TW202144511A - Polyimide varnish - Google Patents

Abstract

Provided is a polyimide varnish which can be inhibited from suffering blushing due to moisture absorption, changes little in viscosity, has excellent storage stability, is less apt to cause foreign matter, clogging, etc. when used in obtaining films, the obtained films having little surface roughness and being able to have properties inherent in the polyimide material even after drying and heating, and is suitable for use in forming, for example, a liquid-crystal alignment film. The polyimide varnish is characterized by comprising the following ingredient (A) and ingredient (B). Ingredient (A): a polyimide (A) which is a product of imidization of a polyimide precursor. Ingredient (B): an amine compound (B) having, in the molecule, a secondary or tertiary amino group and a cyclic group that is either a nitrogenous aromatic heterocycle or an aromatic hydrocarbon group, the amino group having been bonded to an acyclic aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group.

Description

Polyimide coating

The present invention relates to a polyimide paint capable of suppressing suitable hygroscopic whitening as a liquid crystal aligning agent or the like.

Polyimide is widely used as a protective material and insulating material in the electrical and electronic fields due to its high mechanical strength, heat resistance, and solvent resistance. Specifically, when used as an insulating film for semiconductors, a polyimide film with a thickness of 1 to 10 μm is formed on a silicon substrate processed by wiring, and when used as a liquid crystal alignment film, a transparent electrode is attached. It is generally used to form a polyimide film with a thickness of 0.05 to 0.2 μm on a transparent substrate of , and to form a thin polyimide film on various support substrates. In the aspect of forming the polyimide film, it is generally a polyimide paint in which polyimide is dissolved in a suitable organic solvent, and is used for spin coating, offset printing, gravure printing, flexographic printing, inkjet printing, etc. The method is applied to a substrate, and the obtained coating film is subjected to heat treatment.

On the other hand, polyimide has excellent properties as various protective materials and insulating materials, and has a disadvantage of lack of solubility in organic solvents. Therefore, when dissolving polyimide in an organic solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylene, Highly soluble organic polar solvents such as methylphosphamide. However, these solvents, on the other hand of high solubility, have the disadvantage of high hygroscopicity.

Therefore, when a film is obtained using such an organic solvent-containing polyimide varnish, the obtained film tends to be easily influenced by the formation environment such as coating. In particular, when coating is performed in a high-humidity environment, there is a problem that the solubility of the composition decreases due to moisture absorption before the heat treatment, polyimide is deposited, and the film becomes white (moisture absorption whitening). Moreover, even if drying or heating is performed to the film which produces a hygroscopic whitening, there arises the problem that the characteristic of the original polyimide cannot be acquired, or the problem that surface roughness of the obtained film arises. In addition, when the film is obtained by flexographic printing using polyimide paint, there are cases where polyimide is formed on the flexo, resulting in printing foreign matter, or polyimide on the discharge head of the inkjet device. The amine composition is analyzed, causing head blockage, etc., and it is related to the failure of the procedure.

As a method of suppressing the above-mentioned hygroscopic whitening of the polyimide paint and the analysis of the polyimide composition, it is proposed to use a solvent with a high boiling point such as N-vinylpyrrolidone or N-cyclohexylpyrrolidone, which is more than 50% of the solvent. solvent (Patent Document 1). Moreover, the method of adding the C3-C15 polyol compound which has a tertiary nitrogen atom and a quaternary carbon atom to a polyimide paint is proposed (patent document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-117587 [Patent Document 2] International Publication (WO) Publication No. 2011/129414

[The problem to be solved by the invention]

In view of the above-mentioned circumstances, the object of the present invention is to provide a film that can suppress the phenomenon of hygroscopic whitening, has less viscosity change, and is excellent in storage stability, and is also less likely to generate foreign matter or clogging when obtaining a film, and the obtained film has less surface roughness. Moreover, even if it is dried or heated, the characteristics of the original polyimide material can be obtained, and the polyimide paint suitable for use as a liquid crystal aligning agent or the like can be obtained. [means to solve the problem]

The inventors of the present invention, as a result of diligent research in order to achieve the above-mentioned problems, have noticed that the above-mentioned whitening can be solved by increasing the water-solubility of polyimide in paint, and found that in order to improve the water-solubility of polyimide, the By adding an amine compound having a secondary amine group or a tertiary amine group and having a specific cyclic group to the polyimide paint, the phenomenon of hygroscopic whitening is suppressed. On the other hand, when the above-mentioned amine compound is the first-order amine compound, the viscosity of the paint is unstable, and the storage stability is remarkably deteriorated.

The present invention is based on the above-mentioned knowledge, and has the following gist. It is a polyimide paint featuring the following (A) components and (B) components. (A) Component: polyimide (A) which is an imide compound of a polyimide precursor. (B) Component: any one group having a second-order amino group or a third-order amino group and any one cyclic group of a nitrogen-containing aromatic heterocycle or an aromatic hydrocarbon group in the molecule, and the above-mentioned amino group is bonded An amine compound (B) based on an acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. [Effect of invention]

According to the present invention, the phenomenon of hygroscopic whitening can be suppressed, the viscosity change is small, and the storage stability is excellent, and when the film is obtained, foreign matter or clogging of the discharge head of the ink jet apparatus is not easily generated, and the obtained film has a rough surface. Polyimide paint which produces little and can obtain the characteristics of the original polyimide material even if it is dried or heated. Although the mechanism for obtaining the above-mentioned effects of the present invention is not necessarily clear, one of the reasons is considered as follows. In general, although polyimide is known to have low solubility, in the case of partially imidized polyimide, since carboxylic acid derived from tetracarboxylic dianhydride remains, the carboxylic acid and amine are formed by forming Salt. Can improve water solubility. By forming a salt of the amine and the polyimide in this way, precipitation of the polyimide in the case of moisture absorption of the polyimide paint can be suppressed. On the other hand, since polyimide has abundant electrophilic carbonyl groups, it is susceptible to nucleophilic attack by nucleophiles such as aliphatic amine compounds. In particular, it is considered that the polyimide derived from an aromatic tetracarboxylic dianhydride easily acquires a planar structure and has little steric hindrance, and thus is more susceptible to nucleophilic attack by aliphatic amines. Therefore, it is preferable to use alicyclic and aliphatic tetracarboxylic dianhydride as a raw material for polyimide from the viewpoint of ensuring less viscosity change and ensuring storage stability. In this way, aliphatic amine becomes Nucleophile can reduce the risk of nucleophilic addition to polyimide, and can obtain polyimide paint with less viscosity change and high storage stability. Furthermore, from the viewpoint of less viscosity change and ensuring storage stability, it is preferable that the basicity of the polyimide paint should be low. In this way, the molecular weight of the polyimide and the polyimide can be reduced. The viscosity of imide paints is reduced. Although the amine compound of the present invention having any one of the secondary amine group or the tertiary amine group in the molecule is difficult to cause nucleophilic attack due to the large steric hindrance, it is considered to cause the formation of the salt of the amine and the carboxylic acid, and It can inhibit the precipitation caused by the moisture absorption of polyimide paint. The polyimide paint of the present invention is suitable for use as a protective material, an insulating material and the like represented by a liquid crystal alignment agent.

[The best form of implementing the invention]

<Polyimide (A)> The polyimide paint of the present invention contains the following (A) component. (A) Component: polyimide (A) which is an imide compound of a polyimide precursor. The polyimide (A) may be used alone or in combination of two or more. The above-mentioned polyimide precursors are polyimide, polyimide, etc., which are produced by imidization reaction of polyimide, among which, tetracarboxylic acid containing tetracarboxylic dianhydride or its derivative is used. The polyamide acid obtained by the (polycondensation) reaction of a component and a diamine component is preferable. As a derivative of tetracarboxylic dianhydride, tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid diester dichloride, tetracarboxylic acid diester, etc. are mentioned, for example.

For the tetracarboxylic dianhydride or derivatives thereof, various tetracarboxylic dianhydrides or derivatives thereof can be used. As said tetracarboxylic dianhydride or its derivative(s), aromatic, acyclic aliphatic, or alicyclic tetracarboxylic dianhydride, or these derivatives are mentioned, for example. Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by performing intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. The acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to be composed of only the chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure. Moreover, an alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by containing at least one carboxyl group bonded to an alicyclic structure and dehydrating four carboxyl groups in the molecule. However, none of these four carboxyl groups are bonded to the aromatic ring. Moreover, it does not need to consist only of an alicyclic structure, and a part may have a chain hydrocarbon structure or an aromatic ring structure.

In the present invention, it is preferable to use an acyclic aliphatic or alicyclic tetracarboxylic dianhydride, or a derivative thereof, as the tetracarboxylic acid derivative component from the viewpoint of less viscosity change and ensuring storage stability. Among them, tetracarboxylic dianhydride or derivatives thereof containing at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure are more preferable. In addition, the usage amount is preferably 1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more, based on 1 mol of the all-tetracarboxylic acid derivative component used. When the above-mentioned tetracarboxylic acid derivative includes the above-mentioned tetracarboxylic dianhydride, tetracarboxylic dianhydride other than these derivatives, or these derivatives, the upper limit is preferably 95 mol% or less, 90 mol% or less is better.

