WO2017217465A1

WO2017217465A1 - Liquid crystal aligning agent for coating of boa substrate or substrates with bcs, and liquid crystal display element

Info

Publication number: WO2017217465A1
Application number: PCT/JP2017/021996
Authority: WO
Inventors: 暁子杉山; 亮一芦澤; 政太郎大田; 徳俊三木
Original assignee: 日産化学工業株式会社
Priority date: 2016-06-14
Filing date: 2017-06-14
Publication date: 2017-12-21
Also published as: JP7067472B2; KR20190019133A; JPWO2017217465A1; TW201815893A; TWI749019B; KR102420192B1; CN109564370A; CN109564370B

Abstract

Provided are: a liquid crystal aligning agent for coating of a BOA substrate or a substrate with a BCS; and a liquid crystal display element that is provided with a BOA substrate or a substrate with a BCS, which is obtained using the liquid crystal aligning agent and has good display quality. A liquid crystal aligning agent for coating of a BOA substrate or a substrate with a BCS, which contains at least one polymer selected from the group consisting of polyimide precursors obtained by reacting a tetracarboxylic acid dianhydride component with a diamine component that contains a diamine containing a nitrogen atom or a carboxylic acid group in a structure other than two amino groups and polyimides obtained by imidizing the polyimide precursors; and a liquid crystal display element that comprises a BOA substrate or a substrate with a BCS, which is provided with a liquid crystal alignment film obtained from the liquid crystal aligning agent.

Description

Liquid crystal aligning agent and liquid crystal display element for coating substrate with BOA substrate or BCS

The present invention relates to a liquid crystal aligning agent for coating a BOA substrate or a substrate with BCS, and a liquid crystal display element having a BOA substrate or a substrate with BCS obtained using the same.

In general, a liquid crystal display element includes an array substrate on which a thin film transistor is formed, and a counter substrate on which a color filter is formed facing the array substrate, and includes a liquid crystal layer interposed between the array substrate and the counter substrate. Including. The color filter requires a black matrix at the boundary between colored layers such as red, green, and blue for the purpose of enhancing the contrast and coloring effect. In recent years, due to manufacturing yield, etc., color filter on array (COA) in which color filters are formed on the array substrate, and black matrix that forms a black matrix on the COA substrate. Black matrix on array (BOA) substrates have been developed.
From the viewpoint of further manufacturing yield and the like, attempts have been made to use the black colored resin composition as a column spacer material for supporting the space between the array substrate and the counter substrate (such a column spacer is used as a black column spacer). (Also referred to as BCS: Black Colum Spacer)), the black matrix material may be used for the black colored resin composition.

Japanese Unexamined Patent Publication No. 2014-167492 Japanese Unexamined Patent Publication No. 2015-191234

Due to the structure of the BOA substrate, it is difficult to ensure the reliability when the liquid crystal display element is manufactured as compared with the COA substrate, and the display quality of the liquid crystal display element may be deteriorated. Furthermore, the above problem becomes more noticeable by using the substrate with BCS.
This invention is made | formed in view of said situation, Comprising: The BOA board | substrate or BCS which has a favorable display quality obtained using the liquid crystal aligning agent for board | substrate coating with a BOA board | substrate or BCS, and the said liquid crystal aligning agent An object of the present invention is to provide a liquid crystal display element having a substrate.

As a result of intensive studies, the present inventors have completed the present invention.
That is, the present invention has the following gist.
1. A polyimide precursor obtained by reacting a diamine component containing a diamine containing nitrogen or a carboxylic acid group with a tetracarboxylic dianhydride component in a structure other than two amino groups, and the polyimide precursor A liquid crystal aligning agent for coating a substrate with a BOA substrate or BCS, which contains at least one polymer selected from the group consisting of imidized polyimides.
2. 2. The liquid crystal aligning agent according to 1 above, wherein the diamine has at least one structure selected from the group consisting of the following formulas as a partial structure.

(In the formula, Cy is a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and a substituent may be bonded to these ring portions. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group or * —CONH— (where a bond marked with “*” is bonded to a piperidine ring) R ₁₅ is hydrogen or a monovalent organic group R ₁₈ and R ₁₉ are each independently a hydrogen atom or a single bond.)
3. 3. The liquid crystal aligning agent according to 1 or 2 above, wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulas (1) to (9).
4). 4. The liquid crystal aligning agent according to any one of the above 1 to 3, wherein the diamine component contains a diamine represented by the following formula (10) or (11).
5. The liquid crystal according to any one of the above 1 to 4, wherein the tetracarboxylic dianhydride component is at least one tetracarboxylic dianhydride selected from the group consisting of the following formulas (12) to (14): Alignment agent.
6). 6. The liquid crystal aligning agent according to any one of 1 to 5, wherein the liquid crystal aligning agent comprises a polymer other than the polyimide precursor or a polymer other than polyimide obtained by imidizing the polyimide precursor.
7). 7. The liquid crystal aligning agent according to any one of the above 1 to 6, wherein the liquid crystal aligning agent further contains at least one selected from the group consisting of an adhesion assistant, a crosslinking agent, a dielectric, a conductive material, and an organic solvent.
8). 8. The liquid crystal aligning agent according to 7, wherein the crosslinking agent is at least one compound selected from the following formula (17), formula (19), and formula (21).
9. 9. The liquid crystal aligning agent according to 8, wherein the crosslinking agent is at least one compound selected from the group consisting of formulas CL-1 to CL-3 described later.
10. 10. A liquid crystal display device comprising a BOA substrate or a substrate with BCS on which a liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of 1 to 9 above is formed.
11. 10. A method for producing a liquid crystal alignment film on a BOA substrate or a substrate with BCS, wherein the liquid crystal aligning agent according to any one of 1 to 9 is applied to a BOA substrate.
12 A BOA substrate or a substrate with BCS, and a liquid crystal alignment film formed on the BOA substrate or the substrate with BCS using the liquid crystal aligning agent for coating a BOA substrate described in any one of 1 to 9 above. A substrate for a liquid crystal display element.

According to the present invention, there is provided a liquid crystal aligning agent for applying a BOA substrate or a substrate with BCS, and a liquid crystal display element having a BOA substrate or a substrate with BCS having good display quality obtained by using the same.

The liquid crystal aligning agent of the present invention comprises a diamine component containing a diamine containing a nitrogen or carboxylic acid group in the structure other than the two amino groups (hereinafter also referred to as a specific diamine) and a tetracarboxylic dianhydride. A BOA substrate containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting components and a polyimide obtained by imidizing the polyimide precursor (hereinafter also referred to as a specific polymer) or It is a liquid crystal aligning agent for substrate application | coating with BCS. Moreover, the liquid crystal display element of this invention is a liquid crystal display element which comprises the BOA board | substrate or the board | substrate with BCS in which the liquid crystal aligning film obtained from the said liquid crystal aligning agent was formed.

