure to a surface of a polyimide film formed on a substrate by rubbing or lining, or the like, by performing a so-called "friction treatment". In the rubbing treatment, the alignment direction of the liquid crystal molecules is determined as a means for increasing the pretilt angle of the liquid crystal. A method of introducing a long-chain alkyl group into the structure of the polyimine forming the liquid crystal alignment film is known (for example, see Patent Document 1). . As a means for forming a polyimide film on a substrate, there are a method of coating a solution of polyacrylic acid, a method of imidating ruthenium on a substrate, and a method of applying a solution of soluble polyimine. In the method of using a solution of soluble polyimine, even when it is a relatively low-temperature calcination, a polyimine film having a good characteristic -5 - 200844139 can be formed as a liquid crystal alignment film, but formed on the other hand. The strength of the film is low, and the rubbing treatment is liable to cause damage to the surface of the film and peeling of the film. Further, in the production of a liquid crystal alignment film, as a means for applying a polymer solution to a substrate, an offset printing method is now widely used in the industry. However, since a solution of a soluble polyimine having a high ruthenium iodide ratio is inferior in printability, it is necessary to mix polylysine or a soluble polyimine having a low ruthenium amination ratio, etc. (for example, Refer to Patent Document 2). Further, in order to impart a large pretilt angle to the liquid crystal, when a long-chain alkyl group is introduced into the structure of the soluble polyimine, the printability tends to be deteriorated. As a means for improving the printability of the polymer solution to the substrate, a method of adding a solvent such as butyl cellosolve is known (for example, see Patent Document 3). However, in general, in comparison with soluble polyimine and polylysine, since a solvent is low, a large amount of a solvent such as butyl cellosolve cannot be used. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 9-2973 No. Hei 9-2973 No. 2 Patent Publication No. Hei. Problem It is an object of the present invention to provide a liquid crystal alignment film having a large pretilt angle of a liquid crystal (for example, 4° or more), and a polyimide having a high imidization ratio and excellent printability. Amine-based liquid crystal alignment treatment agent-6 - 200844139 Means for Solving the Problems In order to achieve the above object, the present inventors have carefully studied the results and finally completed the present invention. That is, the present invention has the following points. (1) A liquid crystal alignment treatment agent comprising the following polyimine (A) and the following polyimine (B), polyimine (A): (1) represented by formula (1) a diamine component consisting of a diamine, or a diamine represented by the formula (1) and a group selected from the group consisting of the formula (2), the formula (3), the formula (4), and the formula (5) a polyamine component obtained by reacting a diamine component composed of at least one diamine and a polyamic acid obtained by reacting a tetracarboxylic dianhydride component with a tetracarboxylic acid dianhydride; polyimine (B): Iii) a diamine component consisting of a diamine represented by the formula (1) and a diamine represented by the formula (6), or (W) a diamine represented by the formula (1) and a diamine represented by the formula (6) a diamine component composed of at least one diamine selected from the group consisting of formula (2), formula (3), formula (4), and formula (5), and reacted with a tetracarboxylic dianhydride component Polyacrylamide obtained by ruthenium imidization; [Chemical 1]

(1) [Chemical 2]

H2n

(CH2)n-NH2 (2) (3) 200844139

(In the formula (2), 乂1 represents a single bond, or a bond group selected from a group consisting of ether, ester, and decylamine, and X2 represents a linear alkyl group having 1 to 12 carbon atoms; Wherein η is 1 or 2; in the formula (5), χ3 represents a single bond, or a bond group selected from the group consisting of _〇, -CH2-, -ΝΗ-, and -CONH-, and an R-based hydrogen atom Or methyl) [Chemical 3]

(In the formula (6), χ4 represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and χ5 is a linear alkyl group having a carbon number of 14 to 2 Å. Or a monovalent organic group represented by the following formula (7): (Chemical Formula 4) - 6-χ7 (7) (In the formula (7), Χ6 is a phenyl group or a cyclohexyl group, and the x7 system has a carbon number of i to 12 a cyclohexyl group of a chain alkyl group). (2) The liquid crystal alignment treatment agent according to the above (1), which comprises a polyimine (A) and a polyimine (B) in a mass ratio of from 50:50 to 90:1. In the liquid crystal alignment treatment agent according to the above (1) or (2), the polyamidimide (A) and the polyimine (B) have a sulfhydrylation ratio of 40% or more. . The liquid crystal alignment treatment agent according to any one of the above aspects (1), wherein the amount of the total diamine of 100% by mole in the polyimine (A) is 2 0 to 1 0 0 % of the diamine represented by the formula (1), and when the diamine content of the formula (1) is less than 1 〇〇 mol %, the remaining diamine is from the formula (2), (3) At least one diamine selected from the group consisting of formula (4) and formula (5). (5) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the amount of the total diamine of 100% by mole in the polyimine (B) is 20 ～90 mol% of the diamine represented by the formula (1), 5 to 40 mol% of the diamine represented by the formula (6), and the total of the diamine of the formula (1) and the diamine of the formula (6) When the content is less than 100 mol%, the remaining diamine is at least one selected from the group consisting of formula (2), formula (3), formula (4), and formula (5). (6) The liquid crystal alignment treatment agent according to any one of the above (1) to (5), further comprising an organic solvent component. (7) The liquid crystal alignment treatment agent according to the above (6), which contains γ-butyl propionate, butyl cellosolve, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether as an organic solvent component. The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent is a liquid crystal alignment film which is subjected to rubbing treatment. (9) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (8). (1) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of the above (1) to (8) to a substrate on which an electrode is attached, and baking and rubbing -9-200844139 Processed. (11) A liquid crystal display element comprising the liquid crystal alignment film according to (9) or (10) above. Advantageous Effects of Invention The liquid crystal alignment treatment agent of the present invention is excellent in printability when applied to a substrate, and has less damage to the surface of the film and peeling of the film during rubbing treatment, and a liquid crystal alignment film having a large pretilt angle of liquid crystal is obtained. A liquid crystal display element having good characteristics with few defects is displayed. Moreover, although the liquid crystal alignment treatment agent of the present invention may increase the sulfhydryl imidization ratio of the polyimine contained therein, it has the above characteristics, so that a highly reliable liquid crystal display element can be obtained. BEST MODE OF THE INVENTION The present invention will be described in detail below. The liquid crystal alignment treatment agent of the present invention contains two polyimines of the following polyimine (A) and the following polyimine (B), and contains a mass ratio of 50:50 to 90:10. Polyimine (A) and polyimine (B). The liquid crystal alignment treatment agent of the present invention is particularly suitable for use as a rubbed liquid crystal alignment film. That is, the liquid crystal alignment treatment agent of the present invention is applied onto a substrate on which an electrode is attached and baked, and is used as a liquid crystal alignment film which is treated as a rubbing treatment. <Polyimine (A) &gt; -10- 200844139 The polyimine (A) used in the present invention is a polyamido acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Polyimine. The polyimine (A) is soluble in the organic solvent contained in the liquid crystal alignment treatment agent of the present invention, and the reaction of the polyimine (A) obtained by reacting the diamine component with the tetracarboxylic dianhydride component It is also soluble in the organic solvent used. [Diamine component] The diamine component used for obtaining the polyimine (A) is a diamine represented by the following formula (1) as an essential component. [Chemical 5]

H2N

(1) In the diamine represented by the formula (1), the position of each substituent on the benzene ring is not particularly limited, but the positional relationship of the two amine groups is preferably a meta or a para position. Preferred specific examples of the diamine are listed below, but are not limited thereto. [Chemical 6]

-11 - 200844139 The use of the diamine represented by the formula (1) is effective for suppressing damage to the surface of the film and peeling of the film during the rubbing treatment, and further, the solubility of the polyimine (A) in the organic solvent is also changed. high. The diamine represented by the formula (1) may be used singly or in combination of plural kinds. The content of the diamine represented by the formula (1) is 20 to 100 mol% of the entire diamine component in the polyimine (A), preferably 30 to 100 mol%, more preferably 4 0. ~1 0 0 mole %. The more the ratio of the diamine represented by the formula (1), the higher the effect of suppressing the damage of the surface of the alignment film and the peeling of the film during the rubbing treatment, and the higher the solubility of the polyimine in the organic solvent. When the diamine represented by the formula (1) is less than 100 mol%, the remaining diamine is composed of the following group (2), formula (3), formula (4), and formula (5). At least one of the selected ones. The content of at least one diamine selected from the group consisting of formula (2), formula (3), formula (4), and formula (5) is the entire diamine component of the polyimine (A). 〇 above ~ 80% by mole, preferably 5 to 70 moles. /〇, better for 1〇~60mol%. Specifically, the content of the diamine represented by the formula (2) is preferably from ～40 mol/〇, particularly preferably from 5 to 30 mol. /. More preferably, it is from 1 to 30 mol%, and the remaining content is at least one diamine selected from the group consisting of formula (3), formula (4), and formula (5). [Chemistry 7]