Among tetracarboxylic dianhydrides or derivatives thereof, tetracarboxylic dianhydrides or derivatives thereof represented by the following formula (3) are preferably used.

上述式(3)中，X為下述(x-1)~(x-13)所成群組中選出的構造。

In the above formula (3), X is a structure selected from the group consisting of the following (x-1) to (x-13).

In the above formulas (x-1)～(x-13), R ¹ ～R ⁴ are each independently, and are hydrogen atom, methyl group, ethyl group, propyl group, chlorine atom, fluorine atom, carbon number 1～ containing fluorine atom A monovalent organic group of 6, or a phenyl group. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group. j and k are each independently an integer of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amido. *1 is a bond to one acid anhydride group, and *2 is a bond to another acid anhydride group. The two A _2s may be the same or different. Among them, X is preferably any one of the above formulae (x-1) to (x-7) and (x-11) to (x-13).

Preferred specific examples of the above formula (x-1) include the following formulae (x1-1) to (x1-6). In the formula, * is a bond bond.

The use ratio of the tetracarboxylic dianhydride or its derivative represented by the above formula (3) is preferably 1 mol % or more, and more preferably 5 mol % or more relative to 1 mol of the tetracarboxylic acid component used. , 10 mol% or more is better. When the above-mentioned tetracarboxylic acid derivative includes tetracarboxylic dianhydride represented by the above formula (3), tetracarboxylic dianhydride other than these derivatives, or these derivatives, the upper limit is 95 Molar % or less is preferable, and 90 mol % or less is more preferable. The said tetracarboxylic dianhydride or its derivative(s) can be used individually by 1 type or in combination of 2 or more types.

On the other hand, with respect to the diamine component for obtaining a polyamic acid, various diamines can be used without particular limitation. Among them, in the present invention, when polyimide is used as the liquid crystal aligning agent for vertical alignment mode, as the diamine exhibiting high vertical alignment ability, it is preferable to use the following formulas (S1), (S2) and (S3) ) of a side chain structure of at least one kind of diamine (hereinafter, also referred to as a specific diamine.) selected from the group consisting of.

In the above formula (S1), X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15.), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO-, or -((CH ₂ ) _a1 -A ₁ ) _m1 -. Here, a1 is an integer of 1 to 15, A ₁ is an oxygen atom or -COO-, and m ₁ is 1 to 2. From the viewpoint of availability of raw materials or ease of synthesis, X ₁ and X ₂ are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15.), -O-, -CH ₂ O- Or -COO- is preferred, single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10.), -O-, -CH ₂ O- or -COO- is more preferred.

G ₁ and G ₂ are independently a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group can be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. Alkoxy or fluorine atom substitution. m and n are independently an integer of 0 to 3, and the sum of m and n is 1 to 6, preferably 1 to 4. Here, examples of the divalent aromatic group having 6 to 12 carbon atoms include a phenylene group, a biphenyl group structure, and naphthalene. In addition, examples of the divalent alicyclic group having 3 to 8 carbon atoms include a cyclopropylidene group, a cyclohexylene group, and the like.

R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. R ¹ is formed of any of a hydrogen atom may be substituted with a fluorine atom. When ^{there are two or more X 1} , X ² , G ¹ , G ² , a1 , and A ₁ , the two or more X ¹ , X ² , G ¹ , G ² , a1 , and A ₁ may be the same or the same. can be different.

Preferred specific examples of the above formula (S1) include the following formulae (S1-x1) to (S1-x7).

In formulas (S1-x1)~(S1-x7), R ¹ is an alkyl group with 1~20 carbon atoms, an alkoxy group with 1~20 carbon atoms, or an alkoxyalkyl group with 2~20 carbon atoms, X ^P is -(CH ₂ ) _a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, - CH ₂ OCO-, -COO-, or -OCO-, A ₁ is an oxygen atom or -COO-* (however, the bond marked with "*" is bonded to (CH ₂ ) _a2 ), A ₂ is an oxygen atom or *-COO- (however, the bond marked with "*" is bonded to (CH ₂ ) _a2 ), a ₁ and a ₃ are independent of each other, and are an integer of 0 or 1, and a ₂ is an integer of 1 to 10, Cy is 1,4-cyclohexylene or 1,4-phenylene.

In the above formula (S2), X ³ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO- . Among them, -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO- are preferred from the viewpoint of liquid crystal alignment. R ² is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, ^{and any hydrogen atom forming R 2} may be substituted by a fluorine atom. Among them, from the viewpoint of liquid crystal alignment, an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferable.

In a preferred aspect of formula [S2], X ³ is any one of -O-, -CH ₂ O-, -COO- or -OCO-, and R ² is an alkyl group with 3 to 20 carbon atoms or a carbon number The alkoxyalkyl group is preferably 2-20, and it is more preferable when R ² is an alkyl group having 3-20 carbon atoms, and any hydrogen atom forming R ² may be substituted by a fluorine atom.

In the above formula (S3), X ⁴ is -CONH-, -NHCO-, -O-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. R ³ represents a structure having a steroid skeleton, and specific examples thereof include a structure having a skeleton represented by the following formula (st).

Examples of the above formula (S3) include the following formula (S3-x).

In the formula (S3-x), X is the above-mentioned formula (X1), (X2), or (X3). Moreover, Col is 1 type selected from the group of said formula (Col1)-(Col4), and G is said formula (G1) or (G2). * is the part that is bonded to other bases. As a preferable structure of formula (S3), the structures represented by the following formulae (S3-1) to (S3-6) can be mentioned, for example.

(＊為鍵結位置)

(* is the bond position)

Specific examples of the specific diamine include diamines of the following formulae (V-1) to (V-13).

In the formula, X ^v1 to X ^v4 and X ^p1 to X ^p8 are independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )- , -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, X ^v5 is -O-, -CH ₂ O-, -CH ₂ OCO-, - COO-, or -OCO-, X ^V6 to X ^V7 , X ^s1 to X ^s4 are independently -O-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. X _a to X _f are each independently, single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-, -C(CH ₃ ) ₂ -, -CO-, -COO-, - CONH-, -(CH ₂ ) _m -, -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -NH-, -SO ₂ -(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -SO ₂ -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO-, R ^v1 to R ^v4 , R ^1a to R ^1h are each independently, and are an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. or an alkoxyalkyl group with 2 to 20 carbon atoms. m is an integer from 1 to 8.

The content of the specific diamine is preferably 5 to 95 mol %, more preferably 5 to 90 mol %, and particularly preferably 5 to 80 mol % with respect to the entire diamine component from the viewpoint of imparting alignment to the liquid crystal.

The above-mentioned specific diamines may be used alone or in combination of two or more.

＜Other diamines＞ Diamines other than the above-mentioned specific diamines (also referred to as other diamines) may be used as diamines for obtaining polyamic acid. Moreover, other diamines can be used individually by 1 type or in combination of 2 or more types. Specific examples of other diamines, such as p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-benzene Diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diamine phenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4' -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4' - Biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2 '-Diaminobiphenyl, 2,3'-Diaminobiphenyl, 4,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane,

2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenyl ether Aniline, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, Dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3, 3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diamine diphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diamine benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-amine phenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane,

1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3-aminophenyl)butane ,5-diethyl-4-aminophenoxy)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4 -Aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methylene)]diphenylamine, 4,4'-[1,3-phenylene bis(methylene) )] diphenylamine, 3,4'-[1,4-phenylene bis(methylene)] diphenylamine, 3,4'-[1,3-phenylene bis(methylene)] diphenylamine , 3,3'-[1,4-phenylene bis(methylene)] diphenylamine, 3,3'-[1,3-phenylene bis(methylene)] diphenylamine, 1,4 -Phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4 -aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate),

1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate , bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4 -aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis (3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl) ) terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isoxylylenediamide, N,N'-bis(3-aminophenyl)isoxylamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy) ) Diphenylene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amine yl-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'- Bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy) Propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane alkyl,

(式(R3)~(R5)中，n為2~6的整數。)1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane , 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane , 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane Alkane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy) Decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminobenzene) oxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, diamines represented by the following formulae (nh-1) to (nh-8), the following formula (z -1) Diamines represented by (z-14), diamines represented by the following formulae (R1) to (R5), and other diamines having a radical initiation function, and the following formula (5-1) The diamines represented by ~(5-11) and the like have a group "-N(D)-" (D is a protective group that is removed and replaced by a hydrogen atom by heating, preferably a tert-butoxycarbonyl group.) Diamine, diamine represented by the following formulae (Dp-1) to (Dp-6), 2-(2,4-diaminophenoxy)ethyl methacrylate, and 2,4-diamino Aromatic diamines such as diamines having photopolymerizable groups at the terminals such as N,N-diallylaniline, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methyl) Alicyclic diamines such as cyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane , 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane Aliphatic diamines such as alkane, 1,12-diaminododecane, etc.

(In formulae (R3) to (R5), n is an integer of 2 to 6.)