<Diamine containing nitrogen or carboxylic acid group in structure other than two amino groups>
A diamine containing a nitrogen or carboxylic acid group in a structure other than two amino groups is at least selected from the group consisting of the following formulas in the diamine structure other than the structure in which two amino groups are bonded. It is a diamine having one as a partial structure. The structure of the following formula is preferably monovalent or divalent, and can be bonded to a structure in which two amino groups are bonded at any position.

In the above structure, Cy is a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and a substituent is bonded to these ring portions. Good. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group or * —CONH— (wherein a bond marked with “*” is bonded to a piperidine ring). R ₁₅ represents hydrogen or a monovalent organic group. R ₁₈ and R ₁₉ are each independently a hydrogen atom or a single bond.

Specifically, a diamine component containing at least one diamine selected from diamines represented by the following formulas (1) to (9) (hereinafter also referred to as specific diamines 1 to 9) and tetracarboxylic dianhydride BOA formed with a liquid crystal alignment film obtained from a liquid crystal alignment agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting components and a polyimide obtained by imidizing the polyimide precursor It is a liquid crystal display element which comprises a board | substrate or a board | substrate with BCS.

<Specific diamine 1>
The specific diamine 1 used in the present invention is a diamine represented by the following formula (1).

In the formula (1), X ¹ represents a single bond, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—. , -CON (CH ₃ )-or N (CH ₃ ) CO-. Among these, —O—, —COO—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —CH ₂ O— or OCO— is preferable because diamine can be easily synthesized. Particularly preferred is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) — or CH ₂ O—.
X ² is a non-aromatic heterocyclic ring containing an alkyl group having 1 to 5 carbon atoms or a nitrogen atom. When X ² is an alkyl group having 1 to 5 carbon atoms, the alkyl group may be linear or branched. In particular, the alkyl group preferably has 1 to 3 carbon atoms. Examples of the case where X ² is a non-aromatic heterocyclic ring containing a nitrogen atom include a pyrrolidine ring, piperidine ring, piperazine ring, pyrazolidine ring, quinuclidine ring or imidazolidine ring. In particular, a non-aromatic heterocyclic ring having a 5-membered ring or a 6-membered ring is preferable because good alignment can be obtained when a liquid crystal alignment film is used. In addition, when the non-aromatic heterocycle contains two nitrogen atoms, when a liquid crystal display device is used, ionic impurities in the liquid crystal are adsorbed at the liquid crystal alignment film interface, and the liquid crystal display device has good electrical characteristics. It is desirable to keep.
From the above viewpoint, a piperazine ring is particularly preferable as the non-aromatic heterocyclic ring containing a nitrogen atom. In addition, when X ² is bonded to the nitrogen atom in X ³ or the carbon atom adjacent to the nitrogen atom, the residual charge accumulated by the DC voltage is quickly relaxed when the liquid crystal display element is formed. It is preferable because of its excellent effect.

X ³ is a 5-membered or 6-membered aromatic heterocyclic ring containing one or two nitrogen atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms. Examples of the 5-membered or 6-membered aromatic heterocycle containing 1 or 2 nitrogen atoms include a pyridine ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. Of these, a pyridine ring, an imidazole ring, a pyrazine ring or a pyrimidine ring is preferable. Furthermore, when the aromatic heterocycle in X ³ is substituted with an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms.
n is an integer of 1 to 4. Among these, an integer of 1 or 2 is preferable.

Specifically, the following compounds are exemplified, but not limited thereto.

<Specific diamine 2>
The specific diamine 2 used in the present invention is a diamine represented by the formula (2).

In the formula (2), X ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms. n is an integer of 1 to 4. Preferable examples of the diamine represented by the formula (2) include the following formulas (2-1) to (2-5).

In the formula (2-1), m1 is an integer of 1 to 4. In the formula (2-2), X ₂ represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, — O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ )-, or -N (CH ₃ ) CO-. m2 and m3 each represent an integer of 0 to 4, and m2 + m3 represents an integer of 1 to 4. In the formula (2-3), m4 and m5 are each an integer of 1 to 5. In the formula (2-4), X ₃ is a linear or branched alkyl group having 1 to 5 carbon atoms. m6 is an integer of 1 to 5. In the formula (2-5), X ₄ represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, — O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ )-, or -N (CH ₃ ) CO-. m7 is an integer of 1 to 4.
In formula (2-1), m1 is preferably an integer of 1 to 2. In formula (2-2), X ₂ is preferably a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, or —OCO—, wherein m2 and m3 are both integers of 1. In formula (2-5), X ₄ is preferably a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH. ₂ —, —COO—, or —OCO—, and m7 is an integer of 1 to 2. Of these, the diamine represented by the formula (2-1) is particularly preferable.

Specific examples of the diamine represented by the formula (2) include the following formulas (2-6) to (2-16).

In the formula (2-15), X ₅ represents a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO— or —OCO—. In the formula (2-16), X ₆ represents a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO— or —OCO—.

<Specific diamine 3>
The specific diamine 3 used in the present invention is a diamine represented by the following formula (3).

Q ₁ represents an alkylene having 1 to 5 carbon atoms, and is preferably a linear alkylene having 1 to 5 carbons for the convenience of synthesis.
Cy is a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. Azetidine, pyrrolidine, or piperidine is preferred because of the ease of synthesis. In addition, a substituent may be bonded to these ring portions.
Q ₂ represents the structure of the following formula (3-I) or (3-II). * 1 in formula (3-I) or (3-II) represents a bond with Q ₁ . * 2 represents a bond with a benzene ring. R _{1 in} formula (3-II) represents hydrogen or a monovalent organic group, preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or methyl It is a group.
R ₂ and R ₃ are monovalent organic groups. q and r are each independently an integer of 0 to 4. However, when the sum of q or r is 2 or more, R ₂ and R ₃ are independent from each other. Preferably, R ₂ and R ₃ are methyl groups for ease of synthesis. In addition, the bonding position of the amino group in the benzene ring constituting the diamine is not limited, but the nitrogen atom in which Q ₁ and R ₁ are bonded to the amino group at the 3-position or 4-position with respect to the nitrogen atom on Cy, respectively. It is preferably in the 3rd or 4th position relative to the nitrogen atom, preferably in the 4th position with respect to the nitrogen atom on Cy and in the 4th position with respect to the nitrogen atom to which Q ₁ and R ₁ are bonded. More preferred.

The diamine represented by the above formula (3) of the present invention is preferably the following formula (3-1) or (3-2).

In the formula, R ₁₆ is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group (hereinafter also referred to as a Boc group). R ₁₇ is a hydrogen atom or a methyl group. Q ₁ is a linear alkylene having 1 to 5 carbon atoms.

Specific examples represented by the above formula (3-1) include, for example, the following formulas (3-1-1) to (3-1-10), which are represented by the above formula (3-2). Specific examples thereof include, for example, the following formulas (3-2-1) to (3-2-4).

