KR102420192B1 - Liquid crystal aligning agent and liquid crystal display element for application of BOA substrates or substrates with BCS - Google Patents

Abstract

The liquid crystal display element provided with the liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS, and the BOA board|substrate with favorable display quality obtained using this liquid crystal aligning agent, or board|substrate with BCS is provided.
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 a polyimide obtained by imidizing the polyimide precursor A liquid crystal display element provided with the liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS containing the at least 1 sort(s) of polymer selected from the group, and the BOA board|substrate or board|substrate with BCS in which the liquid crystal aligning film obtained was formed.

Description

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

This invention relates to the liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS, and the liquid crystal display element provided with the BOA board|substrate obtained using it, or the board|substrate with BCS.

In general, a liquid crystal display device includes an array substrate on which a thin film transistor is formed, a counter substrate on which a color filter is formed to face the array substrate, and a liquid crystal layer interposed between the array substrate and the counter substrate. A black matrix is required for a color filter in the boundary part between colored layers, such as red, green, and blue, in order to improve contrast and color development effect. In recent years, from the relationship of manufacturing yield, etc., the color filter on array (COA:Color-Filter On Array) in which the color filter was formed on the array board|substrate, and the black matrix on which forms a black matrix on the COA board|substrate Array (BOA: Black Matrix On Array) substrates have been developed.

From the relationship of better production yield, etc., attempts have been made to use a black colored resin composition as a column spacer material for supporting between the array substrate and the opposing substrate (such a column spacer, a black column spacer (BCS: Black) Also called Colum Spacer), the said black matrix material may be used for the black colored resin composition.

Japanese Patent Laid-Open No. 2014-167492 Japanese Laid-Open Patent Publication No. 2015-191234

Compared with the COA substrate, the BOA substrate has a structure that makes it difficult to secure reliability when a liquid crystal display device is manufactured, and may cause a defect in the display quality of the liquid crystal display device. Moreover, by using the board|substrate with a BCS, the said problem becomes more remarkable.

This invention was made in view of the said situation, The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS, and the liquid crystal provided with the BOA board|substrate or board|substrate with BCS which is obtained using the said liquid crystal aligning agent and has favorable display quality. It is to provide a display element.

MEANS TO SOLVE THE PROBLEM This inventor came to complete this invention, as a result of earnestly researching.

That is, this invention has the following summary.

1. The polyimide precursor obtained by making the diamine component containing the diamine containing nitrogen or a carboxylic acid group, and tetracarboxylic dianhydride component react in structures other than two amino groups, and the polyimide which imidated the polyimide precursor The liquid crystal aligning agent for BOA board|substrate or board|substrate with BCS application|coating containing at least 1 sort(s) of polymer chosen from the group which consists of.

2. The liquid crystal aligning agent of said 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.

[Formula 1]

(Wherein, 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 moieties. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group, or *-CONH- (provided that the hand to which "*" is attached is bonded to the piperidine ring.) R ₁₅ represents hydrogen or a monovalent organic group. R ₁₈ and R ₁₉ is each independently a hydrogen atom or a single bond.)

3. Liquid crystal aligning agent of said 1 or 2 whose said diamine is at least 1 diamine chosen from the group which consists of diamine of following formula (1)-(9).

4. The liquid crystal aligning agent in any one of said 1-3 containing the diamine in which the said diamine component is represented by following formula (10) or (11).

5. Liquid crystal orientation in any one of said 1-4 whose said tetracarboxylic dianhydride component is at least 1 piece(s) of tetracarboxylic dianhydride chosen from the group which consists of following formula (12)-(14) My.

6. Liquid crystal aligning agent in any one of said 1-5 in which said liquid crystal aligning agent contains polymers other than the polyimide which imidated polymers other than the said polyimide precursor, or this polyimide precursor.

7. The liquid crystal aligning agent in any one of said 1-6 in which the said liquid crystal aligning agent further contains at least 1 selected from the group which consists of a close_contact|adherence adjuvant, a crosslinking agent, a dielectric material, an electrically-conductive substance, and an organic solvent.

8. Liquid crystal aligning agent of said 7 whose said crosslinking agent is an at least 1 compound chosen from following formula (17), Formula (19), and Formula (21).

9. The liquid crystal aligning agent as described in said 8 whose said crosslinking agent is an at least 1 compound chosen from the group which consists of following formula CL-1 - CL-3.

10. A liquid crystal display element provided with the BOA board|substrate or board|substrate with BCS in which the liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of said 1-9 was formed.

11. The manufacturing method of the liquid crystal aligning film on the BOA board|substrate or board|substrate with BCS which apply|coats the liquid crystal aligning agent in any one of said 1-9 to a BOA board|substrate.

12. Board|substrate for liquid crystal display elements provided with a BOA substrate or a board|substrate with BCS, and the liquid crystal aligning film formed on the said BOA board|substrate or board|substrate with BCS using the liquid crystal aligning agent for BOA board|substrate application|coating in any one of said 1-9. .

By this invention, the liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS, and the liquid crystal display element provided with the BOA board|substrate or board|substrate with BCS which have the favorable display quality obtained using the same is provided.

The liquid crystal aligning agent of this invention reacts the diamine component and tetracarboxylic dianhydride component containing the diamine (henceforth specific diamine) which contains nitrogen or a carboxylic acid group in structure in structures other than two amino groups. Liquid crystal alignment for application to a BOA substrate or a substrate with BCS containing at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor obtained by making the polyimide precursor and a polyimide obtained by imidizing the polyimide precursor. it's jay Moreover, the liquid crystal display element of this invention is a liquid crystal display element provided with the BOA board|substrate or 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 a carboxylic acid group in a structure other than two amino groups>

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

[Formula 2]

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 may be bonded to these ring portions. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group, or *-CONH- (provided that the bond to which “*” is attached is bonded to the 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.

The diamine component and tetracarboxylic dianhydride component containing at least 1 diamine specifically, selected from the diamine (henceforth specific diamines 1-9) represented by following formula (1) - following formula (9) A BOA substrate or a substrate with BCS on which a liquid crystal aligning film obtained from a liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting the polyimide precursor and a polyimide obtained by imidizing the polyimide precursor is formed It is a liquid crystal display device that

<Specific diamine 1>

The specific diamine 1 used for this invention is a diamine represented by following formula (1).

[Formula 3]

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- are preferable because diamine is easily synthesized. Particularly preferably, -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, as for carbon number of an alkyl group, 1-3 are preferable. Further, in the case where X ² is a non-aromatic heterocyclic ring containing a nitrogen atom, an example of a pyrrolidine ring, a piperidine ring, a piperazine ring, a pyrazolidine ring, a quinuclidine ring or an imidazolidine ring can be heard Since favorable orientation is obtained especially when it is set as a liquid crystal aligning film that a non-aromatic heterocyclic ring is a 5-membered ring or a 6-membered ring, it is preferable. Moreover, when a non-aromatic heterocyclic ring contains two nitrogen atoms, when it is set as a liquid crystal display element, in the liquid crystal aligning film interface, in order to adsorb|suck the ionic impurity in a liquid crystal, and to maintain favorable electrical properties of a liquid crystal display element, desirable.

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, when a liquid crystal display element is formed, the effect of accelerating the relaxation of the residual charge accumulated by the DC voltage is excellent. It is preferable because

X ³ is a 5-membered ring or 6-membered aromatic heterocyclic ring containing 1 or 2 nitrogen atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms. Examples of the 5-membered ring or 6-membered aromatic heterocyclic ring containing 1 or 2 nitrogen atoms include a pyridine ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring or a pyridazine 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 by the alkyl group, as for carbon number of this alkyl group, 1-3 are preferable.

n is an integer of 1-4. Especially, the integer of 1 or 2 is preferable.

Specifically, although the following compounds are illustrated, it is not limited to these.

[Formula 4]

<Specific diamine 2>

The specific diamine 2 used for this invention is a diamine represented by Formula (2).

[Formula 5]

In Formula (2), X< ₁ > is an organic group which has a C6-C30 aromatic ring. n is an integer of 1-4. As a preferable example of the diamine represented by Formula (2), following formula (2-1) - (2-5) are mentioned.

[Formula 6]

In formula (2-1), m1 is an integer of 1-4. 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 each represent the integer of 0-4, and m2+m3 shows the integer of 1-4. In Formula (2-3), m4 and m5 are integers of 1-5, respectively. In Formula (2-4), X ₃ is a C1-C5 linear or branched alkyl group. m6 is an integer of 1-5. 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 of 1-4.

In Formula (2-1), Preferably m1 is an integer of 1-2. In formula (2-2), preferably, X ₂ is 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 both integers of 1. In formula (2-5), Preferably, X ₄ is 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. Especially, the diamine represented by Formula (2-1) is especially preferable.

The following formulas (2-6) - (2-16) are mentioned as a specific example of the diamine represented by Formula (2).

[Formula 7]

[Formula 8]

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 for this invention is a diamine represented by following formula (3).

[Formula 9]

Q< ₁ > represents a C1-C5 alkylene, Preferably, it is a C1-C5 linear alkylene from synthetic|combination simplicity.

Cy is a divalent group representing an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. From the viewpoint of simplicity of synthesis, azetidine, pyrrolidine, or piperidine is preferable. Moreover, the substituent may couple|bond with these ring moieties.

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 it is a hydrogen atom or a C1-C3 linear alkyl group, More preferably, it is a hydrogen atom or a methyl group.

R ₂ and R ₃ are monovalent organic groups. q and r are each independently an integer of 0-4. However, when the sum total of q or r is 2 or more, R< ₂ > and R< ₃ > are each independent. Preferably, from the viewpoint of simplicity of synthesis, R ₂ and R ₃ are methyl groups. Further, the bonding position of the amino group in the benzene ring constituting the diamine is not limited, but the amino group is at the 3-position or 4-position with respect to the nitrogen atom on Cy, respectively, with respect to the nitrogen atom to which Q ₁ and R ₁ are bonded. It is preferably at the 3-position or 4-position, and more preferably at the 4-position with respect to the nitrogen atom on Cy and the 4-position with respect to the nitrogen atom to which Q ₁ and R ₁ are bonded.

[Formula 10]

It is preferable that the diamine represented by the said Formula (3) of this invention is a following formula (3-1) or (3-2).

[Formula 11]

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 formula (3-1) include the following formulas (3-1-1) to (3-1-10), and specific examples represented by the formula (3-2) As examples, the following formulas (3-2-1) to (3-2-4) are mentioned.

[Formula 12]

<Specific diamines 4 to 7>

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 was protected by a Boc group.

[Formula 13]

In formula (4), D represents a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D may have various substituents. m is 1 or 0.

Although the substitution position of the amino group in the formula (4) is not particularly limited, from the viewpoint of synthesis difficulty or reagent availability, the meta or para position is preferable based on the amide bond, and from the viewpoint of liquid crystal orientation, the para position is Especially preferred. Also in aminobenzene having no amino group (i.e. -NHBoc) protected by a Boc group, similarly, the meta or para position is preferable on the basis of the amide bond, and the meta position is preferable from the viewpoint of solubility, and the liquid crystal From the viewpoint of orientation, the position of para is preferable. In addition, hydrogen of aminobenzene having no -NHBoc may be substituted with an organic group or a halogen atom such as fluorine.

D in Formula (4) is not limited, According to structures, such as dicarboxylic acid and tetracarboxylic dianhydride used as a raw material, a structure can be selected variously. As D, a divalent hydrocarbon group is preferable from a soluble viewpoint, and a linear alkylene group, a cyclic alkylene group, etc. are mentioned as a preferable example, This hydrocarbon group may have an unsaturated bond. Moreover, from a viewpoint of liquid-crystal orientation and an electrical characteristic, a bivalent aromatic hydrocarbon group, a heterocyclic ring, etc. are preferable. Although it is preferable that D does not have a substituent from a viewpoint of liquid-crystal orientation, it is preferable that the hydrogen atom is substituted by the carboxylic acid group, a fluorine atom, etc. from a soluble viewpoint.

In formula (5), E is a single bond or a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. F represents a single bond, -O-, -OCO-, or -COO-.

Although the diamine represented by the diamine in case m in Formula (4) is 0 or the diamine represented by Formula (5) is a diamine of an asymmetric structure, preferable D is the same as the above, and preferable E is also the same as said preferable D. Moreover, regarding the diamine represented by Formula (5), the compound whose E and F are both a single bond is also preferable.

In formula (6), A ₁ is at least 1 selected from the group consisting of a single bond, -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO- It is a kind of divalent organic group, or a C1-C3 alkylene group. 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 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. X ⁵ , 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 each independently a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, benzyl group, or 9-fluorenyl group. a is 0 or 1.

As a specific example of the diamine represented by said Formula (4)-(7), the formula chosen from the group which consists of a following formula is mentioned, for example.

[Formula 14]

<Specific diamine 8>

The specific diamine 8 used for this invention is a diamine represented by following formula (8).

[Formula 15]

(In formula (8), R< ₈ > is a hydrogen atom, a C1-C6 alkyl group, a C6-C20 aromatic group, a C7-13 aralkyl group, 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, or t-butyl group. have.

As a C6-C20 aromatic group, a C6-C12 aryl group or another aromatic group is mentioned. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, or 3-chloro- 4-methylphenyl group etc. are mentioned. Examples of the other aromatic group include a 4-pyridinyl group, a 2-phenyl-4-quinolinyl group, a 2-(4'-t-butylphenyl)-4-quinolinyl group, or a 2-(2' -thiophenyl)-4-quinolinyl group etc. are mentioned, respectively.

As a C7-C13 aralkyl group, a benzyl group etc. are mentioned, for example.

X ¹¹ is a single bond, a carbonyl group, or *-CONH- (provided that the bond to which “*” is attached is bonded to the piperidine ring).

Each of R ₆ , R ₇ , R ₉ and R ₁₀ is 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 said aryl group and an aralkyl group may be substituted by the formyl group or a C1-C4 alkoxyl group.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, or t-butyl group; Examples of the aryl group having 6 to 12 carbon atoms (provided that the benzene ring of this aryl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms) is, for example, a phenyl group, a 4-formylphenyl group, or 3,4; 5-trimethoxyphenyl group; Examples of the aralkyl group having 7 to 13 carbon atoms (provided that the benzene ring of the aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms) includes, for example, a benzyl group.

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)- (provided that the bond to which “*” is attached is binds to the peridine ring).

X ¹⁴ is an oxygen atom, *-OCO-, the following formula (X ¹⁴ -1)

[Formula 16]

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

(In the above, the bond to which "*" is attached is bonded to the piperidine ring.), a methylene group, or an alkylene group having 2 to 6 carbon atoms.

As a C2-C6 alkylene group, a 1, 3- propylene group, 1, 6- hexylene group, etc. are mentioned, for example.

It is preferable that the two amino groups couple|bonded with the benzene ring of said formula (8) are at the 2,4 ^- position or 3,5-position with respect to the group X4.

The following formulas (8-1) - formula (8-4) are given as a preferable specific example of diamine represented by Formula (8).

[Formula 17]

<Specific diamine 9>

The specific diamine 9 used for this invention is a diamine represented by said Formula (9).

[Formula 18]

R ₁₁ represents hydrogen or a monovalent organic group. Examples of the monovalent organic group include a group selected from the group consisting of an alkyl group 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. can be heard Preferably, it is a hydrogen atom or a methyl group.

R ₁₂ each independently represents a single bond or a structure represented by the following formula (9-2). Moreover, you may substitute arbitrary hydrogen atoms of a benzene ring with a monovalent organic group.

[Formula 19]

R ₁₃ is selected from the group consisting of a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m O-, -CONH-, and -NHCO- The divalent organic group used is shown (l, m represents the integer of 1-5). * 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 the integer of 1-3. 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 represents the integer of 1-3. Preferably it is 1 or 2.

As a specific example of the diamine represented by said Formula (9), the diamine represented by the following Formula (9-1-1) - Formula (9-1-12) can be illustrated. Among them, from the viewpoint of relaxation of the accumulated charge, formulas (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 preferable, and formulas (9-1-1), (9-1) -2), (9-1-3), (9-1-11), or (9-1-12) is particularly preferable.

[Formula 20]

<Other diamines>

In this invention, other diamines other than a specific diamine can be used together as a part of a diamine component. Although other diamine is not specifically limited, For example, the side chain type diamine described in detail below is mentioned. Side chain diamine is used suitably, when producing the liquid crystal display element of a vertical alignment type.

Specific side chain type diamine is diamine represented by following formula (10).

[Formula 21]

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-. Especially, since a single bond, -(CH2) _a- (a is an integer _of 1-15), -O-, -CH2O-, or COO- is easy to synthesize|combine _a side chain structure, it is preferable. More preferably, they are a single bond, -(CH2) _a- ( _a is an integer _of 1-10), -O-, -CH2O-, or COO-.

Y ² is a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, 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 them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or OCO- is preferable because it is easy to synthesize. More preferably, they are _a single bond, -(CH2) _c- (c is an integer _of 1-10), -O-, -CH2O-, -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 may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine group having 1 to 3 carbon atoms, a fluorine group having 1 to 3 carbon atoms, or a fluorine atom. . ^In addition, Y4 is a C12-C25 divalent organic group which has a steroid skeleton. As Y4, a C12 ^- C25 organic group which has a benzene ring, a cyclohexyl ring, or 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 heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine group having 1 to 3 carbon atoms, a fluorine group having 1 to 3 carbon atoms, or a fluorine atom. .

n is an integer of 0-4. Preferably, it is an integer of 0-2.

^Y6 is a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

m is an integer of 1-4. Preferably, it is an integer of 1.

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

[Formula 22]

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 a C1-C22 alkyl group, an alkoxyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxyl group.

[Formula 23]

In formulas (10-4) to (10-6), R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or CH ₂ - represents. ^R4 is a C1-C22 alkyl group, an alkoxyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxyl group.

[Formula 24]

In formulas (10-7) to (10-8), R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or O-. 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.

[Formula 25]

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

[Formula 26]

In formulas (10-11) to (10-12), R ⁸ is an alkyl group having 3 or more and 12 or less carbon atoms. Each of the cis-trans isomers of 1,4-cyclohexylene is a trans isomer.

[Formula 27]

In Formula (10-13), A4 is a C3 ^- C20 alkyl group which may be substituted by the fluorine atom. A ³ is a 1,4-cyclohexylene group or a 1,4-phenylene group. A ² is an oxygen atom or COO-* (however, the bond to which "*" is attached is bonded to A ³ ). A ¹ is an oxygen atom or COO-* (however, the bond to which "*" is attached is bonded to (CH ₂ )a ₂ ). In addition, a ₁ is an integer of 0 or 1. _a2 is an integer of 2-10. a ₃ is an integer of 0 or 1.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

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

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

[Formula 33]

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

[Formula 34]

In formula, R represents a hydrogen atom or a C1-C4 alkyl group. R ₃ represents -CH ₂ -, -NR-, -O-, or S-.

Specifically, the following diamines are mentioned.

[Formula 35]

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

As another diamine, the diamine of the following formula or the diamine of the 30 pages - 33 pages of international publication 2014/171493 (2014.10.23 publication) is also mentioned.

[Formula 36]

According to characteristics, such as the liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, voltage retention, and accumulated electric charge, said other diamine can also be used 1 type or in mixture of 2 or more types.

<Tetracarboxylic dianhydride component>

Although limitation in particular is not carried out as for the tetracarboxylic dianhydride used as a raw material for the polymer contained in the liquid crystal aligning agent used for this invention, Tetracarboxylic dianhydride represented by following formula (12)-(14) (specific tetra It is also preferable to use carboxylic dianhydride).

[Formula 37]

In Formula (12), Z< ¹ > is a C4-C13 tetravalent organic group, and contains a C4-C10 non-aromatic cyclic hydrocarbon group.

Specifically, it is a group represented by the following formulas (12a) to (12j).

[Formula 38]

In 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 formula (6g), Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group.

In formula (12), particularly preferable Z ¹ is a formula (12a), a formula (12c), a formula (12d), a formula (12e), a formula (12f), or a formula (12g) from the viewpoint of polymerization reactivity and synthesis easiness.

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 dianhydride, tetracarboxylic dianhydride represented by the following formulas (12-1) - (12-5) is preferable, Especially, the viewpoint of the residual image (accumulated electric charge) of the liquid crystal display element obtained In , (12-1), (12-3) or (12-5) is preferable.

[Formula 39]

<Other tetracarboxylic dianhydride>

In this invention, other tetracarboxylic dianhydride other than specific tetracarboxylic dianhydride can be used. As other tetracarboxylic dianhydride, tetracarboxylic dianhydride of tetracarboxylic acid shown below is mentioned.

2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7- Anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3 ,3',4,4'-benzophenonetetracarboxylic 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)di phenylsilane, 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.

According to characteristics, such as the liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, voltage retention, and accumulated electric charge, said other tetracarboxylic dianhydride can be used 1 type or in mixture of 2 or more types.

The liquid crystal aligning agent of this invention may contain components other than a specific polymer component further. As such an additional component, at least selected from the following formulas (17), (19) and (21) for increasing the strength of the adhesion aid for increasing the adhesion between the liquid crystal aligning film and the substrate or the adhesion between the liquid crystal aligning film and the sealing material, and the liquid crystal aligning film One crosslinking agent, the dielectric constant for adjusting the dielectric constant and electric resistance of a liquid crystal aligning film, an electrically-conductive substance, an organic solvent, etc. are mentioned. Specific examples of these additional components are as variously disclosed in known documents related to liquid crystal aligning agents, and are disclosed on page 53 to page 55 of International Publication No. 2015/060357 ingredients, and the like.

[Formula 40]

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 group represented by the formula (18). R ₂₂ and R ₂₄ each independently represent an aromatic ring, and an arbitrary hydrogen atom in 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, or vinyl. You may be substituted by group. R ₂₃ is a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms which may be combined in whole or in part to form a cyclic structure.

[Formula 41]

In 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 may have a substituent. In addition, at least one of R ₂₈ and R ₂₉ has a hydroxyl group as a substituent. Moreover, it is preferable that at least 1 of _R28 and R29 is substituted by the group represented by Formula ( ₂₀ ). In formula (20), R ₃₀ to R ₃₃ are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.

[Formula 42]

In 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, and any of the aromatic rings The hydrogen atom of may be substituted with a hydroxyl group, a C1-C3 alkyl group, a halogen atom, a C1-C3 alkoxy group, or a vinyl group. R ₃₆ is a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms which may be combined in whole or in part to form a cyclic structure, -NH-, -N ( CH ₃ )- or a group represented by the formula (22). In Formula (22), P< ₁ > and P< ₂ > are each independently a C1-C5 alkyl group, and Q< ₁ > represents an aromatic ring. In the formula (21), d and f each independently represent an integer of 1-3, and e and g each independently represent an integer of 1-3.

The following three are mentioned as a specific example of the compound represented by said Formula (17)-(22).

[Formula 43]

<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 - 42 of international publication 2014/171493 (2014.10.23 publication) is mentioned.

<Liquid crystal aligning agent>

The specific polymer which the whole uses for this invention may be sufficient as the polymer component in the liquid crystal aligning agent of this invention, and other polymers other than that may be mixed with the specific polymer of this invention. In that case, content of other polymers other than that with respect to a specific polymer is 0.5-15 mass %, Preferably it is 1-10 mass %.

As another polymer other than that, the polyimide which imidated the polyimide precursor obtained from the diamine component which consists of diamines other than a specific diamine, and tetracarboxylic dianhydride component, or this polyimide precursor is mentioned. Furthermore, as another polymer other than that, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, etc. are mentioned.

It is preferable that content of an organic solvent is 70-99 mass % from a viewpoint of the organic solvent in the liquid crystal aligning agent of this invention forming a uniform polymer film by application|coating. This content can be suitably changed according to the film thickness of the liquid crystal aligning film made into the objective. As an organic solvent in that case, if it is an organic solvent in which the specific polymer mentioned above is dissolved, it will not specifically limit. More specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyr Rollidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethylamylketone, methyl and 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 may be used independently and may be mixed and used for them.

The liquid crystal aligning agent of the present invention is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group, or polymerization It may contain the crosslinking|crosslinked compound etc. which have a sexually unsaturated bond.

Moreover, as a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, or a nonionic surfactant, etc. may be contained, As a compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, You may make it contain a functional silane containing compound or an epoxy group containing compound.

Moreover, you may add the dielectric material and electrically-conductive substance of the objective of changing electrical characteristics, such as the dielectric constant and electroconductivity of a liquid crystal aligning film.

The liquid crystal aligning agent of this invention can contain the organic solvent (it is also mentioned a poor solvent) or compound which improves the uniformity of the film thickness of a polymer film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness. Furthermore, you may contain the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate.

The following specific examples are given as a poor solvent which improves the uniformity of a 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 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, 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-methyl Ethyl oxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutyl propionate, 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-2- Low surface tension such as acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate ester, ethyl lactate ester, lactic acid n-propyl ester, lactic acid n-butyl ester, or lactic acid isoamyl ester organic solvents with can

One type may be sufficient as these poor solvents, and multiple may be mixed and used for it. When using the above poor solvents, it is preferable that it is 5-80 mass % of the whole organic solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass %.

<LCD>

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

Also, in the vertically aligned liquid crystal display device, a nematic liquid crystal having negative dielectric anisotropy may be used. For example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a Schiff-based liquid crystal, an azoxy-based liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal, or a terphenyl-based liquid crystal may be used. Moreover, an alkenyl-type liquid crystal can also be used together. As such an alkenyl-type liquid crystal, a conventionally well-known thing can be used. For example, the compound etc. which are represented by a following formula are mentioned.

[Formula 44]

<Liquid crystal alignment film, liquid crystal display element>

After apply|coating and baking the liquid crystal aligning agent of this invention on a BOA substrate or a board|substrate with BCS, it can orientate-process by a rubbing process, light irradiation, etc., and can use it as a liquid crystal aligning film. Moreover, in the case of a vertical alignment use etc., it can use as a liquid crystal aligning film without an orientation process.

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

Moreover, the board|substrate with BCS is a board|substrate in which the black column spacer was formed using the black colored resin composition as a column spacer material supporting between an array board|substrate and a counter board|substrate, The said black matrix material was used for this black colored resin composition, also be

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

It will not specifically limit as a transparent substrate used at this time, if it is a board|substrate with high transparency, A glass substrate, plastic substrates, such as an acrylic substrate or a polycarbonate substrate, etc. can be used. From a viewpoint of process simplification, it is preferable to use the board|substrate with which the ITO electrode etc. for a liquid crystal drive were formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used as long as it is only a one-sided substrate, and a light-reflecting material such as aluminum can be used as the electrode in this case.

Although the application method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet, etc. is common. As another coating method, there exist a dip, a roll coater, a slit coater, a spinner, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on a BOA board|substrate or a board|substrate with BCS, it is 50-300 degreeC with heating means, such as a hotplate, Preferably a solvent is evaporated at 80-250 degreeC, and it can be set as a polymer film. When the thickness of the polymer film after firing is too thick, it becomes disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease, so preferably 5 to 300 nm, more preferably is 10 to 100 nm. When a liquid crystal is horizontally or diagonally aligned, the polymer film after baking is processed by rubbing, polarization|polarized-light ultraviolet irradiation, etc.

In addition, in a vertically aligned liquid crystal display device, a photopolymerizable compound is added in advance to a liquid crystal composition, used together with a vertical alignment film such as polyimide, and irradiated with ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell, polymerization Polymer sustained alignment (PSA) elements capable of controlling the alignment of liquid crystals and improving the response speed of liquid crystals are known by polymerizing the active compound, and are reported by Japanese Patent Application Laid-Open No. 2003-307720 or the like.

As a polymeric compound, the compound which has 1 or more polymerizable unsaturated groups, such as an acrylate group and a methacrylate group, in a molecule|numerator is mentioned. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid crystal component, More preferably, it is 0.1-5 mass parts. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the orientation of the liquid crystal cannot be controlled. this is lowered

On the other hand, by adding a photopolymerizable compound not in a liquid crystal composition but in a liquid crystal aligning film, the response speed of a liquid crystal display element becomes quick (SC-PVA type liquid crystal display) K. Hanaoka, SID 04 DIGEST, P.1200- It is reported by non-patent literature such as 1202.

Example

Hereinafter, it will be described in more detail based on Examples, but the present invention is not limited by these Examples at all.

The abbreviation is as follows.

(acid dianhydride)

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, PMDA: pyro Melitic acid dianhydride, TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-2 anhydride

(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

[Formula 45]

[Formula 46]

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

[Formula 47]

The photosensitive diamine represented by the following formula DA-1

[Formula 48]

<solvent>

NMP: N-methyl-2-pyrrolidone, BC: butyl cellosolve

<Additives>

3AMP: 3-picolylamine

<Crosslinking agent>

A crosslinking agent represented by the following formulas CL-1 to CL-3

[Formula 49]

(Conditions for measuring molecular weight of polyimide)

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific, Column: Column (KD-803, KD-805) manufactured by Shodex, Column temperature: 50°C, Eluent: N,N'-dimethyl formamide (as an additive, lithium bromide monohydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystals (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) is 10 mL/L), Flow rate: 1.0 ml/min, standard sample for calibration curve preparation: TSK standard polyethylene oxide manufactured by Tosoh (molecular weights about 9000,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratories (molecular weights about 12,000, 4,000, 1,000).

(Imidation rate of polyimide)

20 mg of polyimide powder is put into an NMR sample tube (NMR sampling tube standard _φ5 manufactured by Kusano Science Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) is added, ultrasonic waves are applied to complete dissolved. Proton NMR of 500 MHz was measured for this solution with the NMR measuring machine (JNW-ECA500) by the JEOL datum company. The imidation rate determines a proton derived from a structure that does not change before and after imidization as a reference proton, and the integrated peak of this proton and the integrated value of the proton peak derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm. It was used and calculated|required by the following formula|equation. In addition, in the following formula, x is the proton peak integrated value derived from the NH group of an amic acid, y is the peak integrated value of a reference proton, α is NH of the amic acid in the case of a polyamic acid (imidation rate is 0%) It is the ratio of the number of reference protons to one proton of the group.

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 after reacting at 80° C. for 5 hours, CBDA ( 4.71 g, 24.0 mmol) and NMP (47.2 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (43.1g) and pyridine (13.4g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained 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 (44.0g) was added to the obtained polyimide powder (A) (6.0g), and it stirred at 70 degreeC for 20 hours, and made it melt|dissolve. 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 dissolved in NMP (113.8 g), After reacting at 60° C. for 3 hours, CBDA (11.37 g, 58.0 mmol) and NMP (26.3 g) were added and reacted at 40° C. for 1 hour, PMDA (4.36 g, 20.0 mmol) and NMP (35.00 g) were added After addition, it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (46.3g) and pyridine (14.3g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained 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.

Using the obtained polyimide powder (B) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (B1).

(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 dissolved in NMP (118.3 g), After reacting at 60°C for 3 hours, CBDA (11.37 g, 58.0 mmol) and NMP (27.3 g) were added and reacted at 40°C for 1 hour, PMDA (4.36 g, 20.0 mmol) and NMP (36.41 g) were added After addition, it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (44.5g) and pyridine (13.8g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (C). The imidation ratio of this polyimide was 79 %, the number average molecular weight was 21000, and the weight average molecular weight was 49000.

Using the obtained polyimide powder (C) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (C1).

(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), It was made to react at 60 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (37.6g) and pyridine (11.6g) were added as an imidation catalyst, and it was made to react at 110 degreeC for 4 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained 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.

Using the obtained polyimide powder (D) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (D1).

(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 dissolved in NMP (171.9 g), After making it react at 80 degreeC for 5 hours, CBDA (4.71 g, 24.0 mmol) and NMP (57.32 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (35.5g) and pyridine (11.0g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained 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.

Using the obtained polyimide powder (E) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (E5).

(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) and reacted at 80°C for 5 hours, CBDA (4.12 g, 21.0 mmol) and NMP (52.46 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (38.8g) and pyridine (12.0g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (F). The imidation ratio of this polyimide was 57 %, the number average molecular weight was 10000, and the weight average molecular weight was 24000.

Using the obtained polyimide powder (F) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (F1).

(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 dissolved in NMP (166.6 g), After making it react at 60 degreeC for 3 hours, CBDA (9.51 g, 48.5 mmol) and NMP (41.11 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (180g) and diluting to 6.5 mass %, acetic anhydride (36.6g) and pyridine (11.4g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 2 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 80 degreeC, and obtained polyimide powder (G). The imidation ratio of this polyimide was 73 %, the number average molecular weight was 17000, and the weight average molecular weight was 38000.

Using the obtained polyimide powder (G) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (G1).

(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) and reacted at 60° 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 it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (35.3g) and pyridine (10.9g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained 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 48000.

Using the obtained polyimide powder (H) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (H1).

(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), and after reacting at 60 ° C. for 3 hours, BDA ( 9.41 g, 48.0 mmol) and NMP (37.7 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (200g) and diluting to 6.5 mass %, acetic anhydride (43.7g) and pyridine (13.5g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 2 hours. This reaction solution was thrown into methanol (2700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained 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.

Using the obtained polyimide powder (I) (6.0 g), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (I1).

(Synthesis Example 8)

The liquid crystal aligning agent (H1) obtained by the comparative synthesis example 1 is mixed with 6.0 g as a 1st component, and 14.0 g of the liquid crystal aligning agent (C1) obtained by the synthesis example 3 is mixed as a 2nd component, and by stirring for 1 hour, a liquid crystal aligning agent ( J1) was prepared.

(Synthesis Example 9)

The liquid crystal aligning agent (I1) obtained in the comparative synthesis example 2 is mixed with 6.0 g as a 1st component, and 14.0 g of the liquid crystal aligning agent (C1) obtained by the synthesis example 3 is mixed as a 2nd component, and by stirring for 1 hour, a liquid crystal aligning agent ( K1) was prepared.

(Synthesis Example 10)

A liquid crystal aligning agent (A2) was prepared by adding CL-2 with respect to 10.0 g of liquid crystal aligning agents (A1) obtained by the synthesis example 1 so that it might become 10 wt% of a resin component, and stirring at room temperature for 1 hour.

(Synthesis Example 11)

A liquid crystal aligning agent (D2) was prepared by adding CL-1 with respect to 10.0 g of liquid crystal aligning agents (D1) obtained by the synthesis example 4 so that it might become 10 wt% of a resin component, and stirring at room temperature for 1 hour.

(Synthesis Example 12)

The liquid crystal aligning agent (K2) was prepared by adding CL-3 with respect to 10.0 g of liquid crystal aligning agents (K1) obtained by the synthesis example 9 so that it might become 10 wt% of a resin component, and stirring at room temperature for 1 hour.

(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) and reacted at 60° C. for 3 hours, CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 mass %, acetic anhydride (6.68g) and pyridine (2.07g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (461 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 60 degreeC, and obtained 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), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (L1).

(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 reacted at 60° C. for 3 hours, CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (40g) and diluting to 6.5 mass %, acetic anhydride (6.99g) and pyridine (2.17g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (463 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 60 degreeC, and obtained 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), it carried out similarly to the synthesis example 1, and obtained the liquid crystal aligning agent (M1).

(Example 1)

The liquid crystal cell was produced using the liquid crystal aligning agent (A1) obtained by the synthesis example 1 according to the following procedures, and the measurement of a pretilt angle and the measurement of voltage retention were performed.

<Preparation of colored resin composition>

The colored resin composition (a) for black column spacers (BCS) used in the present invention is a resin composition used also as a black matrix material, and is a resist (VI) described in "0312" to "0314" of JP 2014-67028 A. It was prepared in the same manner as

<Production of ITO board with BCS>

The above-mentioned colored resin composition (a) was applied to a glass substrate with an ITO electrode in which an ITO electrode pattern having a pixel size of 100 µm × 300 µm and a line/space of 5 µm/5 µm was formed, and the film thickness after baking was 4 It applied by spin coating so that it might become micrometer. Then, after drying for 60 second with a vacuum dryer, it was made to dry for 2 minutes with a 110 degreeC hotplate, and the pre-exposure board|substrate with a colored resin composition (a) was obtained.

This pre-exposure substrate was exposed at 50 mJ/cm 2 using an ultra-high 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%. Then, this board|substrate with resist (VI) was baked at 230 degreeC for 30 minute(s) using hot-air circulation oven, and the ITO board|substrate with BCS was obtained.

<Production of liquid crystal cell>

The liquid crystal cell was produced in the procedure as shown below using the liquid crystal aligning agent (A1). After spin-coating a liquid crystal aligning agent (A1) to the ITO surface of an ITO board|substrate with BCS and drying it for 90 second with an 80 degreeC hotplate, 200 degreeC hot-air circulation type oven bakes for 30 minutes, and film thickness 100 A nanometer liquid crystal aligning film was formed.

Moreover, after spin-coating a liquid crystal aligning agent (A1) on the ITO surface in which the electrode pattern is not formed and drying it for 90 second with an 80 degreeC hotplate, 200 degreeC hot-air circulation type oven performs baking for 30 minutes, The liquid crystal aligning film with a film thickness of 100 nm was formed.

With respect to the said board|substrate of 2 sheets, the thermosetting sealing compound (XN-1500T by Kyoritsu Chemical Corporation) was printed on the liquid crystal aligning film of one board|substrate. Next, after turning inside the surface on the side in which the liquid crystal aligning film of the other board|substrate was formed and bonding with the former board|substrate, the sealing compound was hardened and the empty cell was produced. A liquid crystal cell containing a polymerizable compound for PSA MLC-3023 (trade name by Merck Corporation, alkenyl-based liquid crystal) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. The voltage retention (VHR) of this liquid crystal cell was measured.

Next, in the state which applied the DC voltage of 15V to this liquid crystal cell, 10 J/cm<2> irradiation (it is also called primary PSA process) was carried out with UV which passed a 365 nm band pass filter from the outer side of this liquid crystal cell. In addition, UV illuminance was measured using UV-MO3A (attachment: UV-35) by ORC. Thereafter, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A) was used in a state where no voltage was applied using a UV-FL irradiation device manufactured by Toshiba Lightec. -1) was irradiated (also referred to as secondary PSA treatment) for 30 minutes. Then, with respect to the cell after UV irradiation, the measurement of the pretilt angle of a pixel part, and the measurement of voltage retention were performed.

"Measurement of pretilt angle"

It measured using LCD analyzer LCA-LUV42A (made by Meiryo Technica).

"Evaluation of voltage retention"

The voltage of 1V was applied for 60 microseconds in 60 degreeC hot-air circulation oven, the voltage 1667 msec after that was measured and how much the voltage was maintained was calculated as voltage retention. For the measurement of the voltage retention, VHR-1 manufactured by Toyo Technica Corporation was used.

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

Except having changed the liquid crystal aligning agent (A1) used in Example 1 into liquid crystal aligning agents (B1) - (M1), (A2), (D2) or (K2), it carried out operation similar to Example 1, and The measurement of the tilt angle and the measurement of the voltage retention were performed.

(Example 1')

By operation similar to Example 1, the liquid crystal cell was created using the board|substrate with ITO electrode to which BCS is not affixed, and the pretilt angle and voltage retention were measured. In addition, in order to maintain the cell gap, a 4 μm bead spacer was used instead of the black column spacer and spread on the liquid crystal alignment layer.

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

Except having changed the liquid crystal aligning agent (A1) used in Example 1' into liquid crystal aligning agents (B1) - (M1), (A2), (D2) or (K2), the same operation as Example 1' was performed, , the measurement of the pretilt angle and the measurement of the voltage retention were performed.

As shown above, Examples 1 to 7, 13, and 14 and Examples 1' to 7', 13', and 14' were compared with Comparative Examples 1 and 2 and Comparative Examples 1' and 2', and the substrates with BCS were It was confirmed that even when used, high VHR characteristics were exhibited.

Further, as can be seen from Examples 8 and 9, 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. It was confirmed that high VHR characteristics can also be expressed by this. In addition, as shown in Examples 10 to 12 and Examples 10' to 12', even when a BCS-attached substrate is used, even when a crosslinking agent is added to a polymer exhibiting high VHR characteristics, the same high VHR characteristics as when not added are expressed. It has been confirmed that

In addition, the specification of Japanese Patent Application No. 2016-118281 for which it applied on June 14, 2016, a claim, and the abstract are referred here, and it takes in as an indication of this specification.

Claims (12)

The polyimide precursor obtained by making the diamine component containing at least 1 diamine selected from the group which consists of diamine of following formula (1) and (3)-(8), and tetracarboxylic dianhydride component react, and its polyimide precursor The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS containing the at least 1 sort(s) of polymer chosen from the group which consists of polyimide which imidated.

(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. X ³ is an alkyl group having 1 to 5 carbon atoms. It is a 5-membered ring or 6-membered aromatic heterocyclic ring containing 1 or 2 nitrogen atoms which may be substituted with. n is an integer of 1-4.)

(In formula (3), Q ₁ represents alkylene having 1 to 5 carbon atoms. Cy represents an aliphatic heterocyclic ring selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. It is a divalent group, and the substituent may be bonded to these ring moieties.Q ₂ represents the structure of the following formula (3-I) or (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 represents a monovalent It is an organic group. 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 each independent.)

(In 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 may have various substituents. m is 1 or 0 to be.
In formula (5), E is a single bond or a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. F represents a single bond, -O-, -OCO-, or COO-.
In formula (6), A ₁ is at least one selected from the group consisting of a single bond, -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and OCO- 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. 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 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. X ⁵ , 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, each 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, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, benzyl group, or 9-fluorenyl group. a is 0 or 1.)

(In formula (8), R< ⁸ > is a hydrogen atom, a C1-C6 alkyl group, a C6-C20 aromatic group, a C7-C13 alkyl group, or a 1, 3- dioxobutyl group.
X ¹¹ is a single bond, a carbonyl group, or *-CONH- (provided that the bond to which “*” is attached 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 group and the aralkyl group have The benzene ring 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 that “*” is attached to the bond It binds to the piperidine ring).
X ¹⁴ is each independently -O-, *-OCO-, a group represented by the following formula (X ¹⁴ -1) (provided that the bond to which "*" is attached is a piperidine ring in formula (8) ), a methylene group or an alkylene group having 2 to 6 carbon atoms.)

(In formula (X ¹⁴ -1), a is an integer of 1 to 12. b is an integer of 0 to 5.) The method of claim 1,
The liquid crystal aligning agent for BOA board|substrate or board|substrate with BCS application|coating in which the said diamine component contains the diamine represented by 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-.
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, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. Arbitrary hydrogen atoms on these cyclic groups may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. .
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 may be substituted with 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. .
n is an integer of 0-4.
^Y6 is a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group.
m is an integer of 1-4.)

(In 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 a hydrogen atom may be substituted with a halogen atom.
R ₁ and R ₂ each independently represent an alkyl group, alkoxy group, benzyl group, or phenethyl group having 1 to 10 carbon atoms, and in the case of an alkyl group or an alkoxy group, R ₁ , R ₂ may form a ring.
T ₁ , 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 or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms (provided that -CH ₂ - or CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-; When any of the following groups are not adjacent to each other, these groups may be substituted with: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a divalent heterocyclic ring.).
Q represents the following structure.

(Wherein, R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ represents -CH ₂ -, -NR-, -O- or S-.) 3. The method of claim 2,
The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS whose Y< ⁴ > is a C12-C25 organic group which has a benzene ring, a cyclohexyl ring, or steroid skeleton in Formula (10). The method of claim 1,
The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS whose said tetracarboxylic dianhydride component is at least 1 piece(s) of tetracarboxylic dianhydride chosen from the group which consists of following formula (12)-(14).

(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 (14), j and k is each independently 0 or 1. X and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.) The method of claim 1,
The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS in which the said liquid crystal aligning agent contains polymers other than the polyimide which imidated polymers other than the said polyimide precursor, or this polyimide precursor. The method of claim 1,
The liquid crystal aligning agent, the liquid crystal aligning agent for application to a BOA substrate or a substrate with BCS, further comprising at least one selected from the group consisting of an adhesion aid, a crosslinking agent, a dielectric, a conductive material, and an organic solvent. 7. The method of claim 6,
The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS whose said crosslinking agent is an at least 1 compound chosen from 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 alkyl group having 2 to 4 carbon atoms. It is a nyl group, and at least one is a group represented by Formula (18). R ₂₂ and R ₂₄ each independently represent an aromatic ring, and an arbitrary hydrogen atom of the aromatic ring is a hydroxyl group and a C1-C3 group. It may be substituted with an alkyl group, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group, R ₂₃ is a single bond or saturated having 1 to 10 carbon atoms which may be combined in whole or in part to form a cyclic structure. It is a hydrocarbon group, where a is 1 and b is 1.)

(In 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 is 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. In addition, at least one of R ₂₈ and R ₂₉ is , has a hydroxyl group as a substituent.)

(In 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 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, It is a saturated hydrocarbon group having 1 to 10 carbon atoms which may form a cyclic structure and is a group represented by -NH-, -N(CH ₃ )- or formula (22), in which any hydrogen atom may be substituted with a fluorine atom. 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 1 to It is an integer of 3, and e and g are each independently an integer of 1 to 3.) 8. The method of claim 7,
In Formula (19), the liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS by which at least 1 of _R28 and R29 is substituted by group represented by following formula ( ₂₀ ).

(In formula (20), R ₃₀ to R ₃₃ are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.) 8. The method of claim 7,
The liquid crystal aligning agent for BOA board|substrate or board|substrate application|coating with BCS whose said crosslinking agent is at least 1 compound chosen from the group which consists of following formula CL-1 - CL-3.

A liquid crystal display element provided with the BOA board|substrate or board|substrate with BCS in which the liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-9 was formed. The manufacturing method of the liquid crystal aligning film on the BOA board|substrate or board|substrate with BCS which apply|coats the liquid crystal aligning agent in any one of Claims 1-9 to a BOA board|substrate or a board|substrate with BCS. A board|substrate for liquid crystal display elements provided with the board|substrate with BOA board|substrate or BCS, and the liquid crystal aligning film formed on the said BOA board|substrate or board|substrate with BCS using the liquid crystal aligning agent in any one of Claims 1-9.