TW201815893A - Liquid crystal aligning agent for coating of BOA substrate or substrates with BCS, and liquid crystal display element - Google Patents

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

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

Generally speaking, a liquid crystal display device includes an "array substrate" (which is formed with a thin film transistor), and an "opposite substrate" (which is opposite to the array substrate and is formed with a color filter), and includes a sandwich The "liquid crystal layer" between the array substrate and the counter substrate. For color filters, for the purpose of improving the contrast or color development effect, the boundary portion between the colored layers such as red, green, and blue must have a black matrix. In recent years, due to the relationship between manufacturing yield and the like, a "color filter on array" (COA: Color-Filter On Array) formed with color filters on an array substrate or a black matrix formed on a COA substrate has been developed. Black Matrix Array (BOA: Black Matrix On Array) substrate.

Furthermore, because of the relationship between manufacturing yield and the like, an attempt has been made to use a black colored resin composition as a pillar spacer material that supports the array substrate and the counter substrate (a pillar spacer of this kind is also referred to as a black pillar spacer (BCS: Black Column Spacer)), the black coloring resin composition may use the aforementioned black matrix material.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2014-167492

[Patent Document 2] Japanese Patent Laid-Open No. 2015-191234

In terms of the structure of the aforementioned BOA substrate, compared with a COA substrate, it is difficult to ensure reliability when manufacturing a liquid crystal display element, and it may cause a poor display quality of the liquid crystal display element. Furthermore, when a substrate with BCS is used, the above problems are made more apparent.

In view of the foregoing, the present invention is to provide a BOA substrate or a liquid crystal alignment agent for substrate coating with BCS, and a BOA substrate or a substrate with BCS provided with the liquid crystal alignment agent and having good display quality. Liquid crystal display element.

As a result of intensive studies, the present inventors have completed the present invention.

That is, this invention has the following summary.

A liquid crystal alignment agent for coating a BOA substrate or a substrate with BCS, comprising a polyimide selected from a polyimide precursor and polyimide obtained by subjecting the polyimide precursor to polyimide A polymer of at least one of the formed groups, the polyfluorene imide precursor is obtained by reacting a diamine component containing a diamine with a tetracarboxylic dianhydride component, and the diamine system is other than two amine groups The structure contains nitrogen or carboxylic acid groups.

2. The liquid crystal alignment agent according to the above 1, wherein the diamine system has, as a partial structure, a structure selected from at least one group selected from the group consisting of: (In the formula, Cy is a divalent group and is represented by an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and the substituent may be R ₁₄ is a hydrogen atom, a single bond, a carbonyl group, or * -CONH- (but the bond with "*" is bonded to a piperidine ring), and R ₁₅ is hydrogen or Valent organic groups, R ₁₈ and R ₁₉ are each independently a hydrogen atom or a single bond).

3. The liquid crystal alignment 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 formulae (1) to (9).

4. The liquid crystal alignment 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 alignment agent according to any one of the above 1 to 4, wherein the tetracarboxylic dianhydride component is at least one type of tetracarboxylic acid selected from the group consisting of the following formulae (12) to (14) Dianhydride.

6. The liquid crystal alignment agent according to any one of the above 1 to 5, wherein the liquid crystal alignment agent contains a polymer other than the polyfluorene imide precursor, or contains a polyimide precursor. A polymer other than polyimide.

7. The liquid crystal alignment agent according to any one of the above 1 to 6, wherein the liquid crystal alignment agent further comprises a group selected from the group consisting of an adhesion promoter, a cross-linking agent, a dielectric, a conductive substance, and an organic solvent. At least one.

8. The liquid crystal alignment agent according to the above 7, wherein the cross-linking agent is a compound selected from at least one of formula (17), formula (19), and formula (21) described later.

9. The liquid crystal alignment agent according to the above 8, wherein the cross-linking agent is at least one compound selected from the group consisting of formulas CL-1 to CL-3 described later.

10. A liquid crystal display element comprising a BOA substrate or a BCS-attached substrate, the substrates being formed with a liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of 1 to 9 above.

11. A method for manufacturing a liquid crystal alignment film on a BOA substrate or a substrate with BCS, which comprises applying the liquid crystal alignment agent according to any one of the above 1 to 9 to a BOA substrate.

12. A substrate for a liquid crystal display device, comprising: a BOA substrate or a substrate with BCS attached; and a liquid crystal alignment agent for coating a BOA substrate using any one of the above 1 to 9 and a substrate with the BOA substrate or a BCS attached A liquid crystal alignment film formed on a substrate.

According to the present invention, a BOA substrate or a liquid crystal alignment agent for coating a substrate with a BCS and a liquid crystal display element having a BOA substrate or a substrate with a BCS having good display quality obtained by using the liquid crystal alignment agent can be provided.

    [Best Mode for Implementing Invention]    

The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent for coating a BOA substrate or a substrate with BCS. The liquid crystal alignment agent contains a polyimide precursor and a polyimide obtained by subjecting the polyimide precursor to polyimide. A polymer of at least one of the groups referred to as fluorene imine (hereinafter also referred to as a specific polymer), the polyfluorene imide precursor is composed of a diamine component containing a diamine (hereinafter also referred to as a specific diamine) and It is obtained by reacting a carboxylic dianhydride component, and this diamine system contains nitrogen or a carboxylic acid group in the structure other than two amine groups. The liquid crystal display element of the present invention is a liquid crystal display element including a BOA substrate or a BCS-attached substrate, and the substrates are formed with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention.

    <Diamine containing nitrogen or a carboxylic acid group in a structure other than two amine groups>    

A diamine containing nitrogen or a carboxylic acid group in a structure other than two amine groups refers to a structure selected from the following formulae in a structure other than a structure in which two amine groups are bonded in a diamine structure. At least one structure of the group is used as a partial structure of the diamine. The structure of the following formula is preferably monovalent or divalent, and can be bonded to a structure bonded to two amine groups at any position thereof.

In the above structure, Cy is a divalent group and is a fat selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. It is represented by a group heterocyclic ring, and a substituent may be bonded to such a ring portion. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group, or * -CONH- (but the "*" bonded portion 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 liquid crystal display element includes a BOA substrate or a substrate with a BCS. The substrates are formed with a liquid crystal alignment film obtained from a liquid crystal alignment agent described below. The liquid crystal alignment agent contains a liquid crystal alignment agent selected from polyfluorene. An imine precursor and at least one polymer of a group consisting of polyimide obtained by subjecting the polyimide precursor to polyimide, the polyimide precursor system containing a polymer selected from the group consisting of The diamine component of at least one type of diamine represented by the formula (1) to the following formula (9) (hereinafter also referred to as specific diamines 1 to 9) is reacted with a tetracarboxylic dianhydride component .

    <Specific diamine 1>    

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

In 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-. Among them, -O-, -COO-, -NH-, -CONH-, -NHCO-, -CON (CH ₃ )-, -CH ₂ O-, or OCO- is preferred because it is easy to synthesize diamines. Particularly preferred is -O -, - CO -, - NH -, - CONH -, - NHCO -, - CON (CH 3) - or CH ₂ O-.