(Boc為tert-丁氧基羰基。)

(Boc is tert-butoxycarbonyl.)

The method of obtaining a polyamic acid from the said tetracarboxylic-acid component and a diamine component can be performed by a known method. That is, the reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used at this time is not particularly limited if it dissolves the produced polyamide. Specifically, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Dimethyl sulfoxide or 1,3-dimethyl-2-imidazolidinone, etc. In addition, when the solvent solubility of polyamic acid is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D1 ] ~ the solvent of formula [D3].

(D¹ 及D² 為碳數1~3的烷基。D³ 為碳數1~4的烷基。) 此等之有機溶劑可單獨使用，亦可混合使用。更且即使為不溶解聚醯胺酸的溶劑，在生成的聚醯胺酸不析出範圍，亦可與上述溶劑混合使用。

(D ¹ and D ² are alkyl groups having 1 to 3 ^{carbon atoms. D 3} is an alkyl group having 1 to 4 carbon atoms.) These organic solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve a polyamic acid, in the range in which the produced polyamic acid does not precipitate, you may mix and use it with the said solvent.

The concentration of the polyamic acid in the reaction system is not easy to precipitate from the polyamic acid, and it is easy to obtain polymer dots, preferably 1 to 30 mass %, more preferably 5 to 20 mass %. The polyamic acid obtained as described above can be recovered by pouring into a poor solvent while stirring the reaction solution sufficiently to precipitate it. In addition, after performing precipitation several times, washing with a poor solvent, and drying at room temperature or heating, a purified powder of polyamic acid can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene. The polyamic acid ester can be obtained, for example, by subjecting the above-mentioned polyamic acid to an esterification reaction with an esterifying agent.

The polyimide (A) contained in the polyimide varnish of the present invention is obtained by imidizing a polyimide precursor such as the above-mentioned polyimide and polyimide. In the polyimide (A), although the repeating units possessed by the polyimide precursor are ring-closed, the ratio of the repeating units relative to the total repeating units possessed by the polyimide precursor (also known as the closed-ring ratio) (or imidization rate.) does not have to be 100%, preferably 20-90%, more preferably 30-80%, within this range, it can be adjusted arbitrarily according to the application or purpose of the polyimide paint. When the polyimide paint of the present invention is a liquid crystal alignment agent for forming a liquid crystal alignment film, the imidization rate is preferably 20-95%, more preferably 30-95%.

The imidization of the polyimide precursor can be performed, for example, by stirring the polyimide in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the organic solvent used in the aforementioned polymerization reaction can be used. For basic catalysts, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, it is preferable that pyridine has an appropriate basicity to allow the reaction to proceed. In addition, as for the acid anhydride, for example, anhydrous acetic acid, anhydrous trimellitic acid, pyromellitic dianhydride, etc., among them, use of anhydrous acetic acid is preferable because the purification after completion of the reaction is easy.

The temperature during the above imidization reaction is -20 to 140°C, preferably 0 to 100°C, and the reaction time is 0.5 to 100 hours, preferably 1 to 80 hours. The amount of the alkaline catalyst is 0.5-30 mol times, preferably 2-20 mol times, of the amide acid, and the amount of the acid anhydride is 1-50 mol times the amide acid, preferably 3-30 mol times. Ear times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. In the solution after the imidization reaction of polyimide, the added catalyst and the like remained, so the obtained polyimide was recovered by the following means, and redissolved in an organic solvent, which was used as the method of the present invention. The composition of the liquid crystal aligning agent is preferable. The polyimide solution obtained as described above can be polymerized by pouring it into a poor solvent with sufficient stirring. The precipitate is filtered, washed several times with a poor solvent, and then dried at room temperature or by heating to obtain a purified powder of polyimide.

The molecular weight of the polyimide obtained as described above is determined by GPC (Gel Permeation Chromatography). The weight average molecular weight (Mw) measured by the method is preferably 2,000 to 1,000,000, more preferably 10,000 to 150,000. Moreover, the number average molecular weight (Mn) is preferably 3,000 to 100,000, and more preferably 10,000 to 50,000.

<Amine compound (B)> The polyimide paint of the present invention contains the following (B) component. (B) Component: any one group having a second-order amino group or a third-order amino group and any one cyclic group of a nitrogen-containing aromatic heterocycle or an aromatic hydrocarbon group in the molecule, and the above-mentioned amino group is bonded An amine compound (B) based on an acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. The amine compound (B) may be used alone or in combination of two or more. The above-mentioned amine compound (B) is preferably a compound represented by the following formula (1).

In the above formula (1), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms _{, and at least one of R 1} and R ₂ is an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Preferred examples thereof are, for example, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl or pentyl. Ar is a monovalent group having a nitrogen-containing aromatic heterocyclic ring or an aromatic hydrocarbon group. The hydrogen atom of the nitrogen-containing aromatic heterocyclic ring possessed by Ar or the hydrogen atom possessed by the aromatic hydrocarbon group may be replaced by an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group containing halogen atom, alkoxy group containing halogen atom, carboxyl group, hydroxyl group, nitrile group substituted. Preferred examples of the nitrogen-containing aromatic heterocycle include, for example, a cyclic structure containing at least one partial structure selected from the group consisting of the following formula [1a], formula [1b] and formula [1c], and more Preferably, it is a ring-shaped structure including one to four of the above-mentioned partial structures.

(式中，Y₁ 為碳數1~5之直鏈或分枝烷基)

(in the formula, Y ₁ is a straight-chain or branched alkyl group with 1 to 5 carbon atoms)

Preferred examples of nitrogen-containing aromatic heterocycles, such as pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring , carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, phenanthroline ring, indole ring, quinoxaline ring, benzo Thiazole ring, thiodiphenylamine ring, oxadiazole ring, acridine ring. In addition, in terms of preferable examples of the aromatic hydrocarbon group, for example, a benzene ring, a naphthalene ring, an azulene ring, an indene ring, a perylene ring, an anthracene ring, a phenanthrene ring, and a phenacene ring. X is a divalent organic group containing an acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. X is preferably a divalent acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. A preferred example of the acyclic aliphatic hydrocarbon group is, for example, a linear or branched alkylene group having 1 to 10 carbon atoms, or an unsaturated alkylene group having 1 to 10 carbon atoms. Preferred examples of non-aromatic cyclic hydrocarbon groups, such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring ring, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, Alicyclic hydrocarbon groups having 3 to 20 carbon atoms, such as cyclononadecane ring, cycloeicosane ring, tricycloeicosane ring, bicycloheptane ring, decalin ring, norbornene ring, adamantane ring, etc.

_{Among X, the basis represented by *1-X 1} -X ₂ -*2 is preferred for reasons of ease of synthesis or availability of raw materials. However, X ₁ is a divalent group containing a non-cyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. X _{1 is} preferably a divalent acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. Preferred examples of the acyclic aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group of X _{1 are the same as the examples of X described above.} X ₂ is a single bond, -O-, -NH-, -S-, -SO ₂ -, or a divalent organic group having 1 to 19 carbon atoms. In addition, _{the total of carbon atoms possessed by X 1} and X ₂ is 1 to 20, preferably 1 to 10. In addition, *1 is a bond bond to N of formula (1), and *2 is a bond bond to Ar of formula (1).

N to which R ₁ and R _{2 are} bonded is bonded to the above-mentioned acyclic aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group.

Preferred examples of the amine compound (B) include compounds represented by the following formulae (b-1) to (b-14).

Among them, the amine compound (B) is preferably one or more compounds represented by any one of the above formulae (b-1) to (b-3) for reasons of ease of manufacture and availability of raw materials.

＜Polyimide paint＞ The polyimide varnish of this invention contains the polyimide (A) of the said (A) component and the amine compound (B) of the said (B) component. The polyimide paint can be obtained, for example, by dispersing or dissolving these components in an organic solvent. The total content of polyimide (A) in the polyimide paint is 1-20 mass %, more preferably 1-15 mass %, and 1-10 mass % from the point where it is easy to be uniformly mixed with compound (B). % is particularly good. In addition, the content of the amine compound (B) of the component (B) in the polyimide paint is relatively high relative to the polyimide ( A) 100 parts by mass, preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 10 parts by mass.

The organic solvent that can be contained in the polyimide paint of the present invention is preferably one that disperses or dissolves the polyimide (A) of the component (A) and the amine compound (B) of the component (B) above. dissolver. In terms of organic solvents, such as lactone solvents such as γ-valerolactone, γ-butyrolactone, etc., γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and other lactones Amine solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide Amide solvents such as amines; 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone (2,6-dimethyl-4-heptanone), methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, isoamyl lactate, n-butyl acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Butyl propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n- Butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethyl ether Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisoamyl ether; ethylene carbonate, propylene carbonate, etc. carbonate solvent, 1-hexanol, cyclohexanol, 1,2-ethanediol, diisobutylmethanol (2,6-dimethyl-4-heptanol), cyclohexanone, cyclopentanone Wait.