<Specific diamine 4-7>
The specific diamines 4 to 7 used in the present invention are diamines represented by the following formulas (4) to (7) in which an amino group is protected with a Boc group.

In the formula (4), D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D has various substituents. Also good. m is 1 or 0.

The substitution position of the amino group in the above formula (4) is not particularly limited, but from the viewpoint of synthesis difficulty and availability of the reagent, the meta or para position is preferred based on the amide bond, and the viewpoint of liquid crystal orientation Then, the position of para is particularly preferable. Similarly, in aminobenzene having no amino group protected by a Boc group (ie, —NHBoc), the meta or para position is preferable based on the amide bond, and from the viewpoint of solubility, the meta position is preferred. The position of para is preferable from the viewpoint of liquid crystal alignment. In addition, hydrogen of aminobenzene having no —NHBoc may be substituted with an organic group or a halogen atom such as fluorine.

D in the formula (4) is not limited, and various structures can be selected depending on the structure of dicarboxylic acid or tetracarboxylic dianhydride used as a raw material. D is preferably a divalent hydrocarbon group from the viewpoint of solubility, and preferred examples include a linear alkylene group and a cyclic alkylene group, and this hydrocarbon group may have an unsaturated bond. . Further, from the viewpoint of liquid crystal orientation and electrical characteristics, a divalent aromatic hydrocarbon group, a heterocyclic ring, and the like are preferable. From the viewpoint of liquid crystal orientation, it is preferable that D has no substituent, but from the viewpoint of solubility, it is preferable that D be substituted with a carboxylic acid group or a fluorine atom.

In the formula (5), E represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. F represents a single bond, —O—, —OCO—, or —COO—.
The diamine when m in Formula (4) is 0 or the diamine represented by Formula (5) is a diamine having an asymmetric structure, and preferable D is the same as above, and preferable E is the same as the above preferable D. It is. In addition, regarding the diamine represented by Formula (5), the compound whose E and F are both a single bond is also preferable.

Wherein (6), _{A 1} represents a single ^{^{bond, -O -, - NQ 1 -}} , - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- It is a kind of divalent organic group or an alkylene group having 1 to 3 carbon atoms. Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₁₆ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

In formula (7), X ⁴ and X ⁸ are each independently a single bond, —CH ₂ —, or —CH ₂ CH ₂ —. X ⁵ and X ⁷ are each independently —CH ₂ — or —CH ₂ CH ₂ —. X ⁶ is alkylene having 1 to 6 carbon atoms or cyclohexylene. Y ¹ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —C (═O) —, —C (═O) O—, —C (═O) NH—, — C (═O) N (CH ₃ ) —, —OC (═O) —, —NHC (═O) —, or —N (CH ₃ ) C (═O) —. R ₁₇ is independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a benzyl group, or a 9-fluorenyl group. a is 0 or 1;

Specific examples of the diamine represented by the above formulas (4) to (7) include a formula selected from the group consisting of the following formulas.

<Specific diamine 8>
The specific diamine 8 used in the present invention is a diamine represented by the following formula (8).
(In the formula (8), R ₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, and t-butyl group. Can be mentioned.
Examples of the aromatic group having 6 to 20 carbon atoms include an aryl group having 6 to 12 carbon atoms and other aromatic groups. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, and 3 And -chloro-4-methylphenyl group. Examples of the other aromatic group include 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4′-t-butylphenyl) -4-quinolinyl group, and 2- (2′-thiophenyl). Examples thereof include a -4-quinolinyl group.
Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group.

X ¹¹ is a single bond, a carbonyl group, or * —CONH— (where a bond marked with “*” is bonded to the piperidine ring).
R ₆ , R ₇ , R ₉ and R ₁₀ are each an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. However, the benzene ring of the aryl group and aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, and t-butyl group. An aryl group having 6 to 12 carbon atoms (wherein the benzene ring of the aryl group may be substituted by a formyl group or an alkoxyl group having 1 to 4 carbon atoms), for example, a phenyl group, a 4-formylphenyl group; Or a 3,4,5-trimethoxyphenyl group and the like;
Examples of the aralkyl group having 7 to 13 carbon atoms (wherein the benzene ring of the aralkyl group may be substituted by a formyl group or an alkoxyl group having 1 to 4 carbon atoms) include, for example, a benzyl group, respectively. it can.

X ⁹ , X ¹⁰ , X ¹² and X ¹³ are each a single bond, a carbonyl group, * —CH ₂ —CO— or * —CH ₂ —CH (OH) — (where “*” is a bond). Is bound to the piperidine ring.).
X ¹⁴ is an oxygen atom, * -OCO-, the following formula (X ¹⁴ -1)

(In the formula, a is an integer of 1 to 12, and b is an integer of 0 to 5.)
(Wherein, a bond marked with “*” is bonded to the piperidine ring), a methylene group or an alkylene group having 2 to 6 carbon atoms.
Examples of the alkylene group having 2 to 6 carbon atoms include a 1,3-propylene group and a 1,6-hexylene group.
Two amino groups bonded to the benzene ring of the above formula (8) is preferably in the 2,4-position or 3,5-position relative to the group ^{X 4.}

Specific preferred examples of the diamine represented by the formula (8) include the following formulas (8-1) to (8-4).

<Specific diamine 9>
The specific diamine 9 used in the present invention is a diamine represented by the above formula (9).

R ₁₁ represents hydrogen or a monovalent organic group. The monovalent organic group is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkenyl groups, alkoxy groups, cyano groups, hydroxy groups, fluoroalkyl groups, trifluoroalkoxy groups, fluorine atoms, and combinations thereof. Group and the like. Preferably they are a hydrogen atom or a methyl group.
R ₁₂ each independently represents a single bond or a structure of the following formula (9-2). Further, any hydrogen atom in the benzene ring may be substituted with a monovalent organic group.

R ₁₃ is selected from the group consisting of a single bond, —O—, —COO—, —OCO—, — (CH ₂ ) ₁ —, —O (CH ₂ ) _m O—, —CONH—, and —NHCO—. (L and m represent an integer of 1 to 5). * ₁ represents the site | part couple | bonded with the benzene ring in Formula (9). * ₂ represents the site | part couple | bonded with the amino group in Formula (9). n represents an integer of 1 to 3. Among these, R ₁₁ is preferably a single bond, —O—, —COO—, —OCO—, —CONH—, or NHCO— from the viewpoint of relaxation of accumulated charges.
n represents an integer of 1 to 3. Preferably it is 1 or 2.

Specific examples of the diamine represented by the above formula (9) include diamines represented by the following formulas (9-1-1) to (9-1-12). Among these, from the viewpoint of relaxation of accumulated charges, the formulas (9-1-1), (9-1-2), (9-1-1), (9-1-5), (9-1-8) , (9-1-9), (9-1-10), (9-1-11) or (9-1-12) are preferred, and are represented by the formulas (9-1-1), (9-1-2) ), (9-1-3), (9-1-11), or (9-1-12) is particularly preferable.

<Other diamines>
In the present invention, other diamines other than the specific diamine can be used in combination as part of the diamine component. Although other diamine is not specifically limited, For example, the side chain type diamine explained in full detail below is mentioned. The side chain diamine is preferably used when producing a vertical alignment type liquid crystal display element.

The specific side chain diamine is a diamine represented by the following formula (10).

In Formula (10), Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. . Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or COO— is preferable because a side chain structure is easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or COO—.
Y ² is a single bond or (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or OCO—.

Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxyl having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom. Y ⁴ is a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Y ⁴ is preferably a C 12-25 organic group having a benzene ring, a cyclohexyl ring or a steroid skeleton.
Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxyl having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom.
n is an integer of 0-4. Preferably, it is an integer of 0-2.
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
m is an integer of 1 to 4. Preferably, it is an integer of 1.

More specifically, it is a diamine represented by the following formulas (10-1) to (10-31).

In formulas (10-1) to (10-3), R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—. R ² is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group.

In the formulas (10-4) to (10-6), R ³ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or CH ₂ -is shown. R ⁴ is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group.

In formulas (10-7) to (10-8), R ⁵ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or O— is shown. R ⁶ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

In the formulas (10-9) to (10-10), R ⁷ is an alkyl group having 3 to 12 carbon atoms. The cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.

In formulas (10-11) to (10-12), R ⁸ is an alkyl group having 3 to 12 carbon atoms. The cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.

In formula (10-13), A ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom. A ³ is a 1,4-cyclohexylene group or a 1,4-phenylene group. A ² is an oxygen atom or COO- * (where a bond marked with “*” is bonded to A ³ ). A ¹ is an oxygen atom or COO- * (where a bond marked with “*” is bonded to (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1. a ₂ is an integer of 2 to 10. a ₃ is an integer of 0 or 1.

Of the above formulas (10-1) to (10-31), particularly preferred diamines are the formulas (10-1) to (10-6), the formulas (10-9) to the formulas (10-13), and the formulas (10-16), formula (10-19), formula (10-23), formula (10-25), formula (10-29), and the like.

Examples of other diamines include diamines represented by the following formula (11).

In the formula (11), Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene. They may be substituted with organic groups, and hydrogen atoms may be replaced with halogen atoms. R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R ₁ and R ₂ form a ring. May be. T ₁ and T ₂ are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —. , —CON (CH ₃ ) —, or N (CH ₃ ) CO—. S is a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom (wherein the —CH ₂ — or CF ₂ — in the alkylene group is optionally substituted with —CH═CH—) In the case where any of the following groups is not adjacent to each other, these groups may be substituted: —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH-, divalent carbocycle, divalent heterocycle.). Q represents the following structure.

In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ represents —CH ₂ —, —NR—, —O—, or S—.

Specifically, the following diamine is mentioned.

(In the formula, n represents an integer of 1 to 8.)

Examples of other diamines include diamines represented by the following formula, or diamines described on pages 30 to 33 of International Publication No. 2014/171493 (published 2014.10.23).

The above-mentioned other diamines can be used alone or in combination of two or more depending on the properties such as the liquid crystal orientation, the voltage holding ratio, and the accumulated charge when the liquid crystal alignment film is used.

<Tetracarboxylic dianhydride component>
The tetracarboxylic dianhydride used as a raw material for the polymer contained in the liquid crystal aligning agent used in the present invention is not particularly limited, but tetracarboxylic dianhydrides represented by the following formulas (12) to (14) It is preferable to use (also referred to as specific tetracarboxylic dianhydride).

In the formula (12), Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

Specifically, it is a group represented by the following formulas (12a) to (12j).
In the formula (12a), Z ² to Z ⁵ are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring. In the formula (6g), Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group.
In formula (12), particularly preferred Z ¹ is represented by formula (12a), formula (12c), formula (12d), formula (12e), formula (12f) or formula (12g) because of polymerization reactivity and ease of synthesis. ).

In formula (13) or formula (14), j and k are each independently 0 or 1. x and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.
As specific tetracarboxylic dianhydrides, tetracarboxylic dianhydrides represented by the following formulas (12-1) to (12-5) are preferable. Among them, an afterimage (accumulated charge) of the obtained liquid crystal display device is preferable. ) Is preferred from the viewpoint of (12-1), (12-3) or (12-5).

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride can be used. Other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid Acid, 1,2,5,6-anthracenetetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4 '-Benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro- 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, 3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2, 3,4-cyclobutanetetracarboxylic acid.
The above-mentioned other tetracarboxylic dianhydrides can be used alone or in combination of two or more according to properties such as liquid crystal orientation, voltage holding ratio, accumulated charge, etc. when a liquid crystal alignment film is formed.

The liquid crystal aligning agent of the present invention may additionally contain components other than the specific polymer component. As such an additional component, an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, and the following formula (17) for increasing the strength of the liquid crystal alignment film , (19) and (21), at least one cross-linking agent, a dielectric material or conductive material for adjusting the dielectric constant or electric resistance of the liquid crystal alignment film, or an organic solvent. Specific examples of these additional components are as disclosed in various known literatures relating to liquid crystal alignment agents, and are disclosed in International Publication No. 2015/060357, page 53 [0105] to page 55 [0116]. And the like.

In formula (17), R ₂₀ , R ₂₁ , R ₂₅ , and R ₂₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 2 carbon atoms. -4 alkynyl groups, at least one of which is a group represented by formula (18). R ₂₂ and R ₂₄ each independently represent an aromatic ring, and any hydrogen atom of the aromatic ring is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, It may be substituted with a vinyl group. R ₂₃ is a single-bond, saturated hydrocarbon group having 1 to 10 carbon atoms that may be bonded to all or part of it to form a cyclic structure.

In the formula (19), R ₂₇ is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and c is an integer of 2 to 6. R ₂₈ and R ₂₉ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups are substituted It may have a group. At least one of R ₂₈ and R ₂₉ has a hydroxy group as a substituent. Moreover, it is preferable that at least one of R ₂₈ and R ₂₉ is substituted with a group represented by the formula (20). In formula (20), R ₃₀ to R ₃₃ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.

In the formula (21), R ₃₄ and R ₃₈ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₃₅ and R ₃₇ each independently represent an aromatic ring, Any of these hydrogen atoms may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group. R ₃₆ is a saturated hydrocarbon group having 1 to 10 carbon atoms that may form a cyclic structure by combining a single bond or all or a part thereof, and any hydrogen atom may be substituted with a fluorine atom , —NH—, —N (CH ₃ ) —, or a group represented by formula (22). In formula (22), P ₁ and P ₂ are each independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring. In formula (21), d and f are each independently an integer of 1 to 3, and e and g are each independently an integer of 1 to 3.

Specific examples of the compounds represented by the above formulas (17) to (22) include the following three.

<Polymer>
In the present invention, a known polymerization method can be used as a method for synthesizing the polymer. For example, the method described on pages 39 to 42 of International Publication No. 2014/171493 (published 2014.10.23) can be mentioned.