X ² is an alkyl group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing 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 carbon number of the alkyl group is preferably 1 to 3. Examples of the case where X ² is a non-aromatic heterocyclic ring containing a nitrogen atom include a pyrrolidine ring, a piperidine ring, a piperazine ring, a pyrazidine ring, Pyrimidine ring or imidazolidine ring. In particular, a non-aromatic heterocyclic ring having a 5-membered ring or a 6-membered ring is preferred as a liquid crystal alignment film because good alignment can be obtained. When the non-aromatic heterocyclic ring contains two nitrogen atoms, when it is used as a liquid crystal display device, the ionic impurities in the liquid crystal are adsorbed at the interface of the liquid crystal alignment film, so that the good electrical characteristics of the liquid crystal display device are maintained. should.

From the above viewpoints, as the non-aromatic heterocyclic ring containing a nitrogen atom, a piperazine ring is particularly preferable. In addition, when X ^{2 is} bonded to a nitrogen atom in X ³ or a carbon atom adjacent to the nitrogen atom, it is preferable that the effect of accelerating the reduction of the residual charge accumulated by the DC voltage when forming a liquid crystal display element is excellent.

X ³ is a 5- or 6-membered aromatic heterocyclic ring containing 1 or 2 nitrogen atoms, and the nitrogen atom may be substituted by an alkyl group having 1 to 5 carbon atoms. Examples of the 5- or 6-membered aromatic heterocyclic ring containing one or two nitrogen atoms include a pyridine ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, or a ring. Among them, a pyridine ring, an imidazole ring, a pyrazine ring, or a pyrimidine ring is preferable. Furthermore, when the aromatic heterocyclic ring in X ³ is substituted with an alkyl group, the carbon number of the alkyl group is preferably 1 to 3.

n is an integer from 1 to 4. Among them, an integer of 1 or 2 is preferred.

Specifically, the following compounds can be exemplified, but are not limited to these.

    <Specific diamine 2>    

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

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

In the formula (2-1), m1 is an integer of 1 to 4. In formula (2-2), X ₂ is 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 represent integers from 0 to 4, and m2 + m3 represent integers from 1 to 4. In formula (2-3), m4 and m5 represent integers of 1 to 5, respectively. In the formula (2-4), X ₃ is a linear or branched alkyl group having 1 to 5 carbon atoms. m6 is an integer from 1 to 5. In formula (2-5), X ₄ is 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 from 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-, and m2 and m3 are all integers of 1. In formula (2-5), X ₄ series single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH are preferred _2- , -COO- or -OCO-, m7 is an integer from 1 to 2. Among them, the diamine represented by the formula (2-1) is particularly preferred.

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

In formula (2-15), X ₅ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO- or -OCO-. In formula (2-16), X ₆ is 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 group having 1 to 5 carbon atoms. In terms of ease of synthesis, a linear alkylene group having 1 to 5 carbon atoms is preferred.

Cy is a divalent group and is represented by an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. In terms of ease of synthesis, azetidine, pyrrolidine or piperidine is preferred. The substituent may be bonded to such a ring portion.

Q ₂ is a structure represented by the following formula (3-I) or (3-II). * 1 in formula (3-I) or (3-II) represents a bond to Q ₁ . * 2 indicates 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, and still more preferably a hydrogen atom or a methyl group.

R ₂ and R ₃ are monovalent organic groups. q and r are independent integers of 0 to 4. However, if the total of q or r is 2 or more, R ₂ and R ₃ are independent of each other. In terms of ease of synthesis, R ₂ and R _{3 are} preferably methyl. In addition, the bonding position of the amine group in the benzene ring constituting the diamine is not limited, and the amine group is located at the 3 or 4 position with respect to the nitrogen atom on Cy, and is bonded to Q ₁ and R ₁ The nitrogen atom at the 3 or 4 position is preferred; the position at the 4-position relative to the nitrogen atom on Cy and the position at the 4-position relative to the nitrogen atom bonded to Q ₁ and R ₁ is more preferred. good.

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 group having 1 to 5 carbon atoms.

Specific examples represented by the above formula (3-1) include the following formulae (3-1-1) to (3-1-10). As specific examples represented by the above formula (3-2), For example, the following formulae (3-2-1) to (3-2-4).

    <Specific diamines 4 to 7>    

The specific diamines 4 to 7 used in the present invention are diamines represented by the following formulae (4) to (7) in which the amine group is protected by a Boc group.

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

The substitution position of the amine group in the above formula (4) is not particularly limited, but from the standpoint of the ease of synthesis or the availability of reagents, the meta- or para-position is taken as the reference when the amide bond is used as a reference. From the viewpoint of liquid crystal alignment, the position of the alignment is particularly preferred. In addition, even for amine benzenes that do not have an amine group protected by a Boc group (ie, -NHBoc), similarly, if the amide bond is used as a reference, the meta or para position is preferred, and the solubility is good. From a viewpoint, a meta position is preferable, and from a viewpoint of liquid crystal alignment, a para position is preferable. The hydrogen system of the amine benzene which does not have -NHBoc may be substituted with a halogen atom such as an organic group or fluorine.

The D in the formula (4) is not limited, and various structures can be selected depending on the structure using a dicarboxylic acid, a tetracarboxylic dianhydride, or the like as a raw material. As D, from the viewpoint of solubility, a divalent hydrocarbon group or the like is preferable, and a linear alkylene group or a cyclic alkylene group is mentioned as a preferable example. The hydrocarbon group may have an unsaturated bond. Knot. From the viewpoint of liquid crystal alignment and electrical characteristics, a divalent aromatic hydrocarbon group, a heterocyclic ring, or the like is preferred. From the viewpoint of liquid crystal alignment, those in which D does not have a substituent are preferred, but in terms of solubility, those in which a hydrogen atom is replaced by a carboxylic acid group or a fluorine atom are more preferred.

In formula (5), E is a single bond or a divalent saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group, or heterocyclic ring having 1 to 20 carbon atoms. 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 an asymmetrically structured diamine, but the preferred D is the same as above, and the preferred E is also the above The preferred D is the same. Regarding the diamine represented by formula (5), compounds in which both E and F are single bonds are preferred.

In the formula (6), A ₁ based single bond, selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- formed by at least one of the groups This is a bivalent 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 independently -CH ₂ -or -CH ₂ CH _2- . X ⁶ is an alkylene or cyclohexyl group having 1 to 6 carbon atoms. Y ¹ series 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 methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, benzyl or 9-fluorenyl. a is 0 or 1.

Specific examples of the diamine represented by the formulae (4) to (7) include formulae selected from the group consisting of the following formulae.

    <Specific diamine 8>    

The specific diamine 8 used in the present invention is a diamine represented by the following formula (8).

(In 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 1,3-dioxobutane (1,3-dioxobutyl).

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, i-butyl, and t-butyl.

Examples of the aromatic group having 6 to 20 carbon atoms include an aromatic group having 6 to 12 carbon atoms or other aromatic groups. Examples of the aryl group having 6 to 12 carbon atoms include phenyl, 3-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-i-propylphenyl, and 4-n-butyl. Phenyl or 3-chloro-4-methylphenyl and the like. Examples of the other aromatic groups include 4-pyridyl, 2-phenyl-4-quinolinyl, 2- (4'-t-butylphenyl) -4-quinolinyl, and 2- ( 2'-phenylthio) -4-quinolinyl and the like.

Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl and the like.

X ¹¹ is a single bond, a carbonyl group, or * -CONH- (but the bonding part with "*" is bonded to a piperidine ring).