In terms of the preferred combination when using two or more organic solvents, such as N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol mono -n-butyl ether, N-methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether, N-methyl-2- Pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4 -Hydroxy-4-methyl-2-pentanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether , N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and Diisobutyl ketone, γ-butyrolactone with 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol monobutyl Base ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone With propylene glycol monobutyl ether and diisobutyl methanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and Dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate Esters with dipropylene glycol dimethyl ether, N,N-dimethylpropionamide with propylene glycol diacetate, tetramethyl urea with 4-hydroxy-4-methyl-2-pentanone, cyclohexanone with propylene glycol Monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, etc.

The polyimide paint of the present invention may contain various components (also referred to as other components) according to the application in addition to the polyimide (A) and the above-mentioned (B) component of the component (A). For example, polymers other than the above-mentioned polyimide (A), antioxidants (phenol-based, phosphite-based, thioether-based, etc.), ultraviolet absorbers, hindered amine-based light stabilizers, nucleating agents, resin additives ( fillers, talc, glass fibers, etc.), flame retardants, processability improvers, lubricants, etc.

<Liquid crystal alignment agent> In the case of a liquid crystal aligning agent suitable for use in the polyimide paint of the present invention, it is preferable to prepare it so as to be suitable for the formation of a liquid crystal aligning film. The liquid crystal alignment agent of the present invention preferably contains the polyimide paint of the present invention. The liquid crystal alignment agent of the present invention can be obtained by, for example, dispersing or dissolving the polyimide paint of the present invention and other components in an organic solvent as necessary. Moreover, the liquid crystal aligning agent of this invention can also be obtained by mixing 2 or more types of liquid crystal aligning agents. For example, it can be obtained by mixing two or more types of liquid crystal aligning agents containing the polyimide varnish of the present invention, or it can be obtained by mixing the liquid crystal aligning agent containing the polyimide varnish of the present invention with a liquid crystal aligning agent containing other components Alignment agent is mixed. The above-mentioned other components include, for example, polymers other than the above-mentioned polyimide (A), crosslinkable compounds, functional silane compounds, surfactants, compounds having photopolymerizable groups, organic solvents, and the like.

Other polymers are not particularly limited, such as polyimide precursors such as polyamic acid or polyamic acid ester, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose Derivatives, polyacetals, polymers of monomers with polymerizable unsaturated bonds, etc. As for other polymers, a polymer using a monomer having a polymerizable unsaturated bond is preferred. In addition, other polymers may be used alone or in combination of two or more. When another polymer is used, its usage ratio is preferably 50 mass % or less, more preferably 0.1 to 40 mass %, and still more preferably 0.1 to 30 mass % with respect to the total of the polymers contained in the polyimide paint. %.

As for the monomer having the above-mentioned polymerizable unsaturated bond, for example, (meth)acrylic-based compounds (including unsaturated carboxylic acids, unsaturated carboxylic acid esters, and unsaturated polyvalent carboxylic acid anhydrides.), (meth)acrylic acid amides Compounds, aromatic vinyl compounds, conjugated diene compounds, compounds containing maleimide groups, α-methylene-γ-butyrolactone compounds, vinyl compounds other than aromatic vinyl compounds, compounds containing maleimide groups Compounds of acid anhydride structure, etc. In the polymer aspect of the compound containing maleic anhydride structure, for example, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, and the like. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley Co., Ltd.), GSM301 (manufactured by Gifu Shellac Co., Ltd.), etc. Specific examples include ISOBAM-600 (manufactured by Kuraray), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP Japan Corporation) ).

In the polymer of the above-mentioned (meth)acrylic compound (hereinafter, also referred to as polymer (uA).), the usage ratio of the (meth)acrylic compound is 50 with respect to the total amount of the monomers used for synthesis. More than mol%, or more than 60 mol%.

The polymer (uA) can be obtained by, for example, polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. In terms of the polymerization initiator used, for example, azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and the like. The usage ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomers used for the reaction. The above-mentioned polymerization reaction is preferably carried out in an organic solvent. As for the organic solvent used in the reaction, for example, alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, etc., diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate and the like are preferable. The reaction temperature is preferably 30-120°C. The usage amount (a) of the organic solvent is preferably 0.1 to 60 mass % based on the total amount (b) of the monomers used in the reaction relative to the total amount (a+b) of the reaction solution.

(P為(甲基)丙烯醯基氧基、苯乙烯基、乙烯基氧基(CH₂ =CH-O-)、馬來醯亞胺基、α-亞甲基-γ-丁內酯構造。 X為單鍵、-(CH₂ )_a -(a為1~15的整數)、-CONH-、-NHCO-、-CON(CH₃ )-、-NH-、-O-、-COO-、-OCO-或-((CH₂ )_a1 -A₁ )_m1 - (a1為1~15的整數，A₁ 為氧原子或-COO-，m₁ 為1~2的整數。m₁ 為2時，複數的a1及A₁ 各自獨立具有上述定義)、或基「-L-OCO-CR’=CR”-」。但，P為(甲基)丙烯醯基氧基、乙烯基氧基(CH₂ =CH-O-)、馬來醯亞胺基時，X為單鍵、或透過碳原子與P鍵結之連結基。 J為具有由碳數4~40的脂環式烴基及碳數6~40的芳香族烴基所成群組中選出的至少1種基的1價有機基，但是，前述脂環式烴基及芳香族烴基所具有的氫原子的至少一個，被鹵原子、含鹵原子之烷基、含鹵原子之烷氧基、碳數3~10的烷基、碳數3~10的烷氧基、碳數3~10的烯基、以及上述含鹵原子之烷基、含鹵原子之烷氧基、烷基、烷氧基、及烯基的任意亞甲基所具有的碳-碳鍵被氧原子中斷的含雜原子之基所成群組中選出的取代基取代。) 又，上述式(S-mA)的J為具有2個以上由碳數4~40的脂環式烴基及碳數6~40的芳香族烴基所成群組中選出的至少1種基的1價有機基時，至少一個脂環式烴基或芳香族烴基具有上述之取代基即可，上述式(S-mA)的J所具有的其他脂環式烴基或芳香族烴基，亦可具有未取代或上述例示以外的取代基。 基「-L-OCO-CR’=CR”-」中，L為單鍵、或-(B₁ -(CH₂ )_b1 )_m’ -(b1為1~15的整數。B₁ 為單鍵、-CONH-、-NHCO-、-CON(CH₃ )-、-NH-、-O-、-COO-或-OCO-。m^’ 為1~2的整數。m^’ 為2時，複數的b1及B₁ 各自獨立具有上述定義，B₁ 的至少一個為單鍵以外的連結基。)。R’、R”為氫原子或碳數1~5的烷基。As monomers for obtaining the polymer (uA), monomers represented by the following formula (S-mA), monomers having carboxyl groups and polymerizable unsaturated bonds, monomers having epoxy skeletons and polymerizable unsaturated bonds can be used. Monomers with saturated bonds and monomers with other polymerizable unsaturated bonds.

(P is a structure of (meth)acryloyloxy, styryl, vinyloxy (CH ₂ =CH-O-), maleimide, α-methylene-γ-butyrolactone 。 X is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO- , -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 - (a1 is an integer from 1 to 15, A ₁ is an oxygen atom or -COO-, m ₁ is an integer from 1 to 2. m ₁ is 2 when plural a1 and a ₁ each independently have the above defined), or a group "-L-OCO-CR '= CR " - . "However, P is a (meth) Bing Xixi group, a vinyl group ( When CH ₂ =CH-O-) and maleimide group, X is a single bond or a linking group bonded to P through a carbon atom. J is an alicyclic hydrocarbon group having 4 to 40 carbon atoms and a carbon A monovalent organic group of at least one group selected from the group consisting of aromatic hydrocarbon groups of 6 to 40, but at least one of the hydrogen atoms possessed by the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is replaced by a halogen atom, a Halogen atom-containing alkyl group, halogen atom-containing alkoxy group, carbon number 3-10 alkyl group, carbon number 3-10 alkoxy group, carbon number 3-10 alkenyl group, and the above-mentioned halogen atom-containing alkyl group , Substituents selected from the group of heteroatom-containing groups whose carbon-carbon bonds are interrupted by oxygen atoms in alkoxy, alkyl, alkoxy, and alkenyl containing any methylene group Also, J in the above formula (S-mA) is at least one selected from the group consisting of two or more alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. In the case of a monovalent organic group, at least one alicyclic hydrocarbon group or aromatic hydrocarbon group may have the above-mentioned substituents, and other alicyclic hydrocarbon groups or aromatic hydrocarbon groups possessed by J of the above formula (S-mA) may also be It has unsubstituted or substituents other than those exemplified above. In the base "-L-OCO-CR'=CR"-", L is a single bond, or -(B ₁ -(CH ₂ ) _b1 ) _m' -(b1 is an integer of 1 to 15. B ₁ is a single bond , -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO- or -OCO-. m ^' is an integer from 1 to 2. When m ^' is 2, a complex number b1 and B ₁ is independently as defined above having at least a linking group other than a single bond, B ₁ in.). R', R" is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(X¹ 為單鍵、-(CH₂ )_a -(a為1~15的整數。)、-CONH-、 -NHCO-、-CON(CH₃ )-、-NH-、-O-、-COO-、-OCO-、   -((CH₂ )_a1 -A₁ )_m1 -(a1為1~15的整數。A₁ 為氧原子或-COO-，m₁ 為1~2的整數。m₁ 為2時，複數的a1及A₁ 各自獨立具有上述定義。)、或基「-L-OCO-CR’=CR”-」。 G¹ 為碳數6~12的2價芳香族烴基、碳數4~8的2價脂環式烴基所選出的2價環狀基。前述環狀基上的任意氫原子，可被碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子取代。但，m為1~4的整數。m為2以上時，複數的X¹ 、G¹ 各自獨立具有上述定義。 R¹ 為氟原子、碳數1~10的含氟原子之烷基、碳數1~10的含氟原子之烷氧基、碳數3~10的烷基、碳數3~10的烷氧基、或碳數3~10的烷氧基烷基。 基「-L-OCO-CR’=CR”-」中，L為單鍵、或-(B₁ -(CH₂ )_b1 )_m’ -(b1為1~15的整數。B₁ 為單鍵、-CONH-、-NHCO-、-CON(CH₃ )-、-NH-、-O-、-COO-或-OCO-。m^’ 為1~2的整數。m^’ 為2時，複數的b1及B₁ 各自獨立具有上述定義，B₁ 的至少一個為單鍵以外的連結基。)。 基「-L-OCO-CR’=CR”-」中，上述R’、R”為氫原子或碳數1~5的烷基。