-12- 200844139

In the formula (2), the meaning 1 represents a single bond or a bonding group selected from the group consisting of ether, ester, and decylamine, and X2 represents a linear alkyl group having 1 to 12 carbon atoms. In the formula (3), η is 1 or 2, preferably in the formula (5), X3 represents a single bond, or consists of 〇_, -CH2-, _NH-, and _ (: 01^11_ The bonding group selected by the group, R is a hydrogen atom or a methyl group, preferably a hydrogen atom. When the diamine of the formula (2) is used, the effect of increasing the solubility and the pretilt angle of the liquid crystal is obtained. The diamines represented by the formulae (3) to (5) have an effect of improving the alignment property of the liquid crystal. Specific examples of the diamines represented by the formulae (2) to (5) are given below. Examples of the diamine represented by the formula (2) include a diamine of the following formula (Π) to (14), etc. [Chemical 8] nh2 h2N^CH2)m-CH3 (11 NH2 h2n〇- 〇-(CH2)m - CH3 (12) 200844139

Ο—(CH2)m-CH3

(13) (14) In the formulae (11) to (14), m is an integer of 0 to 11, preferably 5 to 11, and examples of the diamine represented by the formula (3) include 2 -aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2-(2-aminophenyl)ethylamine, 2-(3-aminophenyl)ethylamine, 2-(4 -Aminophenyl)ethylamine and the like. Examples of the diamine represented by the formula (4) include p-phenylenediamine, meta-phenylenediamine, o-phenylenediamine, and the like. Examples of the diamine represented by the formula (5) include 4,4 '-diaminobiphenyl, 4,4,-diamino-2,2,-dimethylbiphenyl, 4,4. ,-Diamino-3,3'-dimethylbiphenyl, 4,4,-diaminodiphenyl ether, 3,3,-diaminodiphenylmethyl, 4,4,-di Aminodiphenylmethane, 4,4,-diamino-3,3'-dimethyldiphenylmethane, 4,4,-diaminodiphenylamine, 4,4'-diamino A base of guanamine and the like. Among these, it is particularly preferred that the 3-aminobenzylamine or the 4-aminoamine is because of its high solubility as a polyimine. [Tetracarboxylic dianhydride component] In order to obtain the polyimine (A), the tetrahydrogen-14-200844139 acid dianhydride component which reacts with the above diamine component is not limited to the printability and the rubbing treatment when the coated substrate is improved. In the case of the damage of the surface of the liquid crystal alignment film and the peeling of the film, it is of course possible to make various choices depending on other characteristics. In the present invention, the tetracarboxylic dianhydride to be used may be used alone or in combination of plural kinds. For example, even a polyimine having a high sulfonium imidization ratio is preferably used from the viewpoint of easily obtaining a polyimide having a relatively high solubility and a voltage holding ratio of the liquid crystal cell. An alicyclic structure or an aliphatic structure of tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3. , 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, ι, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro·1 -naphthyl succinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3, 3,4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-monobutylcyclopenta-1,5-one -1-1,2,5,6·tetraresidic acid dianhydride, tricyclo[4.2.1.02'5]-nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-two Anhydride, Hexacyclo[6.6.0·12'7·03,6·19'14·01()'13]hexadecane-4,5,11,12-tetracarboxylic acid-4,5 ·· 1 1 , 1 2 -dianhydride, etc. In particular, when aromatic tetracarboxylic dianhydride is used, 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, -15-200844139 3,3',4,4'-biphenyltetrahydro acid dianhydride, 2,2,3,3. ,-biphenyl liver, 2,3,3',4-biphenyltetrahydro acid di野,3,3,4,4,-diphenyl dianhydride, 2,3,3',4 - Benzophenone tetracarboxylic dianhydride, bis(3,4-yl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfonic anhydride, 1,2,5 acid dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, and the like. When considering the balance between the solubility of polyimine (A), the alignment retention of liquid crystal, and the characteristics of accumulated charge, tetracarboxylic dianhydride having an aliphatic structure or an aromatic structure is considered. The ratio, the former/the latter's molar ratio, is preferably j 60/40, more preferably 80/20 to 70/30. Particularly good tetradecanoic acid dianhydride 1,2,3,4-cyclobutanine tetraresin dianhydride and pyromellitic dianhydride. [Manufacturing Method of Polylysine] The reaction of reacting the above diamine component with a tetracarboxylic dianhydride component to obtain an acid is usually carried out by mixing a tetracarboxylic dianhydride amine component in an organic solvent. The tetracarboxylic dianhydride component and the diamine are mixed in an organic solvent, and are not particularly limited. For example, a method in which a diamine component is dispersed or a solution in a solvent is stirred, and a tetracarboxylic dianhydride component is dissolved as it is in an organic solvent, and is added to a tetracarboxylic dianhydride or a solution dissolved in an organic solvent. A method in which a dicarboxylic acid component is added to a dicarboxylic acid component and a diamine component. Further, when the dianhydride component or the diamine component is composed of a plurality of compounds, the plurality of components are polymerized in a premixed state to carry out tetracarboxylic acid dimethyl ketone tetramine residue benzene, 6-naphthalene tetracarboxylate The combination of the alicyclic carboxylic acid diterpenoid dry thin 90/1〇~ to the polydecylamine component and the dichotomous method in the organic solvent or dispersion or component dispersion method, interacting with the tetracarboxylic acid, can also make the reaction, Also -16- 200844139 allows individual polymerization to be carried out sequentially. When the tetracarboxylic dianhydride component and the diamine component are polymerized in an organic solvent, the temperature is usually from 〇 to 150 ° C, preferably from 5 to 100 ° C, more preferably from 10 to 80 ° C. When the temperature at the time of the polymerization reaction is high, the polymerization reaction is rapidly completed, but if it is too high, a polymer having a high molecular weight is not obtained. Further, the polymerization reaction system can be carried out at any concentration of the produced polymer. If the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid is excessively high, and it is difficult to uniformly Stir. Therefore, the concentration at the time of carrying out the polymerization reaction is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. Further, it is also possible to use a method in which the initial stage of the polymerization reaction is carried out at a high concentration, and then the organic solvent is added to lower the concentration. The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the produced polyamine. For example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylene Anthracene, tetramethylurea, pyridine, dimethylhydrazine, hexamethylarylene, gamma-butylpropyl ester, and the like. These organic solvents may be used singly or in combination of plural kinds. In addition, the organic solvent which does not dissolve the polyamic acid may be used in the organic solvent as long as it does not precipitate in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and causes the produced polyamic acid to be hydrolyzed, the organic solvent is preferably dried as much as possible. -17- 200844139 The ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization of polylysine is preferably 0.8:1 to 1.2:1, more preferably 0.9:1 to 1 in terms of molar ratio: 1. The closer the molar ratio is to 1: 1, the greater the molecular weight of the polylysine obtained. By controlling the molecular weight of the polyaminic acid, the molecular weight of the polyimine obtained after the ruthenium imidization can be adjusted. In the present invention, the molecular weight of the polyproline is not particularly limited, but particularly, as a precursor for obtaining a polyimine (A) suitable for the present invention, the weight average molecular weight is preferably 2,000 to 200,000, more Preferably, it is 5,000 to 5,0 0 0 〇 [manufacturing method of polyimine (A)] The ruthenium imidization of the polylysine obtained as described above can be obtained by alkaline exposure in an organic solvent. The mixture is stirred for 1 to 100 hours in the presence of a solvent and an acid anhydride. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because the reaction can be carried out to be moderately alkaline. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because the obtained polyimine can be easily purified after the imidization of hydrazine. As the organic solvent used for the ruthenium imidization of the polyamic acid, the same organic solvent as the organic solvent used in the polymerization reaction of the above polyamic acid can be used. The oxime imidization ratio of the polyimine (A) can be adjusted by the amount of the catalyst, the reaction temperature, the reaction time, and the like. The amount of the basic catalyst is preferably from -18 to 200844139 醯 2 to 10 times the molar amount of the prolyl group, more preferably 0.5 to 5 times the mole. Preferably, the valeric acid group is 1 to 30 times moles, more preferably 1 temperature is preferably _20 to 250 ° C, more preferably 〇 180 ° C 1 hour, preferably 1 to 1 〇 hour. The ruthenium imidization ratio of the polyimine (A) is not particularly 40% or more, and is particularly preferably 80% or more in order to obtain a high voltage holding ratio'. In the solution of the obtained polyimine (A), a medium or the like remains, and it is preferred to recover and wash the liquid crystal alignment treatment agent of the invention. The polyimine (A) can be recovered by adding hydrazine to a weak solvent in a stirred state to precipitate a polyimine as a weak solvent, and examples thereof include methanol, acetone, hexane, an alkane, and a methylethyl group. The ketone, methyl isobutyl ketone, ethanol, and the recovered polyimine are washed, and the weak solvent and the washed polyimine are dried under normal pressure or reduced pressure to become a powder. . The sub-amount of the liquid crystal alignment agent of the present invention is not particularly limited, but the weight is 2,000 to 200, more preferably 5, from the viewpoint of the coating film strength and the ease of handling of the agent. , 〇〇〇~5〇, 〇〇〇. <Polyimine (B) &gt; Polyimine (B) is a diamine component and a tetracarboxylic acid, and the amount of the acid anhydride is 1 Torr. Reaction. The reaction time is 1 to other limits, preferably more preferably 60% or more. After the contact with the amine, the solution after the imidization is used, and then filtered. Butyl cellosolve, heptylene, benzene, and the like. Come here. The polyamidimine obtained by recovering the normal temperature or heating the pain imine (A) as the liquid crystal alignment and the average molecular weight is preferably the dianhydride component -19- 200844139 . Polyimine (B) is soluble in an organic solvent contained in the liquid crystal alignment agent of the present invention, and reacts with a polyimine (B) obtained by reacting a diamine component with a tetracarboxylic dianhydride component. It is also soluble in the organic solvent used. [Diamine component] The diamine component of the polyimine (B) is used as an essential component of the diamine represented by the formula (1) and the diamine represented by the formula (6). [Chemistry 9]