<Liquid crystal aligning agent>
The polymer component in the liquid crystal aligning agent of the present invention may all be a specific polymer used in the present invention, and other polymers may be mixed with the specific polymer of the present invention. In that case, the content of the other polymer with respect to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
As another polymer other than that, the polyimide precursor obtained from the diamine component which consists of diamines other than specific diamine, and the tetracarboxylic dianhydride component, or the polyimide which imidated this polyimide precursor is mentioned. Furthermore, as other polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, and the like can be given.

The organic solvent in the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70 to 99% by mass from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. The organic solvent in that case will not be specifically limited if it is an organic solvent in which the specific polymer mentioned above is dissolved. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, Examples thereof include ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.
The liquid crystal aligning agent of the present invention is a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group or an alkoxyl group, or A crosslinkable compound having a polymerizable unsaturated bond can also be contained.
In addition, as a compound for improving film thickness uniformity and surface smoothness, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, or the like can be contained, and a liquid crystal alignment film As a compound which improves adhesiveness with a board | substrate, a functional silane containing compound or an epoxy group containing compound can also be contained.
Further, a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film may be added.
The liquid crystal aligning agent of the present invention can contain an organic solvent (also called a poor solvent) or a compound that improves the uniformity of the film thickness and surface smoothness of the polymer film when the liquid crystal aligning agent is applied. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be contained.

The following specific examples are given as poor solvents for improving the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Low surface tension such as 2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, or lactate isoamyl ester The organic solvent which has is mentioned.
These poor solvents may be used alone or in combination. When the above poor solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total organic solvent contained in the liquid crystal aligning agent.

<LCD>
As the liquid crystal composition used in the liquid crystal display element of the present invention, a nematic liquid crystal having a positive dielectric anisotropy is used in a horizontal alignment type liquid crystal display element, and a nematic liquid crystal having a negative dielectric anisotropy is used in some applications. Also good.
In the vertical alignment type liquid crystal display element, nematic liquid crystal having negative dielectric anisotropy can be used. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, or terphenyl liquid crystal can be used. An alkenyl liquid crystal can also be used in combination. A conventionally well-known thing can be used as such an alkenyl type liquid crystal. For example, a compound represented by the following formula can be exemplified.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film by applying and baking on a BOA substrate or a substrate with BCS and then performing alignment treatment by rubbing treatment, light irradiation or the like. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment.
In the present invention, the BOA substrate is a substrate in which a black matrix is formed on a COA substrate. As a material used for the black matrix, a column spacer (black column spacer (BCS)) that supports the space between the array substrate and the counter substrate may be used.
Further, the substrate with BCS is a substrate in which a black column spacer is formed by using the black colored resin composition as a column spacer material that supports between the array substrate and the counter substrate. A black matrix material may be used.

For the BOA substrate or the substrate with BCS, for example, a colored resin composition is applied to a transparent substrate by spin coating or the like, dried using a vacuum dryer or a hot plate, and then using an ultrahigh pressure mercury lamp or the like through a photomask. After exposure and development using an aqueous KOH solution, the film can be formed by baking using a hot air circulating oven. As the colored resin composition, for example, a black matrix and a colored resin composition for BCS prepared according to the method described in “0312” to “0314” of JP-A-2014-67028 can be used.
The transparent substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, ink jet, or the like is generally used. Other coating methods include dip, roll coater, slit coater, or spinner, and these may be used depending on the purpose.
After applying the liquid crystal aligning agent on the BOA substrate or the substrate with BCS, the solvent can be evaporated at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the polymer film after baking is treated with rubbing or irradiation with polarized ultraviolet rays.

In a vertical alignment type liquid crystal display element, a photopolymerizable compound is added to the liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. In addition, there is known a PSA (Polymer Sustained Alignment) element that can control the alignment of liquid crystal and improve the response speed of liquid crystal by polymerizing a polymerizable compound, and is reported in Japanese Patent Application Laid-Open No. 2003-307720. Yes.
Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display element The seizure characteristics of the steel deteriorate.
On the other hand, adding a photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition may increase the response speed of the liquid crystal display element (SC-PVA liquid crystal display). K. Hanaoka, SID 04 It is reported by non-patent literature such as DIGEST, P.1200-1202.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.
The abbreviations are as follows.
(Acid dianhydride)
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, PMDA: pyromellitic acid Dianhydride, TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride (diamine)
PDA: p-phenylenediamine, DDM: 4,4′-methylenedianiline, DBA: 3,5-diaminobenzoic acid,
Nitrogen-containing diamines represented by the following formulas DA-N1 to DA-N7

Vertically oriented side chain diamines represented by the following formulas DA-S1 to DA-S3

Photosensitive diamine represented by the following formula DA-1

<Solvent>
NMP: N-methyl-2-pyrrolidone, BC: Butyl cellosolve <Additive>
3AMP: 3-picolylamine <crosslinking agent>
Crosslinking agents represented by the following formulas CL-1 to CL-3

(Polyimide molecular weight measurement conditions)
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805), column temperature: 50 ° C., eluent: N, N ′ -Dimethylformamide (as additives, lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) L), flow rate: 1.0 ml / min, standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and Polymer Laboratories Manufactured polyethylene glycol (molecular weight about 12,000, 4,000, 1,000).

(Imidation rate of polyimide)
Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidization rate (%) = (1−α · x / y) × 100

(Synthesis Example 1)
BODA (18.77 g, 75.0 mmol), DBA (10.65 g, 70.0 mmol), and DA-S2 (13.04 g, 30.0 mmol) were dissolved in NMP (141.5 g) at 80 ° C. After reacting for 5 hours, CBDA (4.71 g, 24.0 mmol) and NMP (47.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (43.1 g) and pyridine (13.4 g) were added as an imidization catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 78%, the number average molecular weight was 22000, and the weight average molecular weight was 56000.
NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was dissolved by stirring at 70 ° C. for 20 hours. 3AMP (1 mass% NMP solution) 6.0g, NMP (4.0g), and BC (40.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 2)
BODA (5.00 g, 20.0 mmol), DA-N1 (7.27 g, 30.0 mmol), DA-S1 (11.42 g, 30.0 mmol), and PDA (4.33 g, 40.0 mmol) were mixed with NMP. (113.8 g) was dissolved and reacted at 60 ° C. for 3 hours. After adding CBDA (11.37 g, 58.0 mmol) and NMP (26.3 g) and reacted at 40 ° C. for 1 hour, PMDA (4.36 g, 20.0 mmol) and NMP (35.00 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (46.3 g) and pyridine (14.3 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 76%, the number average molecular weight was 13000 and the weight average molecular weight was 32000.
A liquid crystal aligning agent (B1) was obtained in the same manner as in Synthesis Example 1 using the resulting polyimide powder (B) (6.0 g).