(X² 為-CONH-、-NHCO-、-O-、-CH₂ O-、-OCH₂ -、  -COO-或-OCO-。G² 為具有類固醇骨架的構造。前述具有類固醇骨架的構造所具有的氫原子的至少一個，被鹵原子、含鹵原子之烷基、含鹵原子之烷氧基、碳數3~10的烷基、碳數3~10的烷氧基、碳數3~10的烯基、以及上述含鹵原子之烷基、含鹵原子之烷氧基、烷基、烷氧基、及烯基的任意亞甲基所具有的碳-碳鍵被氧原子中斷的含雜原子之基所成群組中選出的取代基取代。)As a preferable specific example of the said group "-XJ", the group represented by any one of following formula (S1)-(S2) is mentioned, for example.

(X ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15.), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, - COO-, -OCO-, -((CH ₂ ) _a1 -A ₁ ) _m1 -(a1 is an integer of 1 to 15. A ₁ is an oxygen atom or -COO-, and m ₁ is an integer of 1 to 2. m ₁ is 2, a plurality of a1 and a ₁ each independently have the above defined), or a group "-L-OCO-CR '= CR " - ".. G ¹ is a divalent aromatic hydrocarbon group having a carbon number of 6 to 12 carbons, A bivalent cyclic group selected from a bivalent alicyclic hydrocarbon group with a number of 4 to 8. Any hydrogen atom on the aforementioned cyclic group may be replaced by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. , a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having a carbon number of 1 to 3, or a fluorine atom substitution. However, m is an integer of 1 to 4. When m is 2 or more, plural X ¹ , G ¹ each independently has the above definition. R ¹ is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having a carbon number of 1 to 10 fluorine atom-containing atoms, an alkyl group having 3 to 10 carbon atoms, a carbon An alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms. In the group "-L-OCO-CR'=CR"-", L is a single bond, or -(B ₁ -( CH ₂ ) _b1 ) _m' -(b1 is an integer from 1 to 15. B ₁ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO- or -OCO-.m ^'is an integer of 1 to 2 ^.m' is 2, a plurality of b1 and B ₁ each independently as defined above having at least a linking group other than a single bond B is ₁₎ group ". - In L-OCO-CR'=CR"-", the above R' and R" are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

(X ² is -CONH-, -NHCO-, -O-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. G ² is a structure having a steroid skeleton. The aforementioned structure having a steroid skeleton At least one of the hydrogen atoms it has is selected from a halogen atom, an alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, and an alkoxy group having 3 to 10 carbon atoms. Alkenyl group of ~10, and the carbon-carbon bond of any methylene group of the above-mentioned halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom Substituents selected from the group consisting of heteroatom-containing groups.)

In the above formula (S1), ^{the divalent cyclic group in G 1} is, for example, a cycloextended propyl group, a cyclohexylene group, and a phenylene group. Any hydrogen atom on these cyclic groups may be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Fluoroalkoxy or fluorine atom substitution.

In the above formula (S2), G ² has a structure of a steroid skeleton, such as a structure including a cholestanyl group, a cholestenyl group or a lanostannyl group.

Specific examples of the above-mentioned monomers having a carboxyl group and a polymerizable unsaturated bond include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-hydroxyethyl (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, 2-acryloyloxyethylsuccinic acid, 2- Carboxyl-containing (meth)acrylate compounds such as methacryloyloxyethylsuccinic acid; vinyl-containing aromatic carboxylic acids such as 4-vinylbenzoic acid; 4-maleimidebenzoic acid, etc. carboxyl-containing maleimide; carboxyl-containing (meth)acrylamide compounds such as N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

The above-mentioned monomers having epoxy skeleton and polymerizable unsaturated bonds, such as allyl glycidyl ether, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, α- Glycidyl ethyl (meth)acrylate, α-n-propyl (meth)acrylate, α-n-butyl (meth)acrylate, 3,4-(meth)acrylate Epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Glyceryl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexyl alkene, 1,7-octadiene monoepoxide.

As for the monomer which has the said other polymerizable unsaturated bond, the following monomers are mentioned, for example.

Amino-group-containing (meth)acrylate compounds such as aminoethyl (meth)acrylate and aminopropyl (meth)acrylate; N-Hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (Meth)acrylamide compounds containing hydroxymethyl or alkoxymethyl groups such as (meth)acrylamide; 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyl oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane Compounds with oxetane skeleton such as alkane, 3-(methacryloyloxymethyl)-3-ethyl oxetane, etc.; 2-(2-Pyridylcarbonyloxy)ethyl(meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl(meth)acrylate, 2-(4-pyridylcarbonyloxy) ) compounds with nitrogen-containing aromatic heterocycles such as ethyl (meth)acrylate; Methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2,2, 2-Trifluoroethyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (Meth)acrylate, Methoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, 3-methoxy butyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 8-methyl-8 - (meth)acrylate compounds such as tricyclodecyl (meth)acrylate and 8-ethyl-8-tricyclodecyl (meth)acrylate; Acrylic amide compounds such as acrylamide, methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc.; Vinyl ether compounds such as methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, etc.; aromatic vinyl compounds such as styrene, methyl styrene, chlorostyrene, and bromostyrene ; Maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide and other compounds containing maleimide groups.

In terms of the monomer components used to obtain the polymer (uA), the above-mentioned monomer having a carboxyl group and a polymerizable unsaturated bond, the above-mentioned monomer having an epoxy skeleton and a polymerizable unsaturated bond, and the above-mentioned formula (S-mA ), the total of the monomers is preferably 10 mol% or more, more preferably 20 mol% or more. In the case where the above monomers having other polymerizable unsaturated bonds are used in combination, the sum of the above monomers having carboxyl groups and polymerizable unsaturated bonds and the monomers represented by the above formula (S-mA) is 99 mol% or less. best, more preferably below 95 mol %, still more preferably below 90 mol %.

The molecular weight of the polymer (uA) obtained as described above is preferably 2,000 to 1,000,000, more preferably 10,000 to 150,000, as measured by GPC (Gel Permeation Chromatography) method. Moreover, the number average molecular weight (Mn) is preferably 3,000 to 100,000, and more preferably 10,000 to 50,000.

The crosslinkable compound can be used for the purpose of improving the strength of the liquid crystal alignment film. In terms of the crosslinkable compound, for example, the compound having a hydroxyalkylamide bond or the compound having an alkoxyalkylamide bond described in Japanese Patent Laid-Open No. 2016-118753 or WO2015/156314, [0109 of WO2016/047771] ] ~ [0113] described in having at least one selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group, hydroxyalkyl group, isocyanate group, cyclocarbonate, and lower alkoxyalkyl group based compounds, and compounds with blocked isocyanate groups, etc.

Aspects of the compound having an epoxy group above, wherein ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether base ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1 , 3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resin such as EPIKOTE828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin such as EPIKOTE807 (manufactured by Mitsubishi Chemical Corporation) Epoxy resin, hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), epoxy resin containing biphenyl skeleton such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), EPPN-201 (Japan Gunpowder Co., Ltd.) Novolak-type epoxy resin such as EOCN-102S (manufactured by Nippon Gunpowder Co., Ltd.), (o,m,p-) cresol novolak-type epoxy resin, TEPIC (manufactured by Nissan Chemical Co., Ltd.), etc. Alicyclic epoxy resins such as glycidyl isocyanurate, Celloxide2021P (manufactured by Daicel Chemical Industry Co., Ltd.), N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4, 4'-diaminodiphenylmethane , Four (glycidyloxymethyl)methane is preferred.