R ₆ , R ₇ , R ₉ and R ₁₀ are an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 13 carbons, respectively. However, the benzene ring possessed by the aryl group and the aralkyl group may be substituted by a formamyl group or an alkoxy group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, i-butyl, or t-butyl; As an aryl group having 6 to 12 carbons (but the benzene ring of the aryl group may be substituted by a methylamino group or an alkoxy group having 1 to 4 carbon atoms), for example, a phenyl group and a 4-methylfluorenylbenzene Or 3,4,5-trimethoxyphenyl, etc .; as an aralkyl group having 7 to 13 carbon atoms (but the benzene ring having the aralkyl group may be formed by a methylamino group or an alkoxy group having 1 to 4 carbon atoms) Substituted), for example, benzyl and the like.

X ⁹ , X ¹⁰ , X ¹² and X ¹³ are single bonds, carbonyl groups, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(but the bonds with "*" are linked with The piperidine ring is bonded).

X ^14- based oxygen atom, * -OCO-, and the following formula (X ¹⁴ -1)

(Where a is an integer from 1 to 12 and b is an integer from 0 to 5)

The indicated group (but the "*" bonded portion is bonded to a 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 1,3-propenyl and 1,6-hexyl.

The two amine groups bonded to the benzene ring of the formula (8) are preferably at the 2,4-position or the 3,5-position with respect to the group X ⁴ .

Preferred specific examples of the diamine represented by the formula (8) include the following formulae (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. Examples of the monovalent organic group include an alkyl or alkenyl group having 1 to 10 carbon atoms, an alkoxy group, a cyano group, a hydroxyl group, a fluoroalkyl group, a trifluoroalkoxy group, a fluorine atom, and combinations thereof. The base of the formed group. A hydrogen atom or a methyl group is preferred.

R ₁₂ is a structure that independently represents a single bond or the following formula (9-2). An arbitrary hydrogen atom of the benzene ring may be substituted by a monovalent organic group.

R ₁₃ represents a single bond system, selected from the group consisting of -O -, - COO -, - OCO-, - (CH 2) l -, - O (CH 2) m O -, - CONH- and -NHCO- group formed by the Bivalent organic group (l and m are integers of 1 to 5). * ₁ represents a site bonded to a benzene ring in formula (9). * ₂ represents a site bonded to an amine group in the formula (9). n is an integer of 1 to 3. Among these, from the viewpoint of relaxation of the accumulated charge, R _{11 is} preferably a single bond, -O-, -COO-, -OCO-, -CONH-, or NHCO-.

n is an integer of 1 to 3. It is preferably 1 or 2.

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

    <Other diamines>    

In the present invention, a diamine other than the specific diamine may be used in combination as a part of the diamine component. Other diamines are not particularly limited, and examples thereof include side chain diamines described in detail below. The side chain diamine system can be preferably used when manufacturing a liquid crystal display element of a vertical alignment type.

The specific side chain type 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 them, a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, or COO- is preferable because it is easy to synthesize a side chain structure. It is more preferably 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 from 1 to 15). Among them, a single bond or (CH ₂ ) _b- (b is an integer of 1 to 10) is preferred.

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- are preferable because they are easy to synthesize. It is more preferably 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 hetero ring. An arbitrary hydrogen atom on such a cyclic group may be 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. Substituted by fluorine-containing alkoxy or fluorine atom. Furthermore, Y ⁴ is a divalent organic group having 12 to 25 carbon atoms in a steroid skeleton. As the Y ⁴ system, a benzene ring, a cyclohexyl ring, or an organic group having 12 to 25 carbon atoms having a steroid skeleton is preferable.

Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring. An arbitrary hydrogen atom on such a cyclic group may be 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. Substituted by fluorine-containing alkoxy or fluorine atom.

n is an integer from 0 to 4. It is preferably an integer of 0 to 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 alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. Still more preferred is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is a C1-C9 alkyl group or a C1-C9 alkoxy group.

m is an integer from 1 to 4. An integer of 1 is preferred.

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

In the formulae (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, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.

In formulae (10-4) to (10-6), R ³ represents -COO-, -OCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or CH _2- . R ⁴ is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.

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-. R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formamyl group, an ethenyl group, an ethenyloxy group, or a hydroxyl group.

In the formulae (10-9) to (10-10), R ⁷ is an alkyl group having 3 to 12 carbon atoms. The cis-trans isomers of 1,4-cyclohexyl are the trans isomers, respectively.

In the formulae (10-11) to (10-12), R ⁸ is an alkyl group having 3 to 12 carbon atoms. The cis-trans isomers of 1,4-cyclohexyl are the trans isomers, respectively.

In the formula (10-13), A ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom. A ³ is 1,4-cyclohexyl or 1,4-phenylene. A ² is an oxygen atom or COO- * (but the bonding part with "*" is bonded to A ³ ). A ¹ is an oxygen atom or COO- * (but the bonding part with "*" is bonded to (CH ₂ ) a ₂ )). In addition, a ₁ is an integer of 0 or 1. a ₂ is an integer from 2 to 10. a ₃ is an integer of 0 or 1.

Among the above formulas (10-1) to (10-31), particularly preferred diamine formulas (10-1) to (10-6), (10-9) to (10-13), Formula (10-16), Formula (10-19), Formula (10-23), Formula (10-25) or Formula (10-29) and the like.

As another diamine, the diamine represented by following formula (11) is mentioned.

In formula (11), Ar is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthyl, and biphenyl. These aromatic hydrocarbon groups may be substituted with an organic group, and a hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently an alkyl group, alkoxy group, benzyl group, or phenethyl group having 1 to 10 carbon atoms. If it is an alkyl group or alkoxy group, R ₁ and R ₂ may also be used. Form a ring. 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- bonding group. S is a single bond or an unsubstituted or alkylene group having 1 to 20 carbon atoms (but -CH ₂ -or CF ₂ -of an alkylene group may be optionally substituted with -CH = CH- When any of the groups listed below are not adjacent to each other, they can also be replaced by these groups: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, two Valent carbocyclic ring, divalent heterocyclic ring.). 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-.

Specific examples thereof include the following diamines.

(Where n is an integer from 1 to 8)

As another diamine, the diamine of the following formula, or the diamine described in pages 30 to 33 of International Publication Gazette 2014/171493 (published on 2014.10.23) can also be mentioned.

The other diamines described above may be used singly or as a mixture of two or more kinds in accordance with characteristics such as liquid crystal alignment, voltage retention, and accumulated charge when used as a liquid crystal alignment film.

    <Tetracarboxylic dianhydride component>    

The polymer contained in the liquid crystal alignment agent used in the present invention is not particularly limited as the tetracarboxylic dianhydride used as a raw material, but a tetracarboxylic acid represented by the following formulae (12) to (14) is used A dianhydride (also referred to as a specific tetracarboxylic dianhydride) is preferred.

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.

Specifically, it is a base represented by the following formulae (12a) to (12j).

In the formula (12a), Z ² to Z ⁵ are each independently selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring. In formula (6g), Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group.

In formula (12), in terms of polymerization reactivity or ease of synthesis, particularly preferred Z ¹ is formula (12a), formula (12c), formula (12d), formula (12e), formula (12f), or formula (12g).

In formula (13) or formula (14), j and k are each independently 0 or 1. x and y are each independently a single bond, a carbonyl group, an ester group, a phenylene group, a sulfonyl group, or a fluorenyl group.

The specific tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the following formulae (12-1) to (12-5). Among them, the residual image (charge accumulation) of the obtained liquid crystal display element From the viewpoint of), (12-1), (12-3) or (12-5) is more preferable.

    <Other tetracarboxylic dianhydride>    

In the present invention, a tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride may be used. As another tetracarboxylic dianhydride, the tetracarboxylic dianhydride of the tetracarboxylic acid shown below is mentioned.