(Synthesis Example 3)
BODA (5.00 g, 20.0 mmol), DA-N1 (7.27 g, 30.0 mmol), DA-S1 (11.42 g, 30.0 mmol), and DBA (6.09 g, 40.0 mmol) were mixed with NMP. (118.3 g) and dissolved at 60 ° C. for 3 hours. After adding CBDA (11.37 g, 58.0 mmol) and NMP (27.3 g) and reacting at 40 ° C. for 1 hour, PMDA (4.36 g, 20.0 mmol) and NMP (36.41 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (44.5 g) and pyridine (13.8 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 79%, the number average molecular weight was 21,000, and the weight average molecular weight was 49000.
A liquid crystal aligning agent (C1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (C) (6.0 g).

(Synthesis Example 4)
TCA (22.19 g, 99.0 mmol), DDM (9.91 g, 50.0 mmol), DA-N2 (7.64 g, 25.0 mmol), and DA-S3 (12.37 g, 25.0 mmol) were added to NMP. (208.4 g) was dissolved and reacted at 60 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (37.6 g) and pyridine (11.6 g) were added as imidation catalysts, and the reaction was carried out at 110 ° C. for 4 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (D). The imidation ratio of this polyimide was 68%, the number average molecular weight was 11000, and the weight average molecular weight was 25000.
A liquid crystal aligning agent (D1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (D) (6.0 g).

(Synthesis Example 5)
BODA (18.77 g, 75.0 mmol), DA-N3 (11.78 g, 30.0 mmol), DBA (3.04 g, 20.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) were mixed with NMP. (171.9 g), and after reacting at 80 ° C. for 5 hours, CBDA (4.71 g, 24.0 mmol) and NMP (57.32 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Got.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (35.5 g) and pyridine (11.0 g) were added as an imidization catalyst, and the mixture was reacted at 100 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 75%, the number average molecular weight was 16000, and the weight average molecular weight was 39000.
A liquid crystal aligning agent (E5) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (E) (6.0 g).

(Synthesis Example 6)
BODA (18.77 g, 75.0 mmol), DA-N4 (9.96 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) were dissolved in NMP (157.4 g). After reacting at 5 ° C. for 5 hours, CBDA (4.12 g, 21.0 mmol) and NMP (52.46 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (38.8 g) and pyridine (12.0 g) were added as an imidization catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 57%, the number average molecular weight was 10,000, and the weight average molecular weight was 24000.
A liquid crystal aligning agent (F1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (F) (6.0 g).

(Synthesis Example 7)
BODA (12.51 g, 50.0 mmol), PDA (3.24 g, 30.0 mmol), DA-N5 (11.13 g, 20.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) were mixed with NMP. (166.6 g), and after reacting at 60 ° C. for 3 hours, CBDA (9.51 g, 48.5 mmol) and NMP (41.11 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Got.
After adding NMP to this polyamic acid solution (180 g) and diluting to 6.5% by mass, acetic anhydride (36.6 g) and pyridine (11.4 g) were added as imidization catalysts, and the mixture was reacted at 80 ° C. for 2 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 80 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 73%, the number average molecular weight was 17000, and the weight average molecular weight was 38000.
A liquid crystal aligning agent (G1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (G) (6.0 g).

(Comparative Synthesis Example 1)
BODA (12.51 g, 50.0 mmol), DA-1 (16.52 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) were dissolved in NMP (192.2 g). After reacting at 3 ° C. for 3 hours, PMDA (4.36 g, 48.5 mmol), CBDA (9.61 g, 49.0 mmol) and NMP (38.4 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Got.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (35.3 g) and pyridine (10.9 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (H). The imidation ratio of this polyimide was 73%, the number average molecular weight was 17000, and the weight average molecular weight was 48,000.
Using the obtained polyimide powder (H) (6.0 g), a liquid crystal aligning agent (H1) was obtained in the same manner as in Synthesis Example 1.

(Comparative Synthesis Example 2)
BODA (12.51 g, 50.0 mmol), PDA (5.41 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) were dissolved in NMP (147.7 g) at 60 ° C. After reacting for 3 hours, BDA (9.41 g, 48.0 mmol) and NMP (37.7 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5% by mass, acetic anhydride (43.7 g) and pyridine (13.5 g) are added as an imidization catalyst and reacted at 80 ° C. for 2 hours. It was. This reaction solution was poured into methanol (2700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (I). The imidation ratio of this polyimide was 72%, the number average molecular weight was 13000, and the weight average molecular weight was 25000.
A liquid crystal aligning agent (I1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (I) (6.0 g).

(Synthesis Example 8)
6.0 g of the liquid crystal aligning agent (H1) obtained in Comparative Synthesis Example 1 as the first component and 14.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as the second component were mixed for 1 hour. A liquid crystal aligning agent (J1) was prepared by stirring.
(Synthesis Example 9)
The liquid crystal aligning agent (I1) obtained in Comparative Synthesis Example 2 was mixed with 6.0 g as the first component, and the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was mixed with 14.0 g as the second component, and 1 hour A liquid crystal aligning agent (K1) was prepared by stirring.
(Synthesis Example 10)
CL-2 was added to 10.0 g of the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 so as to be 10 wt% of the resin component, and the liquid crystal aligning agent (A2) was stirred at room temperature for 1 hour. Prepared.

(Synthesis Example 11)
CL-1 was added to 10.0 g of the liquid crystal aligning agent (D1) obtained in Synthesis Example 4 so as to be 10 wt% of the resin component, and the liquid crystal aligning agent (D2) was stirred at room temperature for 1 hour. Prepared.
(Synthesis Example 12)
CL-3 was added to 10.0 g of the liquid crystal aligning agent (K1) obtained in Synthesis Example 9 so as to be 10 wt% of the resin component, and the liquid crystal aligning agent (K2) was stirred at room temperature for 1 hour. Prepared.

(Synthesis Example 13)
BODA (2.50 g, 10.0 mmol), DA-N6 (3.97 g, 10.0 mmol), and DA-S1 (3.81 g, 10.0 mmol) were dissolved in NMP (41.1 g). After reacting at 3 ° C. for 3 hours, CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (40 g) and diluting to 6.5% by mass, acetic anhydride (6.68 g) and pyridine (2.07 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (461 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (L). The imidation ratio of this polyimide was 72%, the number average molecular weight was 15000, and the weight average molecular weight was 28000.
Using the obtained polyimide powder (L) (6.0 g), a liquid crystal aligning agent (L1) was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 14)
BODA (2.50 g, 10.0 mmol), DA-N7 (3.41 g, 10.0 mmol), and DA-S1 (3.81 g, 10.0 mmol) were dissolved in NMP (38.9 g). After reacting at 3 ° C. for 3 hours, CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (40 g) and diluting to 6.5% by mass, acetic anhydride (6.99 g) and pyridine (2.17 g) are added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (463 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyimide powder (M). The imidation ratio of this polyimide was 70%, the number average molecular weight was 14000, and the weight average molecular weight was 30000.
Using the obtained polyimide powder (M) (6.0 g), a liquid crystal aligning agent (M1) was obtained in the same manner as in Synthesis Example 1.