The blocked isocyanate compound can be obtained as a commercially available product, for example, CORONATE AP Stable M, CORONATE 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (the above, manufactured by Tosoh Corporation), TAKENATEB-830, B-815N, B -820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), etc.

上述為交聯性化合物的一例，並不限於此等。又，本發明之液晶配向劑所使用的交聯性化合物亦可為2種類以上組合。Specific examples of preferred crosslinkable compounds include compounds represented by the following formulae (CL-1) to (CL-11).

The above is an example of a crosslinkable compound, and it is not limited to these. Moreover, the crosslinkable compound used for the liquid crystal aligning agent of this invention may be a combination of 2 or more types.

In the liquid crystal aligning agent, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass, more preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass with respect to 100 parts by mass of the total polymer components. The functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the base substrate. As a specific example, for example, the silane compound described in paragraph [0019] of International Publication No. 2014/119682. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total polymer components.

The surfactant can be used to improve the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film. Surfactants, such as fluorine-based surfactants, polysiloxane-based surfactants, non-ionic surfactants, etc. Specific examples of these are described in [0117] of WO2016/047771, for example. The usage-amount of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total polymer contained in the liquid crystal aligning agent. The compound having a photopolymerizable group is a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule, for example, any of the following formulae (M-1) to (M-7) a compound represented.

The organic solvent that the liquid crystal aligning agent can contain can be used as described in the polyimide paint. The type and content of the solvent can be appropriately selected according to the coating device, coating conditions, and coating environment of the liquid crystal aligning agent. The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the organic solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected considering viscosity, volatility, etc., but preferably 1~10 mass %.

The particularly preferable solid content concentration varies depending on the method used for coating the liquid crystal aligning agent on the substrate. For example, in the case of the spin coating method, 1 to 10 mass % is particularly preferable. In the case of the printing method, it is 3 to 9 mass %, and the solution viscosity is particularly preferably 12 to 50 mPa･s. In the case of the ink jet method, it is 1 to 5 mass %, and the viscosity of the solution is particularly preferably 3 to 15 mPa･s.

After the liquid crystal alignment agent is coated and fired on the substrate, alignment treatment such as rubbing treatment or light irradiation is performed, and it can be used as a liquid crystal alignment film. In addition, it can also be used as a liquid crystal alignment film without an alignment treatment in applications such as vertical alignment. The substrate used at this time is not particularly limited to a substrate with high transparency. In addition to glass substrates, plastic substrates such as acrylic substrates, polycarbonate substrates, and PET (polyethylene terephthalate) substrates can be used. , and thus their thin films. Also, from the viewpoint of process simplification, metal electrodes such as ITO electrodes for liquid crystal driving, IZO (Indium Zinc Oxide) electrodes, and IGZO (Indium Gallium Zinc Oxide) electrodes, and substrates on which organic conductive films and the like are formed are preferably used. In addition, in the case of forming a reflective liquid crystal display element, if only one side of the substrate is used, a metal such as silicon wafer or aluminum, or a substrate formed with a dielectric multilayer film can be used.

Although the coating method of the liquid crystal aligning agent is not particularly limited, industrially, it is generally performed by screen printing, offset printing, flexographic printing, or inkjet method. As for other coating methods, there are a dip method, a roll coating method, a slit coating method, a spin coating method, a spray method, and the like, and these can be used according to the purpose. After coating the liquid crystal alignment agent on the substrate, the temperature is 30~300°C, preferably 30°C, according to the solvent used by the liquid crystal alignment agent by heating means such as a heating plate, a thermal cycle oven or an IR (infrared) oven. The solvent was evaporated at a temperature of ~250°C to form a liquid crystal alignment film.

If the thickness of the liquid crystal alignment film after firing is too thick, the power consumption of the liquid crystal display element will be disadvantageous. If the thickness of the liquid crystal alignment film is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm. . When aligning the liquid crystal horizontally or diagonally, the liquid crystal alignment film after firing is treated by rubbing or irradiation with polarized ultraviolet rays. In the above-mentioned ultraviolet rays, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser can be used. The ultraviolet rays in the aforementioned preferable wavelength range can be obtained by using the aforementioned light source in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,000 J/m ² or more and less than 100,000 J/m ² , more preferably 1,000 to 50,000 J/m ² . Although the liquid crystal used for the liquid crystal display element is not particularly limited, for example, a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal can be used. At this time, according to the mode of the liquid crystal display element, a liquid crystal having positive or negative dielectric anisotropy can be selected. Moreover, a dichroic dye is melt|dissolved in a liquid crystal, and it may be a guest-host type liquid crystal display element. The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film for a horizontal alignment type or a vertical alignment type liquid crystal display element. In terms of the liquid crystal alignment film for horizontal alignment type liquid crystal display elements, it is suitable to be used as a liquid crystal alignment film for horizontal electric field liquid crystal display elements such as IPS mode or FFS mode, or a liquid crystal alignment film for horizontal alignment liquid crystal display elements such as TN mode. In particular, it is suitable for use as a liquid crystal alignment film for liquid crystal display elements of the FFS system. Among the liquid crystal alignment films obtained from the liquid crystal aligning agent of the present invention, the liquid crystal alignment films for vertical alignment type liquid crystal display elements such as the VA system and the PSA model are suitable. Moreover, the liquid crystal alignment film for vertical alignment type liquid crystal display elements, such as the said VA system and PSA mode, can be obtained by using the alignment treatment including photo-alignment treatment. The preferable aspects of the light irradiated in the photo-alignment treatment, the light source, and the irradiation amount of the light are the same as those described above. In addition, the liquid crystal alignment film obtained by containing the polyimide-painted liquid crystal alignment agent of the present invention can also be used for liquid crystal alignment films for retardation films, liquid crystal alignment films for scanning antennas or liquid crystal array antennas, or transmission-scattering type liquid crystal alignment films. The liquid crystal alignment film for the liquid crystal dimming element, or other uses, such as the protective film of the color filter, the gate insulating film of the flexible display, and the substrate material.

The liquid crystal display element using the liquid crystal aligning agent of the present invention can be applied to various devices. Such as clocks, handheld games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital phase machines, mobile phones, smart phones, various displays, LCD TVs, information displays, etc. [Example]

The following is further detailed based on the examples, but the present invention is not limited to the examples. In addition, the abbreviations, measurement methods, etc. of the compounds used below are as follows. (Tetracarboxylic dianhydride) BODA: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA : Pyromellitic anhydride TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride 13DM- CBDA: 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

(Diamine) PDA: p-phenylenediamine DBA: 3,5-diaminobenzoic acid 3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

下述式DA-2~9所表示之二胺

(Boc表示tert-丁氧基羰基。) (甲基丙烯酸化合物) 下述式MA-1~3所表示之甲基丙烯酸化合物

(自由基聚合起始劑) AIBN：偶氮二異丁腈Vertical alignment diamine represented by the following formula DA-1

Diamine represented by the following formula DA-2~9

(Boc represents a tert-butoxycarbonyl group.) (Methacrylic acid compound) Methacrylic acid compounds represented by the following formulae MA-1 to 3

(Radical Polymerization Initiator) AIBN: Azobisisobutyronitrile

<Solvent> NMP: N-methyl-2-pyrrolidone, BCS: butyl cellosolve <Amine compound (B)> 3AMP: 3-pyridylmethylamine, Me-3AMP: N-methyl-3-pyridylmethylamine MBA: N-methylbenzylamine, DMBA: N,N-dimethylbenzylamine

<Molecular weight measurement> Apparatus: Room temperature colloidal permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific, Column: Column (KD-803, KD-805) manufactured by Shodex Column temperature: 50°C Elution Liquid: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr･H ₂ O): 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid): 30 mmol/L, tetrahydrofuran (THF) 10 mL/L), flow rate: 1.0 ml/min Standard sample for calibration line preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: about 900,000, 150,000, 100,000, 30,000), and, manufactured by Polymer Laboratories Ltd. Ethylene glycol (molecular weight: about 12,000, 4,000, 1,000).

<Measurement of imidization rate> 20 mg of polyimide powder was placed in an NMR sample tube (NMR sample tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), and deuterated dimethylsulfoxide (DMSO-d ₆ , 0.05% TMS was added and mixed) product) 1.0mL, and ultrasonically applied to dissolve it completely. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measuring device (JNW-ECA500) manufactured by JEOL Datum Ltd. The imidization rate was determined by using the proton derived from the structure that did not change before and after imidization as the reference proton, and the peak accumulation value of the proton and the NH group derived from the imidic acid appearing in the vicinity of 9.5 to 10.0 ppm were used. The cumulative value of the proton peaks of , is obtained by the following formula. In the following formula, x is the cumulative peak value of protons derived from the NH group of aramidic acid, y is the cumulative peak value of reference protons, and α is the value of the The ratio of the number of reference protons to one proton of the NH group of the amide acid. Imidization rate (%)=(1-α･x/y)×100

<Viscosity measurement> The viscosity of the liquid crystal aligning agent was measured at a temperature of 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a conical rotor TE-1 (1°34', R24).