(1) (6) In the formula (6), x4 represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and x5 is a linear chain having a carbon number of 14 to 20. A monovalent organic group represented by the formula " or the following formula (7). —X6-X7 (7) -20· 200844139 In the formula (7), hydrazine 6 is a phenyl group or a cyclohexyl group, and fluorene 7 is a cyclohexyl group having a linear alkyl group having 1 to 12 carbon atoms. The diamine represented by the formula (1) is the same as the specific example of the [diamine component] described in the above polyimine. In the polyimine (Β), not only the diamine represented by the formula (1) but also the diamine represented by the formula (6) is also required as the diamine component. The content of the diamine represented by the formula (1) is 20 to 90 mol%, preferably 30 to 60 mol%, more preferably 3, based on the entire diamine component in the polyimine. 0~5 0 mol%. On the other hand, the diamine represented by the formula (6) preferably contains 5 to 40 mol% of the entire diamine component in the polyimine, thereby increasing the pretilt angle of the liquid crystal. The content of the diamine represented by the formula (6) is particularly preferably from 10 to 40 mol%, more preferably from 10 to 30 mol%. In particular, the more the ratio of the diamine represented by the formula (6), the more the pretilt angle of the liquid crystal is larger, which is preferable. The diamine represented by the formula (6) may be used singly or in combination of plural kinds. Further, in the entire diamine component of the polyimine (Β), the total content of the diamine of the formula (1) and the diamine of the formula (6) is less than 100 mol%. In the case of the remaining diamine, at least one selected from the group consisting of the above formula (2), formula (3), formula (4), and formula (5). Preferably, at least one of the diamines selected from the group consisting of formula (3), formula (4), and formula (5) has the effect of maintaining good liquid crystal alignment. The content of the diamines in the polyamine component of the polyimine (Β) is more than 7.5 旲%, preferably 5 to 7.5 mol%, preferably 1 〇 to 60. Mohr % ° The specific examples of the diamine represented by the formula (6) are given below, but are not limited thereto. -21 - 200844139 W 匕 12]

H2N nh2 h2n

-(CH2)p-CH3 (15) nh2o- 〇 one (CH2)p-CH3 (16) nh2

Hpn gas —/ IT0 one (CH2) P—CH3 (17) 〇

(19) In the formula (15) to the formula (19), p is an integer of 13 to 19, preferably 13 1 7

(CH2)q-CH3 (20)

(CH2)q-CH3 (21) NH2

h2n-W^ ~(^y^(CH2)q'CH3 (22) -22- 200844139 nh2

H2n -W t〇 CH3 (23)

(CH2)q-CH3 (24) In the formula (20) to the formula (24), q is an integer of 0 to 11, preferably 2 to 6 W 匕 14]