Example 1
A liquid crystal cell was prepared using the liquid crystal aligning agent A1 obtained in Synthesis Example 1 according to the following procedure, and the pretilt angle and the voltage holding ratio were measured.
<Preparation of colored resin composition>
The colored resin composition (a) for black column spacer (BCS) used in the present invention is a resin composition that is also used as a black matrix material, and is described in “03132” to “0314” of JP-A-2014-67028. It was prepared in the same manner as resist (VI).
<Production of ITO substrate with BCS>
The colored resin composition (a) is applied to a glass substrate with an ITO electrode on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm / 5 μm is formed, and the film thickness after firing is 4 μm. It was applied by spin coating. Then, after drying for 60 seconds with a vacuum dryer, it was dried for 2 minutes with a hot plate at 110 ° C. to obtain a pre-exposure substrate with a colored resin composition (a).
The pre-exposure substrate was exposed at 50 mJ / cm 2 using an ultrahigh pressure mercury lamp through a circular photomask having an opening of 20 μm, and then developed using a KOH aqueous solution having a temperature of 25 ° C. and a concentration of 0.05 mass%. Thereafter, the substrate with the resist (VI) was baked at 230 ° C. for 30 minutes using a hot air circulating oven to obtain an ITO substrate with BCS.

<Production of liquid crystal cell>
Using the liquid crystal aligning agent (A1), a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (A1) was spin-coated on the ITO surface of the ITO substrate with BCS, dried for 90 seconds on a hot plate at 80 ° C., and then baked in a hot air circulation oven at 200 ° C. for 30 minutes. A liquid crystal alignment film was formed.

Moreover, after spin-coating the liquid crystal aligning agent (A1) on the ITO surface in which the electrode pattern is not formed, and drying for 90 seconds with a hot plate at 80 ° C., baking is performed in a hot air circulation oven at 200 ° C. for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.
A thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the two substrates. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. A liquid crystal cell was produced by injecting a PSA polymerizable compound-containing liquid crystal MLC-3023 (trade name, manufactured by Merck, alkenyl-based liquid crystal) into the empty cell by a reduced pressure injection method. The voltage holding ratio (VHR) of this liquid crystal cell was measured.

Next, in a state where a DC voltage of 15 V was applied to the liquid crystal cell, UV was passed through a 365 nm band-pass filter from the outside of the liquid crystal cell to be irradiated with 10 J / cm ² (also referred to as primary PSA treatment). The illuminance of UV was measured using UV-MO3A (attachment: UV-35) manufactured by ORC. Thereafter, for the purpose of deactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 /) was used with a UV-FL irradiation apparatus manufactured by Toshiba Lighting & Technology Co., Ltd. in a state where no voltage was applied. A-1) was irradiated for 30 minutes (also called secondary PSA treatment). Thereafter, the pretilt angle of the pixel portion and the voltage holding ratio of the cell after UV irradiation were measured.
"Measurement of pretilt angle"
Measurement was performed using an LCD analyzer LCA-LUV42A (manufactured by Meiryo Technica).
"Evaluation of voltage holding ratio"
A voltage of 1V was applied for 60 μs in a hot air circulating oven at 60 ° C., then the voltage after 1667 msec was measured, and how much the voltage could be held was calculated as the voltage holding ratio. For measurement of the voltage holding ratio, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

(Examples 2 to 14, Comparative Examples 1 and 2)
The same operation as in Example 1 was performed except that the liquid crystal aligning agent (A1) used in Example 1 was changed to the liquid crystal aligning agents (B1) to (M1), (A2), (D2) or (K2). The pretilt angle and voltage holding ratio were measured.
(Example 1 ')
A liquid crystal cell was prepared using a substrate with an ITO electrode without BCS by the same operation as in Example 1, and the pretilt angle and voltage holding ratio were measured. In order to maintain the cell gap, 4 μm bead spacers were used in place of the black column spacers and dispersed on the liquid crystal alignment film.
(Examples 2 ′ to 14 ′, Comparative Examples 1 ′ and 2 ′)
The same operation as in Example 1 ′ was performed except that the liquid crystal aligning agent (A1) used in Example 1 ′ was changed to the liquid crystal aligning agent (B1) to (M1), (A2), (D2) or (K2). The pretilt angle and the voltage holding ratio were measured.

As shown in the above results, Examples 1 to 7, 13, and 14 and Examples 1 ′ to 7 ′, 13 ′, and 14 ′ have BCS compared to Comparative Examples 1 and 2, and Comparative Examples 1 ′ and 2 ′. It was confirmed that even when the substrate was used, high VHR characteristics were exhibited.
Further, as can be seen from Examples 8 and 9, and Examples 8 ′ and 9 ′, a polymer having no diamine containing a carboxyl group or a nitrogen-containing structure as a monomer unit and a polymer having the diamine as a monomer unit are used in combination. However, it was confirmed that high VHR characteristics can be expressed. Further, as shown in Examples 10 to 12 and Examples 10 ′ to 12 ′, even when a substrate with BCS is used, even when a crosslinking agent is added to a polymer exhibiting high VHR characteristics, it is as high as when not added. It was confirmed that VHR characteristics can be expressed.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2016-118281 filed on June 14, 2016 are incorporated herein by reference. Is.

Claims

A polyimide precursor obtained by reacting a diamine component containing a diamine containing nitrogen or a carboxylic acid group with a tetracarboxylic dianhydride component in a structure other than two amino groups, and imidation of the polyimide precursor A liquid crystal aligning agent for coating a substrate with a BOA substrate or BCS, which contains at least one polymer selected from the group consisting of prepared polyimides.
The liquid crystal aligning agent of Claim 1 in which the said diamine has at least 1 structure chosen from the group which consists of a following formula as a partial structure.

(In the formula, Cy is a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and a substituent may be bonded to these ring portions. R 14 is a hydrogen atom, a single bond, a carbonyl group or * —CONH— (where a bond marked with “*” is bonded to a piperidine ring) R 15 is hydrogen or a monovalent organic group R 18 and R 19 are each independently a hydrogen atom or a single bond.)
The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine is at least one diamine selected from the group consisting of diamines represented by the following formulas (1) to (9).

(In the formula (1), X 1 is a single bond, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—) , -CON (CH 3) - or N (CH 3) CO- and is .X 2 is .X 3 is a non-aromatic heterocyclic ring containing alkyl group or a nitrogen atom having 1 to 5 carbon atoms, the carbon A 5-membered or 6-membered aromatic heterocyclic ring containing one or two nitrogen atoms optionally substituted with an alkyl group of 1 to 5. n is an integer of 1 to 4.)

(In formula (2), X 1 is an organic group having an aromatic ring having 6 to 30 carbon atoms. N is an integer of 1 to 4.)

(In formula (3), Q 1 represents an alkylene having 1 to 5 carbon atoms. Cy represents a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. Q 2 represents a structure of the following formula (3-I) or (3-II): Formulas (3-I), (3-II) * 1 represents a bond with Q 1 , * 2 represents a bond with a benzene ring, R 1 in formula (3-II) represents hydrogen or a monovalent organic group, R 2 , R 3 is a monovalent organic group, q and r are each independently an integer of 0 to 4, provided that when q or r is 2 or more, R 2 and R 3 are each independently Yes.)

(In the formula (4), D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and D has various substituents. M is 1 or 0.
In the formula (5), E is a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. F represents a single bond, —O—, —OCO—, or COO—.
Wherein (6), A 1 represents a single bond, -O -, - NQ 1 - , - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of OCO- Or an alkylene group having 1 to 3 carbon atoms. Q 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 16 is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
In formula (7), X 4 and X 8 are each independently a single bond, —CH 2 —, or —CH 2 CH 2 —. X 5 and X 7 are each independently —CH 2 — or —CH 2 CH 2 —. X 6 is alkylene having 1 to 6 carbon atoms or cyclohexylene. Y 1 is independently a single bond, —O—, —NH—, —N (CH 3 ) —, —C (═O) —, —C (═O) O—, —C (═O ) NH—, —C (═O) N (CH 3 ) —, —OC (═O) —, —NHC (═O) —, or —N (CH 3 ) C (═O) —. R 17 is each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a benzyl group, or a 9-fluorenyl group. . a is 0 or 1; )

(In the formula (8), R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an alkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group.
X 11 is a single bond, a carbonyl group, or * —CONH— (where a bond marked with “*” is bonded to the piperidine ring).
R 6 , R 7 , R 9 and R 10 are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms, provided that the aryl The benzene ring of the group and the aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms.
X 9 , X 10 , X 12 and X 13 are each independently a single bond, a carbonyl group, * —CH 2 —CO— or * —CH 2 —CH (OH) — (provided with “*”). Bond to the piperidine ring).
X 14 each independently represents —O—, * —OCO—, or a group represented by the following formula (X 14 -1) (where a bond marked with “*” is A piperidine ring), a methylene group or an alkylene group having 2 to 6 carbon atoms. )

(In the formula (X 14 -1), a is an integer of 1 to 12. b is an integer of 0 to 5.)

(In formula (9), R 11 represents hydrogen or a monovalent organic group. R 12 each independently represents a single bond or a structure of the following formula (9-2). The hydrogen atom may be replaced with a monovalent organic group, where n is an integer of 1 to 3.)

(In the formula (9-2), R 13 represents a single bond, —O—, —COO—, —OCO—, — (CH 2 ) 1 —, —O (CH 2 ) m O—, —CONH—, And represents a divalent organic group selected from the group consisting of —NHCO— (1, m represents an integer of 1 to 5.) * 1 represents a site bonded to the benzene ring in formula (9). 2 represents the site | part couple | bonded with the amino group in Formula (9).)
The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the diamine component includes a diamine represented by the following formula (10) or (11).

(In the formula (10), Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. is there.
Y 2 is a single bond or (CH 2 ) b — (b is an integer of 1 to 15).
Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—.
Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxyl having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom. Y 4 is a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Y 4 is preferably a C 12-25 organic group having a benzene ring, a cyclohexyl ring or a steroid skeleton.
Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkoxyl having 1 to 3 carbon atoms. It may be substituted with a group or a fluorine atom.
n is an integer of 0-4.
Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
m is an integer of 1 to 4. )

(In the formula (11), Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene. They may be substituted with an organic group, and the hydrogen atom is replaced with a halogen atom. May be.
R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 1 and R 2 form a ring. May be.
T 1 and T 2 are each independently a single bond or —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —. , —CON (CH 3 ) —, or —N (CH 3 ) CO—.
S is a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom (wherein the —CH 2 — or CF 2 — in the alkylene group is optionally substituted with —CH═CH—) In the case where any of the following groups is not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH-, divalent carbocycle or divalent heterocycle.).
Q represents the following structure.

(In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents —CH 2 —, —NR—, —O— or S—).
The tetracarboxylic dianhydride component according to any one of claims 1 to 4, wherein the tetracarboxylic dianhydride component is at least one tetracarboxylic dianhydride selected from the group consisting of the following formulas (12) to (14): Liquid crystal aligning agent.

(In Formula (12), Z 1 is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. Formula (13) or Formula ( 14) j and k are each independently 0 or 1. X and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.)
The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the liquid crystal aligning agent includes a polymer other than the polyimide precursor or a polymer other than polyimide obtained by imidizing the polyimide precursor.
The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the liquid crystal aligning agent further comprises at least one selected from the group consisting of an adhesion assistant, a crosslinking agent, a dielectric, a conductive material, and an organic solvent. .
The liquid crystal aligning agent of Claim 7 whose said crosslinking agent is at least 1 compound chosen from following formula (17), Formula (19), and Formula (21).

(In the formula (17), R 20 , R 21 , R 25 , and R 26 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or the number of carbon atoms. 2 to 4 alkynyl groups, at least one of which is represented by the formula (18): R 22 and R 24 each independently represents an aromatic ring, and any hydrogen atom of the aromatic ring is R 23 may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group, and R 23 may be a single bond or all or a part thereof may be bonded. (It is a saturated hydrocarbon group having 1 to 10 carbon atoms that may form a cyclic structure.)

(In the formula (19), R 27 is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and c is an integer of 2 to 6. R 28 and R 29 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups are substituents In addition, at least one of R 28 and R 29 has a hydroxy group as a substituent, and at least one of R 28 and R 29 is a group represented by the formula (20). (In formula (20), R 30 to R 33 each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.)

(In the formula (21), R 34 and R 38 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 35 and R 37 each independently represent an aromatic ring, Any hydrogen atom in the ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group, R 36 is a single bond, A saturated hydrocarbon group having 1 to 10 carbon atoms which may be bonded to all or part of it to form a cyclic structure, and any hydrogen atom may be substituted with a fluorine atom, —NH—, —N (CH 3 ) — or a group represented by formula (22) In formula (22), P 1 and P 2 are each independently an alkyl group having 1 to 5 carbon atoms, and Q 1 is an aromatic ring In the formula (21), d and f are each independently 1 to 3 Is a number, e, and g are each independently an integer of 1 to 3. )
The liquid crystal aligning agent according to claim 8, wherein the crosslinking agent is at least one compound selected from the group consisting of the following formulas CL-1 to CL-3.
A liquid crystal display device comprising a BOA substrate or a substrate with a BCS on which a liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 9 is formed.
A method for producing a liquid crystal alignment film on a BOA substrate or a substrate with BCS, wherein the liquid crystal alignment agent according to any one of claims 1 to 9 is applied to a BOA substrate or a substrate with BCS.
A liquid crystal display device comprising: a BOA substrate or a substrate with BCS; and a liquid crystal alignment film formed on the BOA substrate or the substrate with BCS using the liquid crystal aligning agent according to any one of claims 1 to 9. Substrate.