(Synthesis Example 1) BODA (15.0 g, 60.0 mmol), DBA (18.3 g, 120 mmol), 3AMPDA (21.8 g, 90.0 mmol), and DA-1 (34.3 g, 90.0 mmol) were dissolved in NMP (357 g) at 60° C. After the reaction for 3 hours, PMDA (13.1 g, 60.0 mmol), CBDA (34.1 g, 174 mmol) and NMP (137 g) were added, and the reaction was performed at 25° C. for 10 hours to obtain a polyamic acid solution. NMP was added to this polyamic acid solution (500 g) and diluted to 6.5 mass %, then anhydrous acetic acid (111 g) and pyridine (34.5 g) were added as an imidization catalyst, and the reaction was carried out at 60° C. for 3 hours. The reaction solution was put into methanol (7000 mL), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (A). The imidization rate of this polyimide was 80%, the number average molecular weight was 12,000, and the weight average molecular weight was 24,000.

(Synthesis example 2) TCA (43.9 g, 196 mmol), DA-2 (30.3 g, 40.0 mmol), DA-4 (9.49 g, 40.0 mmol), DA-5 (13.9 g, 70.0 mmol), DA-6 (16.5 g, 50.0 mmol) were made mmol) in NMP (455 g), and reacted at 60° C. for 15 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. To this polyamic acid solution (100 g), NMP was added and diluted to 6.5% by mass, then anhydrous acetic acid (17.9 g) and pyridine (5.55 g) were added as imidization catalysts, and the reaction was carried out at 100° C. for 3 hours. . The reaction solution was poured into methanol (1160 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a polyimide powder (B). The imidization rate of this polyimide was 72%, the number average molecular weight was 13,300, and the weight average molecular weight was 40,500.

(Synthesis example 3) TDA (30.0 g, 100 mmol), PDA (9.73 g, 90 mmol), and DA-3 (3.77 g, 10.0 mmol) were dissolved in NMP (247 g), and the reaction was carried out at 40° C. for 3 hours to obtain a polyamic acid solution. NMP was added to this polyamic acid solution (50 g), and after diluting to 5 mass %, anhydrous acetic acid (17.6 g) and pyridine (8.20 g) were added as imidization catalysts, and the reaction was carried out at 40° C. for 3 hours. The reaction gets た. This reaction solution was poured into methanol (600 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (C). The imidization rate of this polyimide was 85%, the number average molecular weight was 13,400, and the weight average molecular weight was 27,000.

(Synthesis example 4) 13DM-CBDA (17.1 g, 76.4 mmol), PDA (1.73 g, 16.0 mmol), DA-7 (5.86 g, 24.0 mmol), DA-8 (7.69 g, 24.0 mmol), DA-9 (5.46 g, 24.0 mmol) 16.0 mmol) was dissolved in NMP (277 g), and the reaction was carried out at 50° C. for 15 hours to obtain a polyamic acid solution. NMP was added to this polyamic acid solution (100 g) and diluted to 9 mass %, then anhydrous acetic acid (7.60 g) and pyridine (0.98 g) were added as imidization catalysts, and the reaction was carried out at 55° C. for 3 hours. . The reaction solution was poured into methanol (530 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a polyimide powder (D). The imidization rate of this polyimide was 66%, the number average molecular weight was 14,300, and the weight average molecular weight was 35,800.

(Synthesis Example 5) MA-1 (10.2 g, 20.0 mmol), MA-2 (2.61 g, 30.0 mmol), MA-3 (2.35 g, 16.5 mmol) and NMP (60.6 g) were added to a 4-neck flask to make each monomer component completely dissolved. The solution was degassed with a diaphragm pump, and AIBN (0.550 g, 3.33 mmol) was added as a polymerization initiator, followed by degassing. Then, reaction was performed at 60 degreeC for 13 hours, and the methacrylic acid polymer solution (E) was obtained. The polymer had a number average molecular weight of 15,800 and a weight average molecular weight of 68,200.

(Example 1) NMP (44.0 g) was added to the obtained polyimide powder (A) (6.00 g), and the mixture was stirred at 70° C. for 20 hours to dissolve. Me-3AMP (2 mass % NMP solution, 6.00 g) as an amine compound (B) was added to this solution, and NMP (4.00 g) and BCS (40.0 g) were further added, and the liquid crystal was obtained by stirring at room temperature for 3 hours. Alignment Agent (A1).

(Examples 2 and 3 and Comparative Examples 1 and 2) In Example 1, except having changed the kind of the amine compound (B) added, it implemented similarly, and prepared the liquid crystal aligning agent (A2) - (A5). About each obtained liquid crystal aligning agent and the amine compound (B) used for it, it is as shown in the following Table 1. In addition, in Comparative Example 2, the amine compound (B) was not added.

<Storage stability test> The liquid crystal aligning agents obtained in Examples 1 to 3 and Comparative Example 1 or 2 were placed in a vial, sealed, and allowed to stand at 25° C. in a light-shielding environment. The change of the viscosity of the liquid crystal aligning agent in the standing still and the molecular weight of the polyimide contained in the liquid crystal aligning agent were tracked. The following Table 2 shows the change in the viscosity of the liquid crystal aligning agent, and Table 3 shows the change in the molecular weight (number average molecular weight) of the polyimide contained in the liquid crystal aligning agent.

<Evaluation of whitening properties> 0.1 mL of the liquid crystal aligning agents obtained in Examples 1 to 3 and Comparative Example 1 or 2 were dropped on a chromium substrate, and left to stand still in an environment with a temperature of 23° C. and a humidity of 70%. The edge and center part of the droplet were observed with an optical microscope, and the time until a precipitate was generated was measured. In addition, in this evaluation, the phenomenon that the dissolved polyimide precipitates or aggregates and the droplet becomes cloudy is defined as a whitening phenomenon. The state of the droplet with no whitening at all was evaluated as "0", the state of whitening only at the edge of the droplet was evaluated as "△", and the state of complete whitening of the droplet was evaluated as "X". Table 4 shows the evaluation results of the whitening characteristics after 3 days of the aforementioned storage stability test of the liquid crystal aligning agent.

From the results in Tables 2 and 3, it can be seen that in Examples 1 to 3, compared with the changes in viscosity and molecular weight of Comparative Example 1, the decrease in viscosity and molecular weight was significantly suppressed, and the storage stability of the polyimide paint was improved. From the results of the whitening test in Table 4, it can be seen that the whitening characteristics of Examples 1 to 3 are significantly improved compared to Comparative Example 2. Furthermore, from the result of Table 4, it turns out that Example 1-3 is less likely to deteriorate the whitening characteristic compared with the comparative example 1. This is considered to be because the aliphatic amine of 3AMP is the first-order amine, so it is easy to attack the main chain of polyimide nucleophile, and in the second and third amines, the effect of steric hindrance inhibits the main chain of polyimide. The nucleophilicity of the chain.

(Examples 4 to 8, Comparative Examples 3 to 12, Synthesis Examples 6 to 8) In Example 1, except that the polyimide powder, amine compound, and organic solvent were changed as shown in Table 5 below, the same operation was carried out to prepare liquid crystal aligning agents (B1) to (B2), (C1) to (C3) and (D1)~(D3). Further, 6.00 g of NMP (24.0 g), BCS (40.0 g), and MBA (2 mass % NMP solution) were added to the methacrylic acid polymer solution (E) (30.0 g) obtained in Synthesis Example 5, and the reaction was carried out at room temperature. After stirring for 3 hours, a liquid crystal aligning agent (E1) was obtained (Synthesis Example 6). Furthermore, in Synthesis Example 6, liquid crystal aligning agents (E2) to (E3) were prepared in the same manner except that the amine compound was changed as in Table 5 below (Synthesis Examples 7 and 8). The combination of each liquid crystal aligning agent and the additive used for it is shown in Table 5.

關於上述所得到的液晶配向劑，與上述同樣地實施保存安定性試驗與白化特性的評估。以下的表7~10為結果。Next, the liquid crystal alignment agents (B1) to (B3) and (E1) to (E3) obtained so far were mixed with the liquid crystal alignment agents (A2), (A4) and (A5). Table 6 shows the combination of the mixed liquid crystal alignment agent and the additives contained in the liquid crystal alignment agent.

Regarding the liquid crystal aligning agent obtained above, the storage stability test and the evaluation of whitening characteristics were carried out in the same manner as described above. The following Tables 7 to 10 show the results.

<Storage stability test>

<Evaluation of whitening characteristics> Table 9 shows the evaluation results performed on the day of preparation of the liquid crystal aligning agent, and Tables 9 and 10 show the evaluation results after the above-mentioned storage stability test for 3 days.

From the results in Tables 7 and 8, it can be seen that in Examples 5 to 8, the decrease in viscosity and molecular weight was significantly suppressed, and the storage stability was improved. Furthermore, from the results of the whitening tests in Tables 9 and 10, it can be seen that Examples 5 to 8 have significantly improved whitening properties compared to Comparative Examples 5 to 12. [Industrial Availability]

The polyimide varnish of the present invention is widely used in a wide range of fields, such as a liquid crystal alignment agent for forming a liquid crystal alignment film in a liquid crystal display element, and an insulating film for semiconductors in the electrical and electronic fields, especially a film-like protective material or an insulating material. used.