Nh2 Γ

(CH2)h-CH3

H2N

(CH2)h-CH3 (25) (26) (27) (28) (29) In the formula (25) to the formula (29), b is an integer of 0 to 11, preferably 2 to 6. [Four [acid dianhydride component] In order to obtain the polyimine (B), the tetracarboxylic-23-200844139 acid dianhydride component which reacts with the above-mentioned diamine component is not limited to the printability and the rubbing treatment at the time of coating a board|substrate. In the case of the damage of the surface of the liquid crystal alignment film and the peeling of the film, it is of course possible to make various choices depending on other characteristics. The tetracarboxylic dianhydride to be used may be used singly or in combination of plural kinds. As a preferable specific example, the tetracarboxylic dianhydride exemplified as the [tetracarboxylic dianhydride component] of the polyimine (A) can be mentioned. [Method for Producing Polylysine and Polyimine (B)] A reaction operation in which the above-mentioned diamine component is reacted with a tetracarboxylic dianhydride component to obtain a poly-proline, and the obtained polyaminic acid is obtained. The amination and the recovery operation of the polyimine are the same as those described in the "polyimine acid production method" and the [polyimine (A) production method] of the polyimine (A). Conducted. The molecular weight of the precursor of the polyimine (B), that is, the polyamic acid is not particularly limited, but particularly, as a precursor for obtaining the polyimine (B) suitable for the present invention, the weight average molecular weight is preferred. It is 2,000 to 200,000, more preferably 5,000 to 50,000. Further, the molecular weight of the polyimine (B) is not particularly limited, but the weight average molecular weight is preferably from 2,000 to 200,000, more preferably from the viewpoint of coating film strength and ease of handling as a liquid crystal alignment treatment agent. 5,0〇〇~ 5 0,000. The ruthenium imidization ratio of the polyimine (B) is not particularly limited, but is preferably 40% or more in the same manner as the polyimine (A), and more preferably 60 in order to obtain a high voltage holding ratio. More than %, especially better than 80%. -24- 200844139 &lt;Liquid crystal alignment treatment agent&gt; The liquid crystal alignment treatment agent of the present invention is a solution containing a suitable ratio of polyimine (A) and polyimine (B). For example, the powders of the polyimine (A) and the polyimine (B) are dissolved in an organic solvent to form a polyimine solution, and after mixing the solutions, the solution is diluted to a desired concentration. The solution or the solution of each polyimine is diluted to a desired concentration, and then mixed to form a solution. In the above-mentioned dilution step, in order to control the coating property to the substrate, adjustment of the composition of the organic solvent, addition of an additive for improving the characteristics of the coating film, and the like can be performed. The ratio of the polyimine (A) to the polyimine (B) contained in the liquid crystal alignment agent of the present invention, for the total content of the polyimine (A) and the polyimine (B), The content of the polyimine (A) is 50 to 90% by mass', and good printability and a large pretilt angle can be easily obtained. The content of the polyimine (A) is preferably from 60 to 80% by mass. Namely, the polyimine (A) and the polyimine (B) are 50:50 to 90:10, preferably 60:40 to 80:20, based on the mass ratio of the former to the latter. Examples of the organic solvent for redissolving the powder of the polyimine (A) and/or the polyimide (B) include hydrazine, hydrazine-dimethylformamide, and N,N-dimethyl group. Acetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylene Anthracene, tetramethylurea, dimethylhydrazine, hexamethylene sulfonium, γ-butylpropyl ester, 1,3-dimethyl-imidazolidinone, and the like. Among them, γ-butyl propyl ester is preferred because it is not easily hygroscopic. Examples of the solvent to be added for controlling the applicability to the substrate include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, and B-25-200844139 carbitol acetic acid. Ester, ethylene glycol, diethylene glycol diethyl ether, iota-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-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-acetate, dipropylene glycol Dipropylene glycol monomethyl ether, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. The solvent may not contain a solvent which cannot dissolve the polyimine (A) or the polyimine (B) alone, and may be mixed into the liquid crystal alignment of the present invention in a range in which the polyimide does not precipitate. In the treatment agent. In particular, it is known that by appropriately mixing a solvent having a low surface tension, coating film uniformity can be improved at the time of coating a substrate, and it is also suitable for use in a combination of the above solvents in the liquid crystal alignment treatment agent of the present invention. In addition to γ-butyl propyl ester and butyl cellosolve, it preferably contains dipropylene glycol monomethyl ether or diethylene glycol diethyl ether, particularly preferably γ-butyl propyl ester, butyl cellosolve, and dipropylene glycol single A combination of methyl ethers. The ratio of each solvent is 40 to 80% by mass, preferably 40 to 70% by mass, and the butyl cellosolve is 10 to 30% by mass, preferably 10 to 20% by mass, based on the total solvent. The dipropylene glycol monomethyl ether or diethylene glycol diethyl ether is 10 to 30% by mass, preferably 10 to 20% by mass. By using the liquid crystal alignment treatment agent of the present invention having such a composition, unevenness and pinholes due to variations in film thickness are less likely to occur during printing. Examples of the additive for improving the characteristics of the coating film include 3-aminopropylmethyldiethoxydecane, 3-phenylaminopropyltrimethoxydecane, and 3-amine-26-200844139-propyl A decane coupling agent such as a triethoxy decane or an (aminoethylaminomethyl) phenethyltrimethoxy decane. By adding a decane coupling agent, the adhesion of the coating film to the substrate can be further improved. The content (concentration) of the polyimine contained in the liquid crystal alignment agent of the present invention can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed. In general, the total content of the polyimine (A) and the polyimine (B) is preferably from 1 to 1% by mass, particularly preferably from 2 to 6% by mass, in which case it is easy to form a uniform defect free. The coating film can further improve the storage stability of the liquid crystal alignment agent. Further, the liquid crystal alignment agent of the present invention is preferably filtered before being applied onto a substrate as the case may be. &lt;Liquid Crystal Alignment Film&gt; The liquid crystal alignment film of the present invention can be applied to a substrate by drying, roasting, and curing the liquid crystal alignment film as a coating film, and applying a rubbing treatment to the coating film surface. The alignment process is obtained. The substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed, from the viewpoint of simplification of the process, and in the case of a reflective liquid crystal display device, it is also possible to use only a single-sided substrate. For an opaque substrate such as a wafer, a material such as aluminum that reflects light can be used as the electrode. The coating method of the liquid crystal alignment treatment agent may, for example, be a spin coating method, a printing method, an inkjet method or the like. From the viewpoint of productivity, the industrially widely used offset -27-200844139 printing method is also applicable to the liquid crystal alignment treatment agent of the present invention. The drying step after the application of the liquid crystal alignment agent is not necessarily required. However, it is preferred to carry out the drying step when the time from the application to the calcination is not necessarily the case, or when the baking is not performed immediately after application. The degree of drying is not particularly limited as long as the shape of the coating film is not deformed by the conveyance of the substrate, and the solvent can be evaporated. For example, it can be dried on a hot plate at a temperature of 50 to 150 ° C, preferably at a temperature of 80 to 120 ° C, and dried for 0.5 to 30 minutes, preferably 1 to 5 minutes. method. The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of from 100 to 350 ° C, preferably from 1 to 50 ° to 300 ° C, more preferably from 1 to 80 ° C. C~25 0 °C. When the proline group is present in the polyimide, the rate of oxime imidization of the polyimide film obtained at the calcination temperature may vary, but in the present invention, the yield of oxime may not necessarily be 100%. . If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered, so it is preferably 10 to 200 nm, more preferably 50~1 00 nm. The rubbing treatment of the coating film surface formed on the substrate as described above can be carried out by using an existing friction device. Examples of the material of the rubbing cloth at this time include cotton, enamel, and nylon. The liquid crystal alignment film of the present invention can be obtained by a method. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention is obtained by obtaining the liquid crystal alignment cell from the liquid crystal alignment treatment agent of the present invention by the above-described method, and then forming the liquid crystal cell by the known method of -28-200844139. Become a liquid crystal display element. For the production of the liquid crystal cell, for example, a pair of substrates on which the liquid crystal alignment film is to be formed is preferably sandwiched with a spacer of 1 to 30 μm, and more preferably a spacer of 2 to 10 μm is sandwiched in a rubbing direction. It is set to an arbitrary angle of 0 to 270°, and a sealing agent is used to fix the periphery, and a liquid crystal and a sealing method are injected. The method of encapsulating the liquid crystal is not particularly limited, and a vacuum method in which the liquid crystal is decompressed and then liquid crystal is injected, and the liquid crystal is dropped, and the gastric sputum is dropped. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The abbreviations used in the examples and comparative examples are as follows: &lt;tetracarboxylic dianhydride&gt; CBDA: 1,2,3,4-cyclobutylene tetraphthalic acid dianhydride PMDA: pyromellitic dianhydride TDA : 3,4-dicarboxy-1,2,3,4-tetrahydro-naphthalene succinic dianhydride &lt;diamine&gt; 2,4-DAA: 2,4-diamino-N,N-di Allylaniline PCH7AB ··4-{4-(4-heptylcyclohexyl)phenoxy H,3.diamine basic C12DAB: 4 - dodecyloxy-1,3 - a "fee basic C14DAB: 4-fourth court oxy_1,3 - one * fee basic -29- 200844139 C16DAB: 4-hexadecyloxy-1,3-diaminobenzene 4-ABA: 4-amino amide amide 3- ABA : 3-aminobenzylamine &lt;organic solvent&gt; NMP : N -methyl-2-pyrrolidone γ Β : γ-butyl propyl ester BS : butyl cellosolve DPM : dipropylene glycol monomethyl ether &lt;structural formula &gt; [Chemistry 15]

Ο 〇

[Chem. 16] XX: ΝΗ〇

(CH2)6CH3 H2fsk /Ν%

2,4-DAA

Nh2 nh2 nh2 1CH3 H2N-h^^〇(CH2)13CH3 H2N 0(CH2)15CH3

C12DAB C14DAB C16DAB -30- 200844139 [Chem. 18]

4-ABA 3-ABA ch2nh2 &lt;Determination of molecular weight&gt; The molecular weight of polyimine was determined by GPC (normal temperature gel permeation chromatography) apparatus as polyethylene glycol, poly The number average molecular weight and the weight average molecular weight were calculated by converting oxime to ethylene oxide. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: manufactured by Shodex Co., Ltd. (KD 8 0 3, KD 8 05 series)

Column temperature: 50 °C Eluent: N,N-dimethylformamide (as additive, lithium bromide monohydrate (LiBr*H20) is 30 mmol/L, phosphoric acid·anhydrous crystal (〇-phosphoric acid) ) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1. 〇 ml / minute calibration curve for the standard sample: TSK standard polyethylene oxide made by Tosoh Corporation (molecular weight of about 900,000, 15 0,000, 1〇〇,000, 3 0,000), and polyethylene glycol (molecular weight of about 1 2,000, 4,000 &gt; 1,000) ° manufactured by Polymer Laboratories Co., Ltd. &lt;Determination of sulfhydrylation rate&gt; The oxime imidization ratio of the polyimine was measured as follows. 20 mg of the polyimine powder was placed in the NMR sample tube, and 0.536 ml of dihydrogenated hydrazine (DMSO-d6, 0.05% TMS mixture) was added to completely dissolve. Borrowing -31 - 200844139 This solution was determined by proton NMR at 500 MHz by a NMR analyzer (JNM_ECA5 00) manufactured by Sigma Electronic Data Co., Ltd. The ruthenium imidization rate is determined by using a proton that has not changed before and after imidization as a reference proton, and the peak of the proton is used to accumulate hydrazine and the proline which is present near 9·5 to 10.0 ppm. The proton peak from the NH group accumulates 値, and the imidization ratio (%) = (1 - α· x / y) xl is obtained by the following formula: X is derived from the lysine The proton peak from the NH group accumulates 値, the peak of the y-based proton is cumulatively 値, and the α-poly-proline (0%) is used for a ruthenium matrix of lysine. The ratio of the number of reference protons. (Synthesis Example 1) As the tetracarboxylic dianhydride component, 13.53 g (0.069111〇1) 〇8〇8, 6.54 g (0.030 mol) of PMDA was used; as the diamine component, 8.13 g (0.040 mol) of 2,4 was used. -DAA, 3 · 6 7 g (0.0 3 0 m ο 1) 4 - ABA, 8 · 7 7 g (0.03 0 mol) C12DAB, obtained in a reaction at room temperature for 24 hours at 1 6 1 · 8 g ΝΜP Polylysine solution. To 3 4.8 1 g of this polyaminic acid solution, 62.65 g of NMP was added for dilution, 5 · 15 g of acetic anhydride and 2.1 9 g of pyridine were added, and the reaction was allowed to proceed for 3 hours at a temperature of 50 ° C. . After the reaction solution was cooled to about room temperature, it was poured into methanol of 3 66.8 mA - 32 - 200844 139 liters, and the precipitated solid matter was recovered. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-1). The polyimine had a number average molecular weight of 12,016 and a weight average molecular weight of 35,126. Further, the imidization ratio was 90%. To 1.99 g of the polyimine obtained above, 17·91 g of YBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After the solution was cooled to about room temperature, 7·5 3 g of γ B L , 4.82 g of BS, and 4.82 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Synthesis Example 2) As the tetracarboxylic dianhydride component, H43 g (0.0685 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used. As the diamine component, 8.13 g (0.040 mol) of 2,4-DAA and 5 were used. 50 g (0 · 0 4 5 m ο 1) 4 - ABA, 4 · 3 9 g (0.015 mol) of C12DAB, and reacted at room temperature for 24 hours in 152.0 g of NMP to obtain a polyaminic acid solution. To 3 2.3 9 g of this polyaminic acid solution, 72.88 g of NMP was added for dilution, 5.09 g of acetic anhydride and 2.17 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize. After the reaction solution was cooled to about room temperature, it was poured into 3 93 · 9 ml of methanol to recover the precipitated solid matter. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 〇 ° C to obtain a white powder of polyimine (SP 1-2). The polyimine has a number average molecular weight of 12,6 16, and a weight average molecular weight of 39,703. Further, the sulfhydrylation rate was -33 - 200844139 9 0%. To 3.01 g of the polyimine obtained above, 27.09 g of γΒί was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 10.0 9 g of YBL, 8.21 g of BS, and 8.21 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution (Synthesis Example 3). As a tetracarboxylic dianhydride component, 13.33 g (0·) was used. 068 mol) CBDA, 6.5 4 g (0.0 30 mol) PMDA; as a diamine component, 8.13 g (0.040 mol) of 2,4-DAA, 7.33 g (0.060 mol) of 4-ABA, in 141.4 g of NMP, in the chamber The reaction was allowed to proceed for 24 hours to obtain a polyaminic acid solution. To 3 0.1 5 g of this polyaminic acid solution, 67.84 g of NMP was added for dilution, and 5.11 g of acetic anhydride and 2.18 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize. After the reaction solution was cooled to about room temperature, it was poured into 3 68.5 ml of methanol to recover the precipitated solid matter. Further, after the solid matter was washed with methanol several times, it was dried at a reduced temperature (TC) to obtain a white powder of polyimine (SPI-3). The number average molecular weight of the polyimine was 12,899. The weight average molecular weight was 39,984. Further, the oxime imidization ratio was 85%. To 3.06 g of the polyimine obtained above, 27.54 g of YBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. Point, the polyimine is completely dissolved. After cooling the solution to room temperature, add 1 克. 14 g-34-200844139 yBL, 8·24 g BS, 8.24 g DPM, and stir well to obtain a homogeneous solution. (Synthesis Example 4) As the tetracarboxylic dianhydride component, 13.53 g (〇.〇69 mol) of CBDA, 6.54 g (0.03 0111〇1)?^4〇8, and 6.10 g (0.030 mol) of the diamine component were used. 2,4-DAA, 4.89 g (0.040 mol) of 3-ABA, 9.62 g (0.030 mol) of C14DAB, and reacted at room temperature for 24 hours in 162.7 g of NMP to give a polyaminic acid solution at 3 5.7 9 g. To the polyamic acid solution, 63.91 g of NMP was added for dilution, and 5.16 g of acetic anhydride and 2.20 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C for 3 hours. After the reaction solution was cooled to about room temperature, it was poured into 3 74 · 7 ml of methanol to recover the precipitated solid matter. Further, after washing the solid matter several times with methanol, It was dried under reduced pressure at a temperature of 1 ° C to obtain a white powder of polyimine (SPI-4). The polyamidimide had a number average molecular weight of 13,472 and a weight average molecular weight of 35,859. Further, the imidization The rate was 8 9%. To 2.17 g of the polyimine obtained above, 15.91 g of YBL was added and stirred at a temperature of 50 ° C for 24 hours. At the end of the stirring, the polyimine was completely dissolved. After about room temperature, 6.3 g of yBL, 7.38 g of BS, and 7.38 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Synthesis Example 5) -35- 200844139 As a tetracarboxylic dianhydride component, 13.53 g (0.069111 使用) was used. 1) €80, 6.54 g (0.03 0 mol) PMDA; as a diamine component, 6.10 g (0.03 0 mol) 2,4-DAA, 6 · 1 1 g (0 · 0 5 0 m ο 1) 3 - ABA 6 · 9 7 g (0.020 mol) of C16DAB, reacted in 157.0 g of NMP at room temperature for 24 hours to obtain polydecylamine Solution. To 23.20 g of this polyamide acid solution was added 32.77 grams NMP to carry out dilution, was added 3.49 g of acetic anhydride and 1.49 g of pyridine, at a temperature of 50 ° C for 3 hours the reaction of (PEI). After the reaction solution was cooled to about room temperature, it was poured into 2 1 3.3 ml of methanol, and the precipitated solid matter was recovered. 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-5). The polyimine had a number average molecular weight of 12,498 and a weight average molecular weight of 34,121. Further, the sulfhydrylation rate was 8 9%. To 1.59 g of the polyimine obtained above, 11.66 g of γΒ was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 4.99 g of YBL, 5.78 g of BS, and 5.78 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Synthesis Example 6) As the tetracarboxylic dianhydride component, 13.33 g (〇.〇68 mol) of CBDA and 6.54 g (0.030 mol) of PMDA were used; as the diamine component, 8.13 g (0.040 mol) of 2,4-DAA was used. 6.11 g (0.040 mol) of 4-ABA, 3.81 g (0.010 mol) of PCH7AB, and the reaction was carried out at 151.7 g of NMP at room temperature for 24-36-200844 139 hours to obtain a polyaminic acid solution. To 3 3.3 g of this polyaminic acid solution, 59.61 g of NMP was added for dilution, 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to imidize. After the reaction solution was cooled to about room temperature, it was poured into 3 5 1 · 7 ml of methanol to recover the precipitated solid matter. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SP 1-6). The polyimine has a number average molecular weight of 10,877 and a weight average molecular weight of 34,89 8. Further, the sulfhydrylation rate was 90%. To 1.91 g of the polyimine obtained above, 17.19 g of γΒ was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 2.37 g of YBL, 4.35 g of BS, and 4.35 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Synthesis Example 7) As the tetracarboxylic dianhydride component, 13.53 g (0.069111〇1) 080 八, 6.54 g (0.030 mol) of PMDA was used; as the diamine component, 6.10 g (0.030 mol) of 2,4-DAA was used. 3.6 7 g (0.0 3 0 m ο 1) 3 - ABA, 1 2.8 2 g (0.040 mol) of C14DAB, and reacted at room temperature for 24 hours in 170.6 g of NMP to obtain a polyaminic acid solution. To 5,20 g of this polyaminic acid solution, 102.3 g of NMP was added for dilution, and 8.06 g of acetic anhydride and 3.44 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to carry out the imidization. -37- 200844139 After cooling the reaction solution to about room temperature, 60 1.9 ml of methanol was charged and the precipitated solid matter was recovered. 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 (SP 1-7). The polyimine had a number average molecular weight of 11,013 and a weight average molecular weight of 36,721. Further, the sulfhydrylation rate was 8 9%. To 3.27 g of the polyimine obtained above, 23.9 8 g of γΒ was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 7.75 g of γΒί, 11.95 g of BS, and 11.95 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution (Synthesis Example 8). As a tetracarboxylic dianhydride component, 19.36 g (0.099111 〇1) was used. 080 VIII; as a diamine component, 6.10 g (0.03 0 mol) of 2,4-DAA, 4.89 g (0.040 mol) of 3-ABA, 9.62 g (0.03 mol) of C14DAB, in 159.8 g of ΝP, in the chamber The reaction was allowed to proceed for 24 hours to obtain a poly-broncine solution. To 74.94 g of this polyaminic acid solution, 131.68 g of hydrazine was added for dilution, and 11.09 g of acetic anhydride and 4.73 g of pyridine were added to carry out a reaction at a temperature of 50 ° C for 3 hours to imidize. After the reaction solution was cooled to about room temperature, it was poured into 77 8.5 ml of methanol to recover the precipitated solid matter. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 1 〇 C ° C to obtain a white powder of polyimine (SPI-8). The polyamidimide has a number average molecular weight of -38 to 200844139 16,241 and a weight average molecular weight of 4〇,259. Further, the sulfhydrylation rate was 8 9%. To 4.80 g of the polyimine obtained above, 43.20 g of YBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 3.60 g of YBL, 18.05 g of BS, and 18.05 g of DPM were added, and the mixture was thoroughly stirred to obtain a homogeneous solution (Synthesis Example 9). As a tetracarboxylic dianhydride component, 9.61 g (0.049 mol) of CBDA was used. 15.02 g (0.05 0 mol) of TDA; as a diamine component, 6.10 g (0.03 0 mol) of 2,4-DAA, 4 · 8 9 g (0.0 4 0 m ο 1) 3 - ABA, 9.62 g (0.030 mol) C14DAB was reacted at room temperature for 24 hours in 180.9 g of NMP to give a polyaminic acid solution. To 40.5 4 g of this polyaminic acid solution, 70·66 g of NMP was added for dilution, 5.27 g of acetic anhydride and 2.24 g of pyridine were added, and the reaction was carried out at a temperature of 50 ° C for 3 hours to carry out amination. After the reaction solution was cooled to about room temperature, it was poured into 4 1 5 · 5 ml of methanol to recover the precipitated solid matter. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine (SPI-9). The polyimine has a number average molecular weight of 14, 4, and a weight average molecular weight of 35,977. Further, the sulfhydrylation rate was 90%. To 4.07 g of the polyimine obtained above, 3 6.63 g of γΒί' -39-200844139 was added at a temperature of 5 (TC stirring for 24 hours. At the end of the stirring, the polyimine was completely dissolved. This solution was cooled. After about room temperature, 2,44 g of yBL, 14.1 g of BS, and 14.1 g of DP oxime were added, and the mixture was thoroughly stirred to obtain a homogeneous solution (Synthesis Example 1). As a tetracarboxylic dianhydride component, 19.41 g was used. 0.099 mol) CBDA; as a diamine component, 20.3 g (0.100 mol) of 2,4-DAA was used, and the reaction was allowed to proceed at room temperature for 24 hours in 1 5 9.00 g of NMP to obtain a polyaminic acid solution. To the poly-proline solution, 38.7 9 g of NMP was added for dilution, 3.94 g of acetic anhydride and 1.68 g of pyridine were added, and the reaction was carried out for 3 hours at a temperature of 50 ° C to iodize the reaction solution. After about room temperature, the mixture was poured into 243.4 ml 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 polyfluorene. A white powder of the amine (SPL·10). The polyamidimide has a number average molecular weight of 10,122, weight. The average molecular weight was 21,004. Further, the oxime imidization ratio was 9 7%. To 2.50 g of the polyimine obtained above, 22.50 g of YBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours. The polyimine was completely dissolved. (Synthesis Example 1 1) -40- 200844139 As a tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA and 6.54 g (0.03 mol) of PMDA were used; as a diamine component, it was used. 8.13 g (0.040 mol) 2,4-DAA, 3.6 7 g (0 · 0 3 m m ο 1) 4 - ABA, 8.77 g (0.030 mol) C12DAB, reacted at room temperature for 24 hours in 162.6 g of NMP The poly-proline solution was obtained. In 3 8.3 3 g of this polyaminic acid solution, 68.99 g of NMP was added for dilution, 5.67 g of acetic anhydride and 2.42 g of pyridine were added, and the reaction was carried out at a temperature of 45 ° C for 3 hours. After the reaction solution was cooled to about room temperature, it was poured into 403.9 ml of methanol to recover the precipitated solid matter. Further, after washing the solid matter several times with methanol, the temperature was 1 〇〇 ° C is dried under reduced pressure to obtain a white powder of polyimine (SPI-11). The number average molecule of this polyimine Of 13,513, weight average molecular weight 47,948. Furthermore, acyl imidization was 76% to 5.21 g of the polyimide obtained above was added 46.89 g YBL, stirred at a temperature of 50 ° C 24 h. At the point in time when the stirring was completed, the polyimine was completely dissolved. After cooling the solution to about room temperature, 14.49 g of 761^, 14.49 g: 83, 14.49 g of 0?]\4 was added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Synthesis Example 12) As the tetracarboxylic dianhydride component, 13.53 g (0.069 mol) of CBDA, 6.54 g (〇. 30 mol) of PMDA, and 6.10 g (0.03 mol) of 2,4-DAA were used as the diamine component. 4.89 g (0.040 mol) of 3-ABA, 9.62 g-41 - 200844139 (0.03 〇 111 〇 1) (: 140 VIII, in a 162.7 g of NMP, the reaction was allowed to stand at room temperature for 24 hours to obtain a polyaminic acid solution. To 3.97 g of this polyaminic acid solution, 69.88 g of NMP was added for dilution, 5.79 g of acetic anhydride and 2.47 g of pyridine were added, and the reaction was allowed to proceed for 1 hour at a temperature of 50 ° C to ytify the reaction solution. After about room temperature, the solid matter precipitated was recovered by adding 4 1 2.7 ml of methanol. 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 solid matter. A white powder of polyimine (SPI-12) having a number average molecular weight of 10,734 and a weight average molecular weight of 28,190. Further, the oxime imidization ratio is 7 9%. In the quinone imine, 43.2 g of γΒί was added and stirred at a temperature of 50 ° C for 24 hours. At the end of the stirring, the polyimine After the solution was cooled to about room temperature, 3.6 g of γΒί, 18.0 g of BS, and 18.0 g of D Ρ 添加 were added, and the mixture was thoroughly stirred to obtain a homogeneous solution. (Reference Example 1) As a tetracarboxylic dianhydride The composition was 22.59 g (0.115111 〇1) 〇8〇8; as a diamine component, 14.66 g (0,120 mol) of 4-ABA was used, and in 211.10 g of NMP, the reaction was allowed to proceed at room temperature for 24 hours to obtain a polydecylamine. Acid solution. In 21.22 g of this polyaminic acid solution, 22.74 g of NMP was added for dilution, and 10.12 g of acetic anhydride and 4.71 g of pyridine were added to carry out the reaction at a temperature of 50 ° C, and the result was gelatinized at 30 minutes. Next, the reaction temperature was lowered to 35 ° C. The imidization reaction of the same solution as the above-mentioned solution - 42 - 200844139 was carried out for 3 hours. After the reaction solution was cooled to about room temperature, the reaction was carried out. The precipitated solid matter was recovered in 205.7 ml of methanol. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at a temperature of 100 ° C to obtain a white powder of polyimine. The average molecular weight of the quinone imine is 12,994, the weight average molecule The amount was 30,081. Further, the sulfhydrylation rate was 78%. In 1.64 g of the above obtained polyimine, 14.76 g of YBL was added, and the mixture was stirred at a temperature of 50 ° C for 24 hours, but at the end of the stirring, The dissolved polyimine remained, and it was confirmed that the solubility of the polyimide was poor if 2,4-DAA was not used in the diamine component. Table 1 shows the results of Synthesis Examples 1 to 2 2 and Reference Example 1. -43- 200844139 [Table i] Polyimine diamine (mol) Tetracarboxylic dianhydride (mol) oxime imidization ratio (%) Formula (1) Formula (6) Formula (2) to Formula (5) Synthesis Example 1 A SPI-1 2,4-DAA (0.040) 4-ABA(0.030), C12DAB(0.030) CBDA(0.069), PMDA(0.030) 90 Synthesis Example 2 A SPI-2 2,4-DAA (0.040) 4-ABA (0.045), C12DAB (0.015) CBDA (0.0685), PMDA (0.030) 90 Synthesis Example 3 A SPI-3 2,4-DAA (0.040) 4-ABA (0.060) CBDA (0.068), PMDA (0.030) 85 Synthesis Example 4 B SPI-4 2,4-DAA (0.030) C14DAB (0.030) 3-ABA (0.040) CBDA (0.069), PMDA (0.030) 89 Synthesis Example 5 B SPI-5 2,4-DAA (0.030) C16DAB (0.020) 3-ABA(0.050) CBDA(0.069), PMDA(0.030) 89 Synthesis Example 6 B SPI-6 2,4-DAA (0.040) PCH7AB (0.010) 4-ΑΒΑ(0·040) CBDA(0.068) , PMDA (0.030) 90 Synthesis Example 7 B SPI-7 2,4-DAA (0.030) C14DAB (0.040) 3-ABA (0.030) CBDA (0.069), PMDA (0.030) 89 Synthesis Example 8 B SPI-8 2, 4-DAA (0.030) C14DAB (0.030) 3-ABA(0.040) CBDA(0.099), 89 Synthesis Example 9 B SPI-9 2,4-DAA (0.030) C14DAB (0.030) 3-ABA(0.040) CBDA(0.049 ), TDA(0.050) 90 Synthesis Example 10 A SPI-10 2,4-DAA (0.100) CBDA(0.099) 97 Example 11 A SPI-11 2,4-DAA (0.040) 4-ABA (0.030), C12DAB (0.030) CBDA (0.069), PMDA (0.030) 76 Synthesis Example 12 B SPI-12 2,4-DAA (0.030 C14DAB (0.030) 3-ABA (0.040) CBDA (0.069), PMDA (0.030) 79 Reference Example 1 4-ABA (0.120) CBDA (0.115) 78 (Example 1) Using Synthesis Example 1 and Synthesis Example 4 The polyimine solution was mixed at a mass ratio of SPΙα- 200844139 1 to S PI-4 to obtain a liquid crystal alignment treatment agent of the present invention. &lt;Evaluation of printability&gt; The liquid crystal alignment treatment agent was offset-printed onto the washed Cr plate by using an alignment film printer ("Angstromer" manufactured by Sakamoto Photographic Co., Ltd.). The printed substrate was placed on a hot plate at 70 ° C for 5 minutes to temporarily dry the coating film. In the optical microscope ("ECLIPSE ME600" manufactured by NIKON Co., Ltd.), the surface of the film after the temporary drying was observed at 50 times, and as a result, unevenness due to the change in film thickness did not occur, and pinholes (film pits) were not observed. ). &lt;Evaluation of rubbing resistance&gt; The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C for 5 minutes, and then heated at 230 ° C. The baking was performed for 15 minutes to form a coating film having a film thickness of 1 〇〇 nm. Using a rubbing device with a roll diameter of 120 mm, using a crepe cloth, rubbing the film surface with a roll rotation number of 1 000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a liquid crystal alignment film The substrate. In the confocal laser microscope, the film surface of the liquid crystal alignment film was observed at 200 times, and no damage or peeling of the film was observed. Further, the observation of the film surface was carried out using a laser scanning type laser microscope 1 L Μ 2 1 D manufactured by LASERTEC. -45 - 200844139 (Example 2) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 5, the mass ratio of 1 to SPI-5 was 7:3, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. (Example 3) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 6, the mass ratio of 1 to SP 1-6 was 7:3, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. (Example 4) Using the polyimine solution obtained in Synthesis Example 2 and Synthesis Example 4, the mass ratio of 2 to SPI-4 was 7:3, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. Inhomogeneous printing by SPI· Ming liquid line Printing unevenness by SPI-ming liquid line printing unevenness by SPI-ming liquid line printing -46 - 200844139 (Example 5) Synthesis Example 3 and Synthesis Example 4 were used. The obtained polyimine solution 'mixed in a mass ratio of S PI-3 to SPI-4 was 7:3' to obtain a liquid crystal alignment treatment agent of the present invention. Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, no unevenness due to the change in film thickness occurred, and no pinholes were observed or damage or peeling of the film was observed. (Example 6) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 7, the mass ratio of SPI-1 to SP 1-7 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained. Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, there was no unevenness due to the change in film thickness, no pinholes were observed, and no damage or peeling of the film was observed. (Example 7) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 8, the mass ratio of SPI-1 to SPI-8 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained. Using this liquid crystal alignment treatment agent, evaluation of printing properties and abrasion resistance was carried out in the same manner as in Example 1. As a result, no pinholes were observed in the film thickness change, and no pinholes were observed, and no damage or peeling of the film was observed. -47-200844139 (Example 8) The present invention was obtained by mixing the mass ratio of the polyimine solution '1 and the S P I - 9 obtained in Synthesis Example 1 and Synthesis Example 9 to 7:3 to obtain the present crystal alignment treatment agent. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. (Example 9) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of 1 to SPI-4 was 6:4, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. (Example 10) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of 1 to SPI-4 was 9:1, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, no change in film thickness occurred, no pinholes were observed, and no damage or peeling of the film was observed. Inconsistent printing by SPI-ming liquid line printing unevenness by SPI-ming liquid line printing unevenness by SPI-ming liquid line printing -48- 200844139 (Example 11) Using Synthesis Example 10 and Synthesis Example 4 The obtained polyimine solution 'mixed in a mass ratio of SPI-10 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained. Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, there was no unevenness due to the change in film thickness, no pinholes were observed, and no damage or peeling of the film was observed. (Example 12) The polyimine solution obtained in Synthesis Example 1 and Synthesis Example 1 was mixed at a mass ratio of SPI-1 to SPI-12 of 7:3 to obtain a liquid crystal alignment treatment agent of the present invention. Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, there was no unevenness due to the change in film thickness, no pinholes were observed, and no damage or peeling of the film was observed. (Example 13) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of SPI-11 to SPI-4 was 7:3, and the liquid crystal alignment treatment agent of the present invention was obtained. Using this liquid crystal alignment treatment agent, the printability and the abrasion resistance were evaluated in the same manner as in Example 1. As a result, there was no unevenness due to the change in film thickness, no pinholes were observed, and no damage or peeling of the film was observed. -49 - 200844139 (Comparative Example 1) Using the polyimine solution obtained in Synthesis Example 4 as a liquid crystal formulation, unevenness in film thickness change of printability and abrasion resistance was performed in the same manner as in Example 1. Serious, I also saw most of the pinholes. To the damage and peeling of the film. (Comparative Example 2) Using the polyimine solution obtained in Synthesis Example 1 and Synthesis Example 4, the mass ratio of 1 to SPI-4 was 4:6, and the present crystal alignment treatment agent was obtained. Using this liquid crystal alignment treatment agent, the evaluation of the durability and the abrasion resistance was carried out in the same manner as in the first embodiment. As a result, unevenness due to changes in film thickness is observed in most pinholes. No damage or peeling of the film was observed. (Comparative Example 3) Using the polyimine solution obtained in Synthesis Example 1 as a liquid crystal formulation, the evaluation of printability and abrasion resistance did not cause unevenness in film thickness change as in Example 1. No damage was observed in the pinholes and peeling of the film was observed. &lt;Evaluation of Pretilt Angle&gt; With respect to the liquid crystal alignments used in Examples 1 to 5 and Comparative Examples 1 to 3, the pretilt angle of the liquid crystal cell was evaluated as follows. The liquid crystal alignment treatment agent was spin-coated on the glass-based treatment price of the transparent electrode. The knot was not printed with SPI-ming liquid, and the price was also processed. No, no treatment agent plate, • 50- 200844139 After drying for 5 minutes on a 70 °C hot plate, it was baked on a 23 (TC hot plate for 15 minutes to form a film with a film thickness of 100 nm. Using a rubbing device with a roll diameter of 120 mm, using a crepe cloth, the film surface was rubbed under the conditions of a roller rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.3 mm to obtain a liquid crystal alignment film. Two substrates are prepared, and a spacer of 6 μm is dispersed on one of the liquid crystal alignment film surfaces, and a sealant is printed thereon, and the other substrate is reversed in a direction in which the liquid crystal alignment film faces the opposite rubbing direction. After the bonding, the sealing agent was hardened to prepare a hollow cell. In this empty cell, liquid crystal MLC-2003 (manufactured by MERCK Japan Co., Ltd.) was injected by a reduced pressure injection method, and the injection port was closed to obtain an antiparallel nematic liquid crystal cell. The liquid crystal cell was subjected to measurement of a pretilt angle at a temperature of 23 ° C. The measurement was carried out using TBA 107 manufactured by Autronic Co., Ltd. The evaluation results are shown in Table 2. <Evaluation of voltage holding ratio> Two sheets were prepared in the same manner as described above. a substrate of a liquid crystal alignment film, A spacer of 6 μm is dispersed on one of the liquid crystal alignment film surfaces, and the sealant is printed, and the other substrate is bonded in a straight direction in the opposite rubbing direction of the liquid crystal alignment film surface, and then the sealant is hardened to form a hollow cell. In this empty cell, liquid crystal MLC-2003 (C080, manufactured by MERCK Japan Co., Ltd.) was injected by a vacuum injection method, and the injection port was closed to obtain a twisted nematic liquid crystal cell. The liquid crystal cell was at a temperature of 23 ° C. Apply a voltage of 4 V for 60 microseconds, measure the voltage after 16.67 milliseconds, calculate how much the voltage can be maintained, and use it as the voltage holding ratio. Also, the same measurement is performed at a temperature of 90 ° C. -51 - 200844139 For the measurement of the voltage holding ratio, a VHR-1 voltage holding ratio measuring device manufactured by Toyo Corporation was used. Table 2 shows the evaluation results of the respective characteristics in Examples 1 to 13 and Comparative Examples 1 to 3. In the surface observation of the liquid crystal alignment film, no damage was observed and the peeling of the film was regarded as 〇. [Table 2] Liquid crystal alignment treatment agent pretilt angle (.) Voltage retention ratio (%) Friction resistance Printed polyimine (eight) Polyimine (B) (8) / (B) 23 °C 90 °C uneven pinhole Example 1 SPI-1 SPI-4 7/3 4.5 99.3 93.4 〇^fnr nnt yfriT Mll- j\\\ Example 2 SPI-1 SPI-5 7/3 5.1 99.2 93.1 〇/frrr τγγπ NN M Example 3 SPM SPI-6 7/3 5.9 99.1 92.9 〇4mi Τ1ΙΓ JN NN &gt;fnr iln Example 4 SPI-2 SPI-4 7/3 4.4 99.3 93.3 〇^frrp ΤΤΙΓ J\\\ 4rrr Γ Γ &gt; \ w Example 5 SPI-3 SPI-4 7/3 4.2 99.4 93.4 〇&gt;frrp ΤΤΤΓ J\ w &gt;fnr- ΠΤΓ J \ w Example 6 SPM SPI-7 7/3 5.3 99.3 93.2 〇/frrr ΤΤτΤΓ J\ w 4rrr ittr j\\\ Example 7 SPI-1 SPI-8 7/3 4.3 99.4 93.7 〇&gt;frrr ΤΤΤΓ y \ N\ and j\w Example 8 SPI-1 SPI-9 7/3 4.3 99.4 93.6 〇&gt;frrr Tltt: 4rrr TI1T Example 9 SPI-1 SPI-4 6/4 4.6 99.3 93.4 〇mt j\\\ 4rrc 、川, Example 10 SPI-10 SPI-4 9/1 4.1 99.2 93.2 〇/fnT mi j\\\ 4rrr. ΤΓΓΓ j\\\ Example 11 SPI-1 SPI-4 7/3 4.0 99.4 93.9 〇 ^fnr ItTl /fnr 实施 Example 12 SPI-1 SPI-12 7/3 4.6 99.1 92.3 Disenchant JV \N ^frrr Mll: y\\\ Example 13 SPI-11 SP I-4 7/3 4.7 99.1 92.2 〇M y\\\ &gt;fnT ΠΙΓ J \ \\ Comparative Example 1 SPI-4 5.0 99.4 93.5 〇Comparative Example 2 SPI-1 SPI-4 4/6 4.8 99.4 93.4比较Comparative Example 3 SPI-1 3.1 99.3 93.3 〇 and J\ w Μ j \ \\ From the above evaluation results, it was confirmed that the liquid crystal alignment treatment agent of the present invention-52-200844139 is excellent in printability, and the obtained liquid crystal The liquid crystal of the alignment film has a large pretilt angle and is excellent in abrasion resistance. On the other hand, in the liquid crystal alignment treatment agent of the comparative example, it was confirmed that the obtained liquid crystal alignment film had a large pretilt angle of the liquid crystal, but the printability was poor (Comparative Example 1), or the liquid crystal alignment was obtained even if there was no problem in printability. The pretilt angle of the liquid crystal of the film was also small (Comparative Example 3). Industrial Applicability The liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film which contains a polyimide having a high yield of ruthenium iodide and which is less likely to cause damage to the surface of the film during the rubbing treatment and peeling of the film. Moreover, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is applied to a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an OCB liquid crystal display element, etc. which are highly reliable liquid crystal display devices. . Further, the Japanese Patent Application No. 2006-317529 filed on Nov. 24, 2006, and the Japanese Invention Patent Application No. 2 0 0 6 - 3 2 2 3 9 7 filed on November 29, 2006 The entire contents of the invention, the scope of the invention, and the abstract are incorporated herein by reference. •53-

Claims (1)

200844139 X. Patent Application No. 1 · A liquid crystal alignment treatment agent characterized by containing the following polyimine (A) and the following polyimine (B), polyimine (A): (1) (1) an amine component composed of a diamine, or (Π) composed of a diamine represented by the formula (1) and a compound of the formula (2), the formula (3), the formula (4), and the formula (5). a polyamine imine obtained by reacting a diamine component composed of at least one diamine selected from a group with a polyamic acid obtained by reacting a tetracarboxylic dianhydride component with a tetracarboxylic dianhydride component; (iii) a diamine component consisting of a diamine represented by formula (1) and a diamine represented by formula (6), or (iv) a diamine represented by formula (1) and formula (6) a diamine component and a tetracarboxylic dianhydride comprising a diamine and at least one diamine selected from the group consisting of formula (2), formula (3), formula (4), and formula (5) a polyamidene obtained by reacting a polylysine obtained by a component reaction, -54- 200844139 (In the formula (2), X! represents a single bond, or a bond group selected from the group consisting of ether, ester, and decylamine, and X2 represents a linear alkyl group having 1 to 12 carbon atoms; In the formula (3), η is 1 or 2; in the formula (5), X3 represents a single bond, or a bond group selected from the group consisting of -〇·, -CH2-, -NH-, and -CONH- , R is a hydrogen atom or a methyl group) [Chemical 3] H2N^v (6) (In the formula (6), X4 represents a single bond, or a bond group selected from the group consisting of ether, ester, methylene ether, and decylamine, and X5 is a linear alkyl group having 14 to 20 carbon atoms. Or a monovalent organic group represented by the following formula (7)) (In the formula (7), X6 is a phenyl group or a cyclohexyl group, and χ7 is a cyclohexyl group having a linear alkyl group having 1 to 12 carbon atoms). 2. The liquid crystal alignment treatment agent of claim 1, which comprises a polyimine (fluorene) and a polyimine (yttrium) in a mass ratio of 50:50 to 90:10. 3. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the polyamidene (phosphonium) and the polyimine (yttrium) have a sulfhydrylation ratio of 40% or more. 4. The liquid crystal alignment treatment of any one of claims 1 to 3, wherein the amount of total diamine of i 〇〇 mol% in the polyimine (A) is ' a diamine of the formula (丨) containing 20% to 1% by mole, and when the diamine content of the formula (丨) is less than 100 mol%, the remaining diamine is from the formula (2), (3) At least one diamine selected from the group consisting of formula (4) and formula (5). 5. The liquid crystal alignment treatment agent of any one of claims 1 to 4, wherein the amount of total diamine of 1% by mole of the polyimine (B) is '20 to 90' Mol% of the diamine represented by the formula (1), 5 to 40 mol% of the diamine represented by the formula (6), and the total content of the diamine of the formula (1) and the diamine of the formula (6) is low. When the molar amount is 1%, the remaining diamine is at least one selected from the group consisting of the formula (2), the formula (3), the formula (4), and the formula (5). 6. The liquid crystal alignment treatment agent according to any one of claims 5 to 5, which further comprises an organic solvent component. 7. The liquid crystal alignment treatment agent of claim 6, wherein the organic solvent component contains γ-butyl propanate, butyl cellosolve, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether. The liquid crystal alignment treatment agent according to any one of the above claims, wherein the liquid crystal alignment treatment agent is a liquid crystal alignment film which is subjected to rubbing treatment. A liquid crystal alignment film obtained by using a liquid crystal alignment treatment agent according to any one of claims 1 to 8. A liquid crystal alignment film obtained by applying a liquid crystal alignment treatment agent according to any one of claims 1 to 8 to a substrate on which an electrode is attached, and performing baking and rubbing treatment. A liquid crystal display element having a liquid crystal alignment film according to claim 9 or claim 1. -56- 200844139 Ming said that there is no simple 4tuu: # is the map of the map element on behalf of the map •• refers to the table design represents the book without a set of one or two ^ ((8, if there is a chemical formula in this case, please reveal the best display invention Chemical formula of the feature: none