Examples include 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic 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-pyridine Carboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The other tetracarboxylic dianhydrides mentioned above can be used singly or in combination of two or more kinds in accordance with characteristics such as liquid crystal alignment, voltage retention, and accumulated charge when used as a liquid crystal alignment film.

The liquid crystal alignment agent of the present invention may further contain a component other than the specific polymer component. Examples of such additional components include an adhesion promoter for improving the adhesion between the liquid crystal alignment film and the substrate, or an adhesion between the liquid crystal alignment film and the sealing material, and a selected agent for improving the strength of the liquid crystal alignment film. A cross-linking agent of at least one of the following formulae (17), (19), and (21), a dielectric substance, a conductive substance, or an organic solvent for adjusting the permittivity or resistance of the liquid crystal alignment film. Specific examples of such additional components are as disclosed in various well-known literatures on liquid crystal alignment agents, and examples include [0116] to [0116] on page 53 of International Publication Gazette 2015/060357. Revealed ingredients, etc.

In 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 an alkynyl group having 2 to 4 carbon atoms. And at least one is a base represented by formula (18). R ₂₂ and R ₂₄ are each independently represented as an aromatic ring, and an arbitrary hydrogen atom of the aromatic ring may be substituted by 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. To replace. R ₂₃ is a single bond, all or part of which is a saturated hydrocarbon group having 1 to 10 carbon atoms that can be bonded to form a cyclic structure.

In formula (19), R ₂₇ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing 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 may have a substituent. At least one of R ₂₈ and R ₂₉ has a hydroxyl group as a substituent. It is preferable that at least one of R ₂₈ and R ₂₉ is substituted with a group represented by formula (20). In the formula (20), R ₃₀ to R ₃₃ are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group.

In 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 are each independently represented as an aromatic ring. Any hydrogen atom of the aromatic ring may be It is substituted by 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, all or a part of which can be bonded to form a cyclic structure of a saturated hydrocarbon group having 1 to 10 carbon atoms, and any hydrogen atom may be replaced by a fluorine atom, -NH-, -N (CH ₃ )- Or the base 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), and in formula (21), d and f are each independently 1 to 3 Integer, e and g are each independently an integer of 1 ~ 3.

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

    <Polymer>    

In the present invention, as a method for synthesizing a polymer, a known polymerization method can be used. For example, the method described in pages 39 to 42 of International Publication Gazette 2014/171493 (published on 2014.10.23) can be mentioned.

    <Liquid crystal alignment agent>    

The polymer components in the liquid crystal alignment agent of the present invention may be all the specific polymers used in the present invention, or other polymers may be mixed with the specific polymers of the present invention. At this time, the content of the other polymers relative to the specific polymer is 0.5 to 15% by mass, and preferably 1 to 10% by mass.

Examples of other polymers include a diamine component made of a diamine other than a specific diamine, a polyimide precursor obtained from a tetracarboxylic dianhydride component, or a polyimide Polyimide obtained by imidation of an imine precursor. Examples of other polymers include acrylic polymers, methacrylic polymers, polystyrene, and polyamide.

In terms of the organic solvent in the liquid crystal alignment agent of the present invention, the content of the organic solvent is preferably from 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 thickness of the liquid crystal alignment film to be targeted. The organic solvent at this time is not particularly limited as long as it is an organic solvent capable of dissolving the specific polymer described above. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethylsulfine, tetramethylurea, pyridine, dimethylfluorene, hexamethylfluorene, γ-butane Lactone, 1,3-dimethyl-imidazolinone, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone , Ethylene carbonate, propylene carbonate, diglyme, or 4-hydroxy-4-methyl-2-pentanone. These systems can be used alone or in combination.

The liquid crystal alignment agent system of the present invention may contain a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group, or a cyclic carbonate group, and at least 1 selected from the group consisting of a hydroxyl group or an alkoxy group. A crosslinkable compound of a kind of a substituent or a crosslinkable compound having a polymerizable unsaturated bond.

In addition, as a compound that improves the uniformity or surface smoothness of the film thickness, it may contain a fluorine-based surfactant, a polysiloxane-based surfactant, or a non-ionic surfactant, etc., as a liquid crystal alignment film and a substrate The compound having improved adhesion may also contain a compound containing a functional silane or a compound containing an epoxy group.

Further, a dielectric substance or a conductive substance may be added for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film.

The liquid crystal alignment agent of the present invention may contain an organic solvent (also referred to as a poor solvent) or a compound that improves the uniformity or surface smoothness of the film thickness of the polymer film when the liquid crystal alignment agent is applied. It may further contain a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate.

As a poor solvent which improves the uniformity of a film thickness or surface smoothness, the following specific examples are mentioned.

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 monoisopropyl 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 , Dipropylene glycol 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, pentyl 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-methoxypyruvate, 3-ethoxy Methyl ethyl pyruvate, ethyl 3-methoxypyruvate, 3-ethoxypyruvate, 3-methoxypyruvate, propyl 3-methoxypyruvate, 3-methoxyacetone Acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol mono Acetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Organic solvents with low surface tension, such as propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, or isoamyl lactate.

These poor solvents can be used singly or in combination. When a poor solvent as described above is used, 5 to 80% by mass of the entire organic solvent contained in the liquid crystal alignment agent is preferred, and 20 to 60% by mass is more preferred.

    <Liquid crystal>    

As the liquid crystal composition used in the liquid crystal display element of the present invention, a horizontally aligned liquid crystal display element is a nematic liquid crystal having a positive dielectric anisotropy, and a negative dielectric may be used depending on the application. Anisotropic nematic liquid crystal.

In the case of a vertically aligned liquid crystal display device, a nematic liquid crystal having a negative dielectric anisotropy can be used. For example, dicyanobenzene-based liquid crystal, Based liquid crystal, Schiff base based liquid crystal, azo oxide based liquid crystal, biphenyl based liquid crystal, phenylcyclohexane based liquid crystal, or triphenyl based liquid crystal, and the like. The liquid may be used in combination with an alkenyl-based liquid crystal. As such an alkenyl-based liquid crystal, a conventionally known one can be used. Examples thereof include a compound represented by the following formula.

    <Liquid crystal alignment film and liquid crystal display element>    

The liquid crystal alignment agent of the present invention is applied to a BOA substrate or a substrate with BCS and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, etc., and can be used as a liquid crystal alignment film. Moreover, in the case of vertical alignment applications, etc., it can be used as a liquid crystal alignment film without performing alignment processing.

In the present invention, the BOA substrate is a substrate on which a black matrix is formed on a COA substrate. As the material used in the aforementioned black matrix, a column spacer (black column spacer (BCS)) that supports the array substrate and the counter substrate may also be used.

In addition, the substrate with BCS uses a black colored resin composition as a pillar spacer material that supports the array substrate and the counter substrate, and forms a substrate for the black pillar spacer. The aforementioned black matrix material may be used.

The BOA substrate or the substrate with BCS can be coated with a colored resin composition on a transparent substrate by spin coating, etc., and dried using a vacuum dryer or a heating plate, etc., and then passed through a photomask and an ultra-high pressure mercury lamp. After exposure and development using a KOH aqueous solution or the like, it is formed by firing using a hot-air circulation baking oven. As the colored resin composition, for example, a black matrix prepared by the method described in "0312" to "0314" of Japanese Patent Application Laid-Open No. 2014-67028 and a colored resin composition for BCS can be used.

The transparent substrate used at this time is not particularly limited as long as the substrate has high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate may be used. From the viewpoint of simplification of the manufacturing process, it is preferable to use a substrate formed with an ITO electrode or the like for liquid crystal driving. In the case of a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. As an electrode in this case, a material that reflects light may also be used.

The application method of the liquid crystal alignment agent is not particularly limited, and it is generally carried out by screen printing, lithography, flexographic printing, or inkjet in the industry. Other coating methods include dipping, roll coating, slit coater, spinner, etc., and these can be used depending on the purpose.

After the liquid crystal alignment agent is coated on a BOA substrate or a substrate with BCS, the solvent is evaporated at a temperature of 50 to 300 ° C, preferably 80 to 250 ° C by heating means such as a hot plate, so that a polymer film can be prepared. . If the thickness of the fired polymer film is too thick, it is disadvantageous in terms of the power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 ~ 300nm, and more preferably 10 ~ 100nm. When the liquid crystal is aligned horizontally or obliquely, the polymer film after firing is treated by rubbing or polarized ultraviolet radiation.

In addition, in a vertical alignment type liquid crystal display element, it is known to add a photopolymerizable compound to a liquid crystal composition in advance, and use it together with a vertical alignment film such as polyimide to apply an alternating current to the liquid crystal cell side. Or, a PSA (Polymer Sustained Alignment) device that can improve the response speed of liquid crystals by controlling the alignment of liquid crystals by irradiating ultraviolet rays to direct-current voltage to polymerize a polymerizable compound is disclosed in Japanese Patent Application Laid-Open No. 2003-307720 .

Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal component, and more preferably 0.1 to 5 parts by mass. If the polymerizable compound is less than 0.01 parts by mass, the alignment of the liquid crystal cannot be controlled because the polymerizable compound cannot be polymerized. If it exceeds 10 parts by mass, the number of unreacted polymerizable compounds will increase and the liquid crystal display device will be made. The afterimage characteristics are reduced.

On the other hand, non-patent documents based on (SC-PVA type liquid crystal display) K. Hanaoka, SID 04 DIGEST, P.1200-1202, etc. have reported that by adding a photopolymerizable compound to a liquid crystal alignment film, Not in the liquid crystal composition, it can accelerate the response speed of the liquid crystal display element.

    [Example]    

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples.

The abbreviations are as follows.

    (Acid dianhydride)    

BODA: Bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride, PMDA: Pyramid Tartaric dianhydride, TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride

    (Diamine)    

PDA: p-phenylenediamine, DDM: 4,4'-methylenebisdiphenylamine, DBA: 3,5-diaminobenzoic acid, nitrogen-containing diamines represented by the following formulas DA-N1 to DA-N7 Amine

Vertically-aligned 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

    <Additives>    

3AMP: 3-picolylamine

    <Crosslinking agent>    

Crosslinking agents represented by the following formulas CL-1 to CL-3

    (Polyimide molecular weight measurement conditions)    

Device: Normal temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Science Corporation, column: Shodex (KD-803, KD-805) column, column temperature: 50 ° C, eluent: N, N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30mmol / L, phosphoric acid‧anhydrous crystal (o-phosphoric acid) is 30mmol / L, tetrahydrofuran (THF) is 10ml / L), flow rate: 1.0ml / min, standard samples for the production of calibration lines: TSK standard polyethylene oxide (molecular weight about 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polymer manufactured by Polymer Laboratories Corporation Glycol (molecular weight approximately 12,000, 4,000, 1,000).

    (Polyimide's imidation rate)    

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube stand, manufactured by Kusano Scientific Corporation) In 5), 1.0 ml of deuterated dimethylarsine (DMSO-d ₆ , 0.05% TMS mixed product) was added, and ultrasonic waves were applied to completely dissolve. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring device (JNW-ECA500) manufactured by Japan Electronics Datum Corporation. The hydrazone imidization rate refers to protons from structures that have not changed before and after hydrazone imidization as the standard protons. The cumulative peak value of the protons and the NH group from sulfamic acid appearing around 9.5 to 10.0 ppm The cumulative value of the proton peaks is calculated by the following formula. In the following formulas, when x is the cumulative peak value of protons derived from the NH group of ammonium acid, y is the cumulative peak value of reference protons, and the case of α-type polyamidic acid (the ratio of fluorinated imine is 0%) Proportion of the number of reference protons relative to one proton of the NH group of amidine.

醯 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), and reacted at 80 ° C for 5 hours, then added CBDA (4.71 g, 24.0 mmol) and NMP (47.2 g) were further reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (43.1 g) and pyridine (13.4 g) were added as the phosphonium imidization catalyst, and the resulting mixture was made at 100 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (A). The polyimide has a hydrazone imidation rate of 78%, a number average molecular weight of 22,000, and a weight average molecular weight of 56,000.

NMP (44.0g) was added to the obtained polyfluorene imine powder (A) (6.0g), and it stirred at 70 degreeC for 20 hours, and was made to melt | dissolve. To this solution, 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BC (40.0 g) were added, and the liquid crystal alignment agent (A1) was obtained by stirring at room temperature for 5 hours.

    (Synthesis example 2)    

BODA (5.00g, 20.0mmol), DA-N1 (7.27g, 30.0mmol), DA-S1 (11.42g, 30.0mmol) and PDA (4.33g, 40.0mmol) were dissolved in NMP (113.8g). After reacting at 60 ° C for 3 hours, CBDA (11.37g, 58.0mmol) and NMP (26.3g) were added. After reacting at 40 ° C for 1 hour, PMDA (4.36g, 20.0mmol) and NMP (35.00g) were added. ) And allowed to react at room temperature for 10 hours to obtain a polyamine solution.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (46.3 g) and pyridine (14.3 g) as the phosphonium imidization catalyst were added, and they were allowed to stand at 50 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (B). The polyimide has a fluorene imidization rate of 76%, a number average molecular weight of 13,000, and a weight average molecular weight of 32,000.

Using the obtained polyfluorene imine powder (B) (6.0 g), a liquid crystal alignment agent (B1) was obtained in the same manner as in Synthesis Example 1.

    (Synthesis example 3)    

BODA (5.00g, 20.0mmol), DA-N1 (7.27g, 30.0mmol), DA-S1 (11.42g, 30.0mmol) and DBA (6.09g, 40.0mmol) were dissolved in NMP (118.3g) to After reacting at 60 ° C for 3 hours, CBDA (11.37g, 58.0mmol) and NMP (27.3g) were added. After reacting at 40 ° C for 1 hour, PMDA (4.36g, 20.0mmol) and NMP (36.41g) were added. ) And allowed to react at room temperature for 10 hours to obtain a polyamine solution.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (44.5 g) and pyridine (13.8 g) as phosphonium imidization catalysts were added, and the mixture was allowed to stand at 50 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (C). The polyimide has a hydrazone imidation rate of 79%, a number average molecular weight of 21,000, and a weight average molecular weight of 49,000.

A liquid crystal alignment agent (C1) was obtained by using the obtained polyfluorene imine powder (C) (6.0 g) in the same manner as in Synthesis Example 1.

    (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 dissolved in NMP (208.4 g), and It was made to react at 60 degreeC for 10 hours, and the polyamic acid solution was obtained.

After adding NMP to this polyamidic acid solution (200g) and diluting to 6.5% by mass, acetic anhydride (37.6g) and pyridine (11.6g) as the phosphonium imidization catalyst were added, and the mixture was made at 110 ° C The reaction took 4 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (D). The polyimide has a fluorene imidization rate of 68%, a number average molecular weight of 11,000, and a weight average molecular weight of 25,000.

Using the obtained polyfluoreneimide powder (D) (6.0 g), a liquid crystal alignment agent (D1) was obtained in the same manner as in Synthesis Example 1.

    (Synthesis example 5)    

BODA (18.77g, 75.0mmol), DA-N3 (11.78g, 30.0mmol), DBA (3.04g, 20.0mmol) and DA-S1 (19.03g, 50.0mmol) were dissolved in NMP (171.9g) to 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.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (35.5 g) and pyridine (11.0 g) as the phosphonium imidization catalyst were added, and they were made at 100 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (E). The polyimide has a hydrazone imidation rate of 75%, a number average molecular weight of 16,000, and a weight average molecular weight of 39,000.

Using the obtained polyfluorene imine powder (E) (6.0 g), a liquid crystal alignment agent (E5) was obtained in the same manner as in Synthesis Example 1.

    (Synthesis example 6)    

After 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) and reacted at 80 ° C for 5 hours Then, CBDA (4.12 g, 21.0 mmol) and NMP (52.46 g) were added, and they were reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (38.8 g) and pyridine (12.0 g) as phosphonium imidization catalysts were added, and they were made at 100 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (F). The polyimide has a fluorene imidization rate of 57%, a number average molecular weight of 10,000, and a weight average molecular weight of 24,000.

Using the obtained polyfluorene imine powder (F) (6.0 g), a liquid crystal alignment agent (F1) was obtained in the same manner as in Synthesis Example 1.

    (Synthesis example 7)    

BODA (12.51g, 50.0mmol), PDA (3.24g, 30.0mmol), DA-N5 (11.13g, 20.0mmol) and DA-S1 (19.03g, 50.0mmol) were dissolved in NMP (166.6g) to 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.

After adding NMP to this polyphosphonic acid solution (180 g) and diluting it to 6.5% by mass, acetic anhydride (36.6 g) and pyridine (11.4 g) as the phosphonium imidization catalyst were added and reacted at 80 ° C. 2 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 80 ° C to obtain a polyfluorene imine powder (F). The polyimide has a hydrazone imidation ratio of 73%, a number average molecular weight of 17,000, and a weight average molecular weight of 38,000.

Using the obtained polyfluorene imine powder (G) (6.0 g), a liquid crystal alignment agent (G1) was obtained in the same manner as in Synthesis Example 1.

    (Comparative Synthesis Example 1)    

BODA (12.51g, 50.0mmol), DA-1 (16.52g, 50.0mmol), and DA-S1 (19.03g, 50.0mmol) were dissolved in NMP (192.2g) and reacted at 60 ° C for 3 hours, then added PMDA (4.36 g, 48.5 mmol), CBDA (9.61 g, 49.0 mmol), and NMP (38.4 g) were reacted at 40 ° C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyphosphonic acid solution (200 g) and diluting it to 6.5% by mass, acetic anhydride (35.3 g) and pyridine (10.9 g) as the phosphonium imidization catalyst were added, and they were allowed to stand at 80 ° C Reaction for 3 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (H). The polyimide has a fluorene imidation rate of 73%, a number average molecular weight of 17,000, and a weight average molecular weight of 48,000.

Using the obtained polyfluorene imine powder (H) (6.0 g), a liquid crystal alignment agent (H1) was obtained in the same manner as in Synthesis Example 1.

    (Comparative Synthesis Example 2)    

BODA (12.51g, 50.0mmol), PDA (5.41g, 50.0mmol), and DA-S1 (19.03g, 50.0mmol) were dissolved in NMP (147.7g), and after reacting at 60 ° C for 3 hours, BDA ( 9.41 g, 48.0 mmol) and NMP (37.7 g), and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamidic acid solution (200g) and diluting to 6.5% by mass, acetic anhydride (43.7g) and pyridine (13.5g) as phosphonium imidization catalysts were added, and they were allowed to stand at 80 ° C. Reaction for 2 hours. This reaction solution was poured into methanol (2700 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (I). The polyimide has a hydrazone imidation ratio of 72%, a number average molecular weight of 13,000, and a weight average molecular weight of 25,000.

Using the obtained polyfluorene imine powder (I) (6.0 g), a liquid crystal alignment agent (I1) was obtained in the same manner as in Synthesis Example 1.

    (Synthesis example 8)    

6.0 g of the liquid crystal alignment agent (H1) obtained in Comparative Synthesis Example 1 as the first component and 14.0 g of liquid crystal alignment agent (C1) obtained in Synthesis Example 3 as the second component were mixed, and the liquid crystal was prepared by stirring for 1 hour. Aligning agent (J1).

    (Synthesis example 9)    

6.0 g of the liquid crystal alignment agent (I1) obtained in Comparative Synthesis Example 2 as the first component and 14.0 g of liquid crystal alignment agent (C1) obtained in Synthesis Example 3 as the second component were mixed, and the liquid crystal was prepared by stirring for 1 hour. Aligning agent (K1).

    (Synthesis example 10)    

To 10.0 g of the liquid crystal alignment agent (A1) obtained in Synthesis Example 1, CL-2 was added so that the resin content reached 10% by weight, and the liquid crystal alignment agent (A2) was prepared by stirring at room temperature for 1 hour.

    (Synthesis example 11)    

To 10.0 g of the liquid crystal alignment agent (D1) obtained in Synthesis Example 4, CL-1 was added so that the resin content reached 10% by weight, and the liquid crystal alignment agent (D2) was prepared by stirring at room temperature for 1 hour.

    (Synthesis example 12)    

To 10.0 g of the liquid crystal alignment agent (K1) obtained in Synthesis Example 9, CL-3 was added so that the resin content reached 10% by weight, and the liquid crystal alignment agent (K2) was prepared by stirring at room temperature for 1 hour.

    (Synthesis example 13)    

BODA (2.50g, 10.0mmol), DA-N6 (3.97g, 10.0mmol) and DA-S1 (3.81g, 10.0mmol) were dissolved in NMP (41.1g), and the reaction was carried out at 60 ° C for 3 hours. CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were reacted at 40 ° C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyphosphonic acid solution (40 g) and diluting it to 6.5% by mass, acetic anhydride (6.68 g) and pyridine (2.07 g) as the phosphonium imidization catalyst were added, and they were made at 80 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (461 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluoreneimide powder (L). The polyimide has a hydrazone imidation ratio of 72%, a number average molecular weight of 15,000, and a weight average molecular weight of 28,000.

Using the obtained polyfluorene imine powder (L) (6.0 g), a liquid crystal alignment 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), and the reaction was carried out at 60 ° C for 3 hours. CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were reacted at 40 ° C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyphosphonic acid solution (40 g) and diluting it to 6.5% by mass, acetic anhydride (6.99 g) and pyridine (2.17 g) were added as the phosphonium imidization catalyst, and the mixture was allowed to stand at 80 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (463 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyfluorene imine powder (M). The polyimide has a fluorene imidation rate of 70%, a number average molecular weight of 14,000, and a weight average molecular weight of 30,000.

Using the obtained polyfluorene imide powder (M) (6.0 g), a liquid crystal alignment 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 alignment agent A1 obtained in Synthesis Example 1 according to the following procedure, and the measurement of the pretilt angle and the measurement of the voltage holding ratio were performed.

    <Preparation of colored resin composition>    

The colored resin composition (a) for a black column spacer (BCS) used in the present invention can also be used as a resin composition of a black matrix material, and uses "0312" to "0314" of JP 2014-67028. The photoresist (VI) described in the above method is used for modulation.

    <Production of ITO substrate with BCS>    

The above-mentioned colored resin composition (a) was spin-coated so that the film thickness after firing became 4 μm to an ITO electrode pattern with a pixel size of 100 μm × 300 μm and a line width / space of 5 μm / 5 μm. ITO electrode on a glass substrate. After that, it was dried with a vacuum dryer for 60 seconds, and then dried on a hot plate at 110 ° C. for 2 minutes to obtain a pre-exposure substrate with a colored resin composition (a).

The pre-exposure substrate was exposed at a rate of 50 mJ / cm2 using an ultra-high pressure mercury lamp through a circular mask with an opening of 20 μm, and then developed at a temperature of 25 ° C. using a 0.05% by mass KOH aqueous solution. After that, the substrate with the photoresist (VI) was fired at 230 ° C. for 30 minutes in a hot-air circulation baking oven to obtain an ITO substrate with BCS.

    <Making a Liquid Crystal Cell>    

Using the liquid crystal alignment agent (A1), a liquid crystal cell was produced according to the procedure shown below. The liquid crystal alignment agent (A1) was spin-coated on the ITO surface of the ITO substrate with BCS, dried on a heating plate at 80 ° C for 90 seconds, and then fired in a hot air circulation baking oven at 200 ° C for 30 minutes. Thus, a liquid crystal alignment film with a film thickness of 100 nm was formed.

In addition, the liquid crystal alignment agent (A1) was spin-coated on the ITO surface without an electrode pattern, and dried on a heating plate at 80 ° C for 90 seconds, and then subjected to a hot-air circulation baking oven at 200 ° C for 30 minutes. Firing is performed to form a liquid crystal alignment film having a thickness of 100 nm.

For the two substrates described above, a thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the side surface of the other substrate on which the liquid crystal alignment film is formed is located inside, and after being bonded to the substrate, the sealant is hardened to produce an empty cell. Liquid crystal MLC-3023 (a trade name of Merck, an alkenyl-based liquid crystal) containing a polymerizable compound for PSA was injected into the empty cell by a reduced-pressure injection method to prepare a liquid crystal cell. The voltage holding ratio (VHR) of the liquid crystal cell was measured.

Next, in a state where a DC voltage of 15 V was applied to the liquid crystal cell, 10 J / cm ^{2 was} irradiated from the outside of the liquid crystal cell with UV at a band-pass filter of 365 nm (also called primary PSA treatment). The UV illuminance was measured using UV-MO3A (accessory: UV-35) manufactured by ORC Corporation. Thereafter, in order to passivate the unreacted polymerizable compounds remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 / A-1) was irradiated with a UV-FL irradiation device manufactured by Toshiba Lighting without applying a voltage. ) 30 minutes (also known as 2 PSA treatments). Then, the unit cell after UV irradiation was measured for the pretilt angle of the pixel portion and the voltage retention ratio.

    "Determination of pretilt angle"    

The measurement was performed using an LCD analyzer LCA-LUV42A (manufactured by Meishi Ryo Technica).

    `` Evaluation of voltage holding ratio ''    

A voltage of 60V for 1V was applied to a 60 ° C hot-air circulation baking oven, and then the voltage after 1667msec was measured, and the degree to which the voltage could be maintained was calculated as the voltage retention rate. For the measurement of the voltage holding ratio, VHR-1 manufactured by Toyo Technica was used.

    (Examples 2 to 14, Comparative Examples 1 and 2)    

Except changing the liquid crystal alignment agent (A1) used in Example 1 to the liquid crystal alignment agent (B1) to (M1), (A2), (D2), or (K2), the same operation as in Example 1 was performed, and The measurement of the pretilt angle and the measurement of the voltage holding ratio were performed.

    (Example 1 ')    

In accordance with the same operation as in Example 1, a liquid crystal cell was produced using a substrate with an ITO-attached electrode without BCS, and the pretilt angle and the voltage holding ratio were measured. In order to maintain the cell gap, a 4 μm bead spacer was used instead of the black pillar spacer and spread on the liquid crystal alignment film.

    (Examples 2 'to 14', Comparative Examples 1 'and 2')    

Except changing the liquid crystal alignment agent (A1) used in Example 1 'to the liquid crystal alignment agent (B1) to (M1), (A2), (D2), or (K2), the same operation as in Example 1' was performed. , And measure the pretilt angle and voltage retention ratio.

As can be confirmed from the above results, compared with Comparative Examples 1, 2, and 1 'and 2', even if Examples 1 to 7, 13, 14 and Examples 1 'to 7', 13 ', and 14' are When a substrate with BCS is used, high VHR characteristics can also be exhibited.

Furthermore, from Examples 8, 9 and 8 'and 9', it can be seen that even if a polymer which does not have a diamine containing a carboxyl group or a nitrogen-containing structure as a monomer unit is used in combination with a polymer having the diamine as a monomer unit, Polymers in monomer units can also exhibit high VHR characteristics. In addition, as shown in Examples 10 to 12 and 10 'to 12', a cross-linking agent is added to a polymer that exhibits high VHR characteristics even when a substrate with BCS is used. When showing the same high VHR characteristics.

The entire contents of the specification, patent application scope, and abstract of Japanese Patent Application No. 2016-118281, filed on June 14, 2016, are hereby incorporated by reference as the disclosure of the present specification.

Claims (12)

    A BOA substrate or a liquid crystal alignment agent for substrate coating with BCS, which is characterized by containing polyimide selected from a polyimide precursor and polyimide obtained by subjecting the polyimide precursor to polyimide. Polymer of at least one of the group, the polyfluorene imide precursor is obtained by reacting a diamine component containing a diamine with a tetracarboxylic dianhydride component, and the diamine system is in a structure other than two amine groups Contains nitrogen or carboxylic acid groups.     The liquid crystal alignment agent according to claim 1, wherein the diamine system has a structure selected from the group consisting of at least one selected from the group consisting of: (In the formula, Cy is a divalent group and is represented by an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and the substituent may be R ₁₄ is a hydrogen atom, a single bond, a carbonyl group, or * -CONH- (but the bond with "*" is bonded to a piperidine ring), and R ₁₅ is hydrogen or Valent organic groups, R ₁₈ and R ₁₉ are each independently a hydrogen atom or a single bond). The liquid crystal alignment agent according to claim 1 or 2, wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulae (1) to (9), (In 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-, X ² is an alkyl group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom, and the X ³ series contains 1 or 2 nitrogen atoms 5-membered or 6-membered aromatic heterocyclic ring, and the nitrogen atom may be substituted by an alkyl group having 1 to 5 carbon atoms, 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, and n is an integer of 1 to 4) (In formula (3), Q ₁ represents an alkylene group having 1 to 5 carbon atoms, and Cy is a divalent group selected from azetidine, pyrrolidine, piperidine, and hexamethyleneimine. This group is represented by an aliphatic heterocyclic ring, and a substituent may be bonded to such a ring portion. Q ₂ represents a structure of the following formula (3-I) or (3-II), and formula (3-I ), (3-II) in the line 1 * denotes the bond to Q _1, * 2 are diagrams of the benzene ring bonding with the formula (3-II) R ₁ represents a hydrogen-based or a monovalent organic group , R ₂ and R ₃ are monovalent organic groups, and q and r are each independently an integer of 0 to 4, but if the total of q or r is 2 or more, R ₂ and R ₃ are respectively independent) (In formula (4), D represents a divalent saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group, or heterocyclic ring having 1 to 20 carbon atoms, and D may have various substituents. M is 1 or 0. In 5), E is a single bond or a divalent saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring having 1 to 20 carbon atoms, and F is a single bond, -O-, -OCO-, or COO-. (6), a ₁ based single bond, selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O- and OCO- group formed by the at least one kind of A 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, and R ₁₆ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. In (7), X ⁴ and X ⁸ are each independently a single bond, -CH ₂ -or -CH ₂ CH _2- , and X ⁵ and X ⁷ are independently -CH ₂ -or -CH ₂ CH _2- , X ⁶ is an alkylene or cyclohexyl having 1 to 6 carbon atoms, and 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 independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, benzyl or 9-fluorenyl, a is 0 or 1) (In 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 1,3-dioxobutyl group , X ¹¹ is a single bond, carbonyl or * -CONH- (but the bond with "*" is bonded to the piperidine ring), and R ₆ , R ₇ , R ₉ and R ₁₀ are each independently carbon 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, but the benzene ring of the aryl group and the aralkyl group may be a methylenyl group or 1 to 6 carbon atoms. Substituted by 4 alkoxy groups, X ⁹ , X ¹⁰ , X ¹² and X ¹³ are each independently a single bond, carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(but with The "*" bond is bonded to the piperidine ring), and X ¹⁴ is independently -O-, * -OCO-, and a base represented by the following formula (X ¹⁴ -1) (with " (*) Is bonded to the piperidine ring in formula (8)), methylene or 2-6 carbon alkylene) (In formula (X ¹⁴ -1), a is an integer of 1 to 12, and b is an integer of 0 to 5) (In the formula (9), R ₁₁ represents hydrogen or a monovalent organic group, and R ₁₂ represents each independently a structure of a single bond or the following formula (9-2), and an arbitrary hydrogen atom of a benzene ring can be (Substituted by a monovalent organic group, n is an integer of 1 to 3) (In formula (9-2), R ₁₃ represents a single bond, and is selected from -O-, -COO-, -OCO-,-(CH ₂ ) _l- , -O (CH ₂ ) _m O-, -CONH -And -NHCO- are divalent organic groups (l and m represent integers of 1 to 5), * ₁ represents a site bonded to a benzene ring in formula (9), and * _{2 represents} Represents the site | part bonded to the amine group in Formula (9)). The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine component contains a diamine represented by the following formula (10) or (11), (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-, and Y ² is Single bond or (CH ₂ ) _b- (b is an integer from 1 to 15), Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O -, -COO- or OCO-, Y ⁴ is a bivalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on such a cyclic group may be C1-C3 alkyl, C1-C3 alkoxy, C1-C3 fluorinated alkyl, C1-C3 fluorinated alkoxy or fluorine atom are substituted, and further Y ⁴ system having carbon steroid skeleton of the number of a divalent organic group having 12 to 25 as Y ⁴ lines to a benzene ring, a cyclohexyl ring or with a carbon-based steroid skeleton of the number of an organic group having 12 to 25 is preferred, Y ⁵ selected from the group Free benzene ring, cyclohexyl ring and heterocyclic group formed by bivalent cyclic groups, any of these hydrogen atoms on the cyclic group can be an alkyl group with 1 to 3 carbon atoms, 1 to 3 carbon atoms Substituted by alkoxy, fluorinated alkyl having 1 to 3 carbon atoms, fluorinated alkoxy having 1 to 3 carbon atoms or fluorine atom, n is an integer of 0 to 4, and Y ⁶ is a carbon number of 1 to 18 Alkyl, fluorinated alkyl with 1 to 18 carbons, alkoxy with 1 to 18 carbons, or (Fluorine-containing alkoxy 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, naphthyl and phenylene. These may be substituted by organic groups, and hydrogen atoms may also be halogen atoms. Instead, R ₁ and R ₂ are each independently an alkyl group, alkoxy group, benzyl group, or phenethyl group having 1 to 10 carbon atoms. In the case of an alkyl group or alkoxy group, R ₁ and R ₂ may also be used. Form a ring, 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- bonding group, S is a single bond or an unsubstituted or substituted carbon atom of 1 to 20 carbon atoms (but -CH ₂ -or CF ₂ -of the alkylene group may be arbitrarily substituted by -CH = CH-, and when any of the groups listed below are not adjacent to each other, they may also be substituted by these groups:- O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a divalent heterocyclic ring), Q represents the following structure, (In the formula, R represents independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents -CH _2- , -NR-, -O-, or S-). The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the tetracarboxylic dianhydride component is at least one type of tetracarboxylic acid di selected from the group consisting of the following formulae (12) to (14). anhydride, (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. In formula (13) or formula (14), j and k is independently 0 or 1, and X and y are each independently a single bond, a carbonyl group, an ester group, a phenylene group, a sulfonyl group, or a fluorenylamino group).     The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the liquid crystal alignment agent contains a polymer other than the aforementioned polyfluorene imine precursor, or includes a polyimide precursor of the polyfluorene imine A polymer other than polyfluorene.         The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the liquid crystal alignment agent system further includes at least one selected from the group consisting of an adhesion promoter, a crosslinking agent, a dielectric, a conductive substance, and an organic solvent. 1 species.     The liquid crystal alignment agent according to claim 7, wherein the cross-linking agent is a compound selected from at least one of the following formula (17), formula (19), and formula (21), (In 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 an alkyne having 2 to 4 carbon atoms. And at least one is a group represented by formula (18), and R ₂₂ and R ₂₄ are each independently represented as an aromatic ring, and any hydrogen atom of the aromatic ring may be a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, It is substituted by halogen atom, alkoxy group with 1 to 3 carbon atoms or vinyl group. R ₂₃ is a single bond, all or part of which can be bonded to form a saturated hydrocarbon group with 1 to 10 carbon atoms.) (In formula (19), R ₂₇ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, c is an integer of 2 to 6, and 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. These groups may have a substituent. However, at least one of R ₂₈ and R ₂₉ has A hydroxyl group is used as a substituent, and it is preferred that at least one of R ₂₈ and R ₂₉ is substituted with a group represented by formula (20). In formula (20), R ₃₀ to R ₃₃ are each independently hydrogen Atom, hydrocarbyl or hydrocarbyl substituted by hydroxy) (In 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 are each independently represented as an aromatic ring. Any hydrogen atom of the aromatic ring may be It is substituted by 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, all or part of which can be bonded to form a cyclic carbon. A saturated hydrocarbon group of 1 to 10 and any hydrogen atom may be substituted by a fluorine atom, -NH-, -N (CH ₃ )-, or a group represented by formula (22). In formula (22), P ₁ and P ₂ is independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ is an aromatic ring), and in formula (21), d and f are each independently an integer of 1 to 3, and e and g are each independently 1 to 3). The liquid crystal alignment 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 element includes a BOA substrate or a substrate with a BCS attached thereto. The substrates are formed with a liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 9.         A method for manufacturing a liquid crystal alignment film on a BOA substrate or a substrate with BCS, which comprises applying the liquid crystal alignment agent according to any one of claims 1 to 9 to a BOA substrate or a substrate with BCS.         A substrate for a liquid crystal display element, comprising: a BOA substrate or a substrate with BCS; and a liquid crystal alignment agent using any one of claims 1 to 9 and formed on the BOA substrate or the substrate with BCS Liquid crystal alignment film.