KR20190019133A - A liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS and a liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS, and a liquid crystal display element comprising a BOA substrate or a BCS-attached substrate having a good display quality obtained by using the liquid crystal aligning agent.
A polyimide precursor obtained by reacting a diamine component containing a diamine containing a nitrogen or carboxylic acid group and a tetracarboxylic acid dianhydride component in a structure other than two amino groups and a polyimide precursor obtained by imidizing the polyimide precursor A liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS containing at least one kind of polymer selected from the group consisting of BOA substrates or BCS substrates with a liquid crystal alignment film obtained therefrom.

Description

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

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

Generally, a liquid crystal display element includes an array substrate on which thin film transistors are formed, and a liquid crystal layer interposed between the array substrate and the counter substrate, including a counter substrate on which a color filter is formed facing the array substrate. For the purpose of increasing the contrast and coloring effect, a black matrix is required at the boundary portion between coloring layers such as red, green and blue. Recently, there has been proposed a color filter-on-array (COA) in which a color filter is formed on an array substrate from a manufacturing yield or the like, a black matrix on- An array (BOA: black matrix on array) substrate has been developed.

An attempt has been made to use a black colored resin composition as a column spacer material for supporting between an array substrate and a counter substrate from such a relationship as to a better manufacturing yield and the like (such a column spacer is referred to as a black column spacer (BCS: Black Colum Spacer), and the black matrix material may be used for the black colored resin composition.

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

Due to the structure of the BOA substrate, it is difficult to ensure reliability when the liquid crystal display element is manufactured as compared with the COA substrate, and the display quality of the liquid crystal display element may be poor. In addition, by using a BCS-attached substrate, the above problem becomes more significant.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS, and a liquid crystal aligning agent having a BOA substrate or a BCS-attached substrate having good display quality obtained using the liquid crystal aligning agent. And to provide a display device.

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

That is, the present invention has the following points.

1. A polyimide precursor obtained by reacting a diamine component containing a diamine or a carboxylic acid group-containing diamine component with a tetracarboxylic acid dianhydride component in a structure other than two amino groups, and a polyimide precursor obtained by imidizing the polyimide precursor A liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS, wherein the liquid crystal aligning agent contains at least one kind of polymer selected from the group consisting of:

2. The liquid crystal aligning agent according to the above 1, wherein the diamine has at least one structure selected from the group consisting of the following formulas as a partial structure.

[Chemical 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 portions.) R ₁₄ Is a hydrogen atom, a single bond, a carbonyl group or * -CONH- (provided that the bond to which * is attached is a bond to a piperidine ring), R ₁₅ represents hydrogen or a monovalent organic group, R ₁₈ and And R < ₁₉ > are each independently a hydrogen atom or a single bond.

3. The liquid crystal aligning agent according to 1 or 2 above, wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulas (1) to (9).

4. The liquid crystal aligning agent according to any one of items 1 to 3, wherein the diamine component comprises a diamine represented by the following formula (10) or (11).

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

6. The liquid crystal aligning agent according to any one of items 1 to 5, wherein the liquid crystal aligning agent comprises a polymer other than the polyimide precursor or a polymer other than polyimide in which the polyimide precursor is imidized.

7. The liquid crystal aligning agent according to any one of the above items 1 to 6, further comprising at least one selected from the group consisting of the liquid crystal aligning agent, the adhesion auxiliary agent, the crosslinking agent, the dielectric substance, the conductive substance and the organic solvent.

8. The liquid crystal aligning agent according to 7 above, wherein the crosslinking agent is at least one compound selected from the following formulas (17), (19) and (21)

9. The liquid crystal aligning agent according to the above 8, wherein the crosslinking agent is at least one compound selected from the group consisting of the following formulas CL-1 to CL-3.

10. A liquid crystal display element comprising a BOA substrate or a BCS-attached substrate on which a liquid crystal alignment film obtained from the liquid crystal aligning agent described in any one of 1 to 9 above is formed.

11. A method for producing a liquid crystal alignment film on a BOA substrate or a BCS-attached substrate, wherein the liquid crystal aligning agent described in any one of 1 to 9 above is applied to a BOA substrate.

12. A liquid crystal display element substrate comprising a BOA substrate or a BCS-attached substrate and a liquid crystal alignment layer formed on the BOA substrate or the BCS-attached substrate using the liquid crystal aligning agent for coating the BOA substrate described in any one of the above 1 to 9 .