In addition, the entire contents of the specification, the scope of application and the abstract of Japanese Patent Application No. 2020-30729 filed on February 26, 2020 are cited as disclosures of the specification of the present invention.

Claims (17)

A polyimide paint is characterized by containing the following (A) components and (B) components, (A) component: polyimide (A) which is an imide of a polyimide precursor, (B) Component: any one group having a second-order amino group or a third-order amino group and any one cyclic group of a nitrogen-containing aromatic heterocycle or an aromatic hydrocarbon group in the molecule, and the aforementioned amino group is bonded An amine compound (B) based on an acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. The polyimide paint according to claim 1, wherein the amine compound (B) is represented by the following formula (1),

(R ₁ and R ₂ are hydrogen atoms or alkyl groups with 1 to 5 carbon atoms _{, at least one of R 1} and R ₂ is an alkyl group with 1 to 5 carbon atoms, and Ar is a nitrogen-containing aromatic heterocycle or aromatic Hydrocarbon group, X is a divalent organic group containing an acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, _{and the N to which R 1} and R ₂ are bonded is bonded to the aforementioned acyclic aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group hydrocarbon group). 2 according to the requested item as polyimide paint, wherein the amine compound (B) is the formula wherein X (1) _{* 1-X 1 -X 2 -} * 2 ( however, X is a C 1 ₁ ~10 divalent organic groups containing acyclic aliphatic hydrocarbon groups or non-aromatic cyclic hydrocarbon groups, X ₂ is a single bond, -O-, -NH-, -S-, -SO ₂ - or carbon number 1~ The divalent organic group of 19, and _{the total number of carbon atoms possessed by X 1} and X ₂ is 1 to 20, *1 is a bond to N of the formula (1), and *2 is a bond to the formula (1) (1) The compound represented by the Ar bonding bond). The polyimide paint according to claim 3, wherein in the aforementioned -X ₁ -X ₂ -, X ₁ is a divalent acyclic aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms . The polyimide paint according to any one of claims 1 to 4, wherein the amine compound (B) is a compound represented by any one of the following formulae (b-1) to (b-14) 1 or more of

The polyimide paint according to any one of claims 1 to 5, wherein the polyimide precursor of the polyimide (A) contains a tetracarboxylic acid represented by the following formula (3) is used obtained from the tetracarboxylic acid component of acid dianhydride or its derivatives,

(X is the structure selected from the following group (x-1)~(x-13))

(R ¹ to R ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, a fluorine atom, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and R ⁵ and R ^{6 is} each independently a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or 1, A ₁ and A ₂ are each independently, a single bond, -O-, -CO-, -COO-, extension Phenyl group, sulfonyl group, or amide group, *1 is a bond bond to one acid anhydride group, *2 is a bond bond to another acid anhydride group, two A ₂ can be the same or the same to be different). The polyimide paint according to claim 6, wherein the tetracarboxylic dianhydride represented by the aforementioned formula (3) or a derivative thereof is X, and X is the aforementioned formulas (x-1) to (x-7), ( x-11)~(x-13) Tetracarboxylic dianhydride or its derivatives. The polyimide paint according to any one of claims 1 to 7, wherein the polyimide precursor of the polyimide (A) is a polyimide precursor having the following formulas (S1) to (S3) Diamine (a) of the indicated structure is obtained,

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -, where a1 is an integer from 1 to 15, A ₁ is an oxygen atom or -COO-, and m ₁ is 1~2, G ¹ and G ² are each independently, and are a bivalent cyclic group of a bivalent aromatic group having a carbon number of 6 to 12 or a bivalent alicyclic group having a carbon number of 3 to 8. Any hydrogen atom can be substituted, m and n are each independently an integer of 0~3, and m+n is 1~6, R ¹ is an alkyl group with 1~20 carbons, an alkoxy group with 1~20 carbons or An alkoxyalkyl group having 2 to 20 carbon atoms, ^{any hydrogen atom forming R 1} may be substituted by a fluorine atom, and when there are two or more ^{X 1} , X ² , G ¹ , G ² , a1 , and A _{1 , two} The above X ¹ , X ² , G ¹ , G ² , a1 , and A ₁ independently may be the same or different)

(X ³ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-, R ² is carbon number 1~20 alkyl group or 2~20 carbon number alkoxyalkyl group, ^{any hydrogen atom forming R 2} can be substituted by fluorine atom)

(X ⁴ is -CONH-, -NHCO-, -O-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-, and R ³ is a structure having a steroid skeleton). The polyimide paint according to claim 8, wherein the diamine (a) is at least one diamine selected from the group consisting of the following formulae (V-1) to (V-13),

(In the above formula, X ^v1 to X ^v4 and X ^p1 to X ^p8 are independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ ) -, - NH -, - O -, - CH 2 O -, - CH 2 OCO -, - COO-, or -OCO-, X ^v5 is _{-O -, - CH 2 O -} , - CH 2 OCO- , -COO-, or -OCO-, X ^V6 ~X ^V7 , X ^s1 ~X ^s4 are independently -O-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-, X _a ~X _f are each independently, single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-, -C(CH ₃ ) ₂ -, -CO-, -COO-, -CONH- , -(CH ₂ ) _m -, -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -NH-, -SO ₂ -(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -SO ₂ -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO -, or -COO-(CH ₂ ) _m -OCO-, R ^v1 to R ^v4 and R ^1a to R ^1h are each independently, and are an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon An alkoxyalkyl group of 2 to 20, m is an integer of 1 to 8). The polyimide paint according to any one of Claims 1 to 9, wherein the polyimide (A) has 20 to 90% of all repeating units of the polyimide precursor relative to the polyimide precursor. structure. The polyimide paint according to any one of claims 1 to 10, wherein the amine compound is contained in a ratio of 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyimide (A). (B). A liquid crystal aligning agent obtained by the polyimide paint according to any one of claims 1 to 11. The liquid crystal alignment agent according to claim 12, wherein the liquid crystal alignment agent further contains a polyimide precursor, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative At least one other polymer selected from the group consisting of a polymer, a polyacetal, and a polymer of a monomer having a polymerizable unsaturated bond. The liquid crystal aligning agent according to claim 12 or 13, wherein the polymer system of the monomer having a polymerizable unsaturated bond is composed of a (meth)acrylic compound, a (meth)acrylic acid amide compound, an aromatic Vinyl compounds, conjugated diene compounds, compounds containing maleimide groups, α-methylene-γ-butyrolactone compounds, vinyl compounds other than aromatic vinyl compounds, and structures containing maleic anhydride obtained from at least one compound selected from the group of compounds. The liquid crystal aligning agent according to any one of Claims 12 to 14, wherein the polymer of the monomer having a polymerizable unsaturated bond uses a monomer represented by the following formula (S-mA), has a carboxyl group and is polymerized It is obtained from a monomer with a unsaturated bond and at least one monomer selected from the group consisting of a monomer having an epoxy skeleton and a polymerizable unsaturated bond,

(P is a structure of (meth)acryloyloxy, styryl, vinyloxy (CH ₂ =CH-O-), maleimide, α-methylene-γ-butyrolactone , X is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15.), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO -, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 -(a1 is an integer from 1 to 15, A ₁ is an oxygen atom or -COO-, m ₁ is an integer from 1 to 2, and m ₁ is 2, a plurality of a1 and a ₁ each independently have the above defined), or a group "-L-OCO-CR '= CR " - ", however, P is (meth) Bing Xixi group, vinyloxy (CH ₂ =CH-O-), maleimide group, X is a single bond or a linking group bonded to P through a carbon atom, J is an alicyclic hydrocarbon group having 4 to 40 carbon atoms, and A monovalent organic group of at least one group selected from the group consisting of aromatic hydrocarbon groups having 6 to 40 carbon atoms, but at least one of the hydrogen atoms possessed by the aforementioned alicyclic hydrocarbon groups and aromatic hydrocarbon groups is replaced by a halogen atom. , halogen-containing alkyl groups, halogen-containing alkoxy groups, alkyl groups with 3 to 10 carbon atoms, alkoxy groups with 3 to 10 carbon atoms, alkenyl groups with 3 to 10 carbon atoms, and the above halogen atoms-containing Alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and any methylene group of alkenyl group selected from the group of heteroatom-containing groups whose carbon-carbon bond is interrupted by an oxygen atom Substituted by a substituent, in the group "-L-OCO-CR'=CR"-", L is a single bond, or -(B ₁ -(CH ₂ ) _b1 ) _m' -(b1 is an integer of 1 to 15, B ₁ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO- or -OCO-, m ^' is an integer from 1 to 2, and m ^' is 2, a plurality of b1 and B ₁ each independently defined above, B ₁ is at least one linking group other than a single bond), R ', R "is a hydrogen atom or an alkyl having 1 to 5). A liquid crystal alignment film formed using the liquid crystal alignment agent described in any one of claims 12 to 15. A liquid crystal display element provided with the liquid crystal alignment film of claim 16.