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

The liquid crystal aligning agent of the present invention is obtained by reacting a diamine component containing a diamine or a carboxylic acid group in a structure other than two amino groups (hereinafter, also referred to as a specific diamine) and a tetracarboxylic acid dianhydride component (Hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor obtained by polymerizing a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor Jay. The liquid crystal display element of the present invention is a liquid crystal display element comprising a BOA substrate or a BCS-attached substrate on which a liquid crystal alignment film obtained from the liquid crystal aligning agent is formed.

<Diamines Containing Nitrogen or Carboxylic Acid Groups in Structures other than the Two Amino Groups>

The diamine having a nitrogen or carboxylic acid group in the structure other than the two amino groups means a diamine structure in which at least one selected from the group consisting of the following formulas is a partial structure in the structure other than the structure in which two amino groups are bonded Lt; / RTI &gt; The structure of the following formula is preferably monovalent or divalent, and can be bonded to a structure in which two amino groups are bonded at arbitrary positions.

(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 bonded bonds with 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.

Specifically, a diamine component containing at least one diamine selected from diamines represented by the following formulas (1) to (9) (hereinafter, also referred to as specific diamines 1 to 9) and a tetracarboxylic acid dianhydride component A BOA substrate or a BCS-attached substrate having a liquid crystal alignment film formed from a liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor As shown in Fig.

&Lt; Specific diamine 1 >

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

(3)

In formula (1), X ¹ represents a single bond, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, , -CON (CH ₃₎ - or N (CH ₃₎ CO- is. Among them, -O-, -COO-, -NH-, -CONH-, -NHCO-, -CON (CH ₃ ) -, -CH ₂ O- or OCO- are preferable because diamine is easy to synthesize. Particularly preferably, it is -O-, -CO-, -NH-, -CONH-, -NHCO-, -CON (CH ₃ ) - or CH ₂ O-.

X ² is a non-aromatic heterocyclic ring containing an alkyl group or a nitrogen atom of 1 to 5 carbon atoms. When X ² is an alkyl group of 1 to 5 carbon atoms, the alkyl group may be linear or branched. In particular, the alkyl group preferably has 1 to 3 carbon atoms. Examples of the case where X ² is a nonaromatic heterocyclic ring containing a nitrogen atom include a pyrrolidine ring, a piperidine ring, a piperazine ring, a pyrazolidine ring, a quinuclidine ring or an imidazolidine ring, . Particularly, it is preferable that the non-aromatic heterocyclic ring is a five-membered ring or a six-membered ring because a good alignment property is obtained when the liquid crystal alignment film is used. In the case where the non-aromatic heterocyclic ring contains two nitrogen atoms, in the case of a liquid crystal display device, ionic impurities in the liquid crystal are adsorbed at the liquid crystal alignment film interface and good electric characteristics of the liquid crystal display element are maintained desirable.

From the above viewpoint, as the non-aromatic heterocyclic ring containing a nitrogen atom, a piperazine ring is particularly preferable. When X &lt; ² &gt; is bonded to the nitrogen atom in X &lt; ³ &gt; or the carbon atom adjacent to the nitrogen atom, the effect of accelerating the relaxation of the residual charge accumulated by the DC voltage when the liquid crystal display element is formed is excellent .

X ³ is a five-membered or six-membered aromatic heterocyclic ring containing one or two nitrogen atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms. Examples of the aromatic heterocyclic ring of a five-membered ring or a six-membered 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 pyridazine ring . Among them, a pyridine ring, an imidazole ring, a pyrazine ring or a pyrimidine ring is preferable. Further, when the aromatic heterocyclic ring in X &lt; ³ &gt; is substituted with an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms.

n is an integer of 1 to 4; Among them, an integer of 1 or 2 is preferable.

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

[Chemical Formula 4]

&Lt; Specific diamine 2 >

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

[Chemical Formula 5]

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

[Chemical Formula 6]

In the formula (2-1), m1 is an integer of 1 to 4. Equation (2-2) of, 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₎ - a, or -N (CH ₃₎ CO-. m2 and m3 each represent an integer of 0 to 4, and m2 + m3 represents an integer of 1 to 4. In the formula (2-3), m4 and m5 are an integer 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 of 1 to 5; Equation (2-5) of, X ₄ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, - O-, -CO-, -NH-, -N ( CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH ₃₎ - a, or -N (CH ₃₎ CO-. m7 is an integer of 1 to 4;

In the formula (2-1), m1 is preferably an integer of 1 to 2. Equation (2-2) of, preferably, X ₂ is a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -O-, -CO-, -NH- , -N (CH ₃₎ -, and -CONH-, -NHCO-, -COO-, or -OCO-, m2 and m3 is an integer of 1 all. 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 m 7 is an integer of 1 to 2. Among them, a diamine represented by the formula (2-1) is particularly preferable.

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

(7)

[Chemical Formula 8]

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

&Lt; Specific diamine 3 >

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

[Chemical Formula 9]

Q ₁ represents an alkylene of 1 to 5 carbon atoms, preferably a linear alkylene of 1 to 5 carbon atoms for simplicity of synthesis.

Cy is a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine. From the simplicity of the synthesis, azetidine, pyrrolidine, or piperidine is preferred. A substituent may be bonded to these ring portions.

Q ₂ represents the structure represented by the following formula (3-I) or (3-II). * 1 in the formula (3-I) or (3-II) represents a bond with Q ₁ . * 2 represents a bond with a benzene ring. R ₁ in the formula (3-II) represents hydrogen or a monovalent organic group, preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ₂ and R ₃ are monovalent organic groups. q and r each independently represent an integer of 0 to 4; Provided that when q or r is 2 or more, R ₂ and R ₃ are independent of each other. Preferably, from the simplicity of synthesis, R ₂ and R ₃ are methyl groups. The bonding position of the amino group in the benzene ring constituting the diamine is not limited, but the 3-position amino group relative to a nitrogen atom in the Cy, respectively, or the 4-position, relative to the nitrogen atom is bonded Q ₁ and R ₁ 3 position or 4 position, more preferably at the 4-position to the nitrogen atom on the Cy-atom, and at the 4-position to the nitrogen atom to which Q ₁ and R ₁ bond.

[Chemical formula 10]

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

(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 straight chain alkylene of 1 to 5 carbon atoms.

Specific examples of the formula (3-1) include, for example, the following formulas (3-1-1) to (3-1-10) For example, the following formulas (3-2-1) to (3-2-4).

[Chemical Formula 12]

&Lt; Specific diamine 4-7 >

Specific diamines 4 to 7 used in the present invention are diamines represented by the following formulas (4) to (7) in which the amino group is protected with a Boc group.

[Chemical Formula 13]

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

The substitution position of the amino group in the formula (4) is not particularly limited, but from the viewpoint of the synthetic degree of difficulty and the availability of a reagent, the position of meta or para is preferable from the viewpoint of amide bond, Particularly preferred. In the aminobenzene not having the amino group protected by the Boc group (i.e., -NHBoc), the position of the meta or para is preferable in view of the amide bond as well as the position of the meta is preferable in view of the solubility, From the viewpoint of orientation, the position of para is preferable. The hydrogen of aminobenzene not having -NHBoc may be substituted by an organic group or a halogen atom such as fluorine.

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

In the formula (5), E is a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring. F represents a single bond, -O-, -OCO-, or -COO-.

The diamine represented by the formula (4) in which m is 0 or the diamine represented by the formula (5) is a diamine having an asymmetric structure, and preferred D is the same as described above. With respect to the diamine represented by the formula (5), a compound in which E and F are both a single bond is also preferable.

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

Specific examples of the diamines represented by the above formulas (4) to (7) include, for example, formulas selected from the group consisting of the following formulas.

[Chemical Formula 14]

<Specific diamine 8>

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

[Chemical Formula 15]

(In the formula (8), R ₈ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms or a 1,3-dioxobutyl group.

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

Examples of the aromatic group having 6 to 20 carbon atoms include an aryl group having 6 to 12 carbon atoms or other aromatic groups. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 4-i-propylphenyl group, A 4-methylphenyl group and the like. Examples of the other aromatic groups include a 4-pyridinyl group, a 2-phenyl-4-quinolinyl group, a 2- (4'-t-butylphenyl) -Thiophenyl) -4-quinolinyl group, and the like.

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

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

R ₆ , R ₇ , R ₉ and R ₁₀ are each an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The benzene ring of the aryl group and the aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-butyl group, an i-butyl group or a t-butyl group; Examples of the aryl group having 6 to 12 carbon atoms (provided that the benzene ring of the aryl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms) includes, for example, phenyl group, 4-formylphenyl group, 5-trimethoxyphenyl group and the like; 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 each represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH) - Bond with a peridine ring).

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

[Chemical Formula 16]

(Wherein a is an integer of 1 to 12 and b is an integer of 0 to 5.)

(In which the bonding hands to which &quot; * &quot; is attached are bonded to the piperidine ring), a methylene group or an alkylene group having 2 to 6 carbon atoms.

Examples of the alkylene group having 2 to 6 carbon atoms include a 1,3-propylene group, a 1,6-hexylene group, and the like.

The two amino groups bonded to the benzene ring of the formula (8) are preferably in the 2,4-position or the 3,5-position with respect to the group X &lt; ^{4 &} gt ;.

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

[Chemical Formula 17]

<Specific diamine 9>

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

[Chemical 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 having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a cyano group, a hydroxyl group, a fluoroalkyl group, a trifluoroalkoxy group, a fluorine atom, . Preferably 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). Any hydrogen atom of the benzene ring may be substituted with a monovalent organic group.

[Chemical 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- (L, m represents an integer of 1 to 5). * ₁ represents a site bonded to the benzene ring in formula (9). * ₂ represents a moiety bonded to the amino group in the formula (9). and n represents an integer of 1 to 3. Among them, R ₁₁ is preferably a single bond, -O-, -COO-, -OCO-, -CONH- or NHCO- in view of the relaxation of the accumulated charge.

n represents an integer of 1 to 3; 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 the relaxation of the accumulated charge, the equations (9-1-1), (9-1-2), (9-1-3), (9-1-5) ), (9-1-9), (9-1-10), (9-1-11) or (9-1-12) -2), (9-1-3), (9-1-11), or (9-1-12).

[Chemical Formula 20]

<Other diamines>

In the present invention, other diamines other than the specific diamine can be used in combination as a part of the diamine component. The other diamines are not particularly limited, and for example, there may be mentioned a side chain type diamine described in detail below. The side chain diamine is preferably used when a vertically aligned liquid crystal display element is produced.

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

[Chemical Formula 21]

In formula (10), Y ¹ represents 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 the side chain structure is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or COO-.

Y ² is a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15). Among 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 since it is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or OCO-.

Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom . Y ⁴ is a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. Y ⁴ is preferably an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a steroid skeleton.

Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. Any hydrogen atom 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom .

n is an integer of 0 to 4; Preferably, it is 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 alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl 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 alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

m is an integer of 1 to 4; It is preferably an integer of 1.

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

[Chemical Formula 22]

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

(23)

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

&Lt; EMI ID =

In the 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 fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy or hydroxyl group.

(25)

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

(26)

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

(27)

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 a 1,4-cyclohexylene group or a 1,4-phenylene group. A ² is an oxygen atom or COO- * (provided that the bonding hands to which &quot; * &quot; is bonded are bonded to A ³ ). A ¹ is an oxygen atom or COO- * (provided that the bond is bonded to (CH ₂ ) a ₂ to which "*" is attached). Also, a ₁ is an integer of 0 or 1. a ₂ is an integer of 2 to 10; a ₃ is an integer of 0 or 1;

(28)

[Chemical Formula 29]

(30)

(31)

(32)

Of the above-mentioned formulas (10-1) to (10-31), particularly preferred diamines are the diamines represented by formulas (10-1) to (10-6), formulas (10-9) 10-16), Equation (10-19), Equation (10-23), Equation (10-25) or Equation (10-29).

As other diamines, diamines represented by the following formula (11) are also exemplified.

(33)

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

(34)

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

Specifically, the following diamines can be mentioned.

(35)

(Wherein n represents an integer of 1 to 8)

Other diamines include the diamines of the following formulas or the diamines described on pages 30 to 33 of International Patent Publication No. 2014/171493 (published on October 22, 2014).

(36)

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

&Lt; Tetracarboxylic acid dianhydride component >

The tetracarboxylic acid dianhydride used as a raw material for the polymer contained in the liquid crystal aligning agent used in the present invention is not particularly limited, but tetracarboxylic acid dianhydrides represented by the following formulas (12) to (14) Carboxylic acid dianhydride) is preferably used.

(37)

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

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

(38)

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

Particularly preferred Z ¹ in the formula (12) is a formula (12a), a formula (12c), a formula (12d), a formula (12e), a formula (12f) or a formula (12g) from polymerization reactivity and ease of synthesis.

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

As specific tetracarboxylic acid dianhydrides, tetracarboxylic acid dianhydrides represented by the following formulas (12-1) to (12-5) are preferable, and among these, tetracarboxylic acid dianhydrides are preferable from the viewpoint of the residual image (accumulated charge) (12-1), (12-3) or (12-5) is preferable.

[Chemical Formula 39]

&Lt; Other tetracarboxylic acid dianhydrides >

In the present invention, other tetracarboxylic acid dianhydrides other than the specific tetracarboxylic acid dianhydrides may be used. Examples of other tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides of the following tetracarboxylic acids.

2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7- Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) , 3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, Bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis Phenyl silane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignability, voltage retention rate, and accumulated charge when the liquid crystal alignment film is used.

The liquid crystal aligning agent of the present invention may further contain components other than the specific polymer component. Examples of such additional components include adhesion auxiliary agents for enhancing adhesion between the liquid crystal alignment film and the substrate, adhesion between the liquid crystal alignment film and the sealing material, and adhesion auxiliary agents for enhancing the strength of the liquid crystal alignment film, One crosslinking agent, a dielectric material and a conductive material for adjusting the dielectric constant and electric resistance of the liquid crystal alignment film, and an organic solvent. Specific examples of these additional components include those disclosed in various publications on liquid crystal aligning agents and disclosed in International Publication No. 2015/060357, page 53, pages [0105] to [555], page 55 And the like.

(40)

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

(41)

In the formula (19), R ₂₇ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an organic group having an n-valent 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. Further, at least one of R ₂₈ and R ₂₉ has a hydroxy 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 each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.

(42)

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

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

(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 to 42 of International Publication No. 2014/171493 (published on October 23, 2014) can be mentioned.

<Liquid Crystal Aligner>

The polymer component in the liquid crystal aligning agent of the present invention may be a specific polymer used in the present invention as a whole or may be a mixture of other polymers with the specific polymer of the present invention. At that time, the content of other polymer relative to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.

Examples of the other polymer include a polyimide precursor obtained from a diamine component comprising a diamine other than a specific diamine and a tetracarboxylic acid dianhydride component, or a polyimide obtained by imidizing the polyimide precursor. Further, examples of the other polymer include acrylic polymer, methacrylic polymer, polystyrene, polyamide and the like.

The organic solvent in the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70 to 99 mass% from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. The organic solvent at this time is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer. More specifically, there may be mentioned N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, Examples of the aminosulfuron compounds include N-vinylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, 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 alone or in combination.

The liquid crystal aligning agent of the present invention is a crosslinkable compound having at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group or an alkoxyl group, A crosslinkable compound having an unsaturated bond, and the like.

As a compound that improves film thickness uniformity and surface smoothness, a fluorine-based surfactant, a silicon-based surfactant, or a nonionic surface-active agent may be contained. As the compound that improves the adhesion between the liquid crystal alignment film and the substrate, A functional silane-containing compound or an epoxy group-containing compound may be contained.

A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

The liquid crystal aligning agent of the present invention may contain an organic solvent (also referred to as a poor solvent) or a compound which improves the uniformity of the film thickness of the polymer film when the liquid crystal aligning agent is applied and the surface smoothness. Further, a compound for improving the adhesion between the liquid crystal alignment film and the substrate may be contained.

Examples of the poor solvent for improving the uniformity of the film thickness and the surface smoothness include the following specific examples.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid, methyl lactate, isobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy- , 1-phenoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, or lactic acid isoamyl ester.

One of these poor solvents may be used, and a plurality of these solvents may be mixed and used. When such a poor solvent is used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total amount of the organic solvent contained in the liquid crystal aligning agent.

<Liquid crystal>

As the liquid crystal composition used in the liquid crystal display element of the present invention, a nematic liquid crystal having a positive dielectric anisotropy is used in a horizontal alignment type liquid crystal display element, and a negative dielectric anisotropy A nematic liquid crystal may be used.

In the vertical alignment type liquid crystal display device, a nematic liquid crystal having negative dielectric anisotropy can be used. For example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a hepta base-based liquid crystal, an agar watch liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal, a terphenyl-based liquid crystal, or the like can be used. In addition, an alkenyl-based liquid crystal may be used in combination. As such alkenyl-based liquid crystals, those conventionally known can be used. For example, compounds represented by the following formulas.

(44)

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a BOA substrate or a BCS-attached substrate, and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment.

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

The BCS-adhered substrate is a substrate in which a black column spacer is formed by using a black colored resin composition as a column spacer material for supporting between an array substrate and a counter substrate, and the black matrix resin material is used for the black colored resin composition .

The BOA substrate or the BCS-attached substrate can be obtained by, for example, applying a colored resin composition to a transparent substrate using a spin coat or the like, drying it with a vacuum drier or a hot plate, and then using a photo- Followed by development, development using a KOH aqueous solution or the like, and baking using a hot air circulating oven. As the colored resin composition, there can be used, for example, a black matrix and a colored resin composition for BCS prepared according to the method described in Japanese Patent Application Laid-Open No. 2014-67028, entitled "0312" to "0314".

The transparent substrate to be used at this time is not particularly limited as long as it is a transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In the reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used only for a substrate on one side, and as the electrode in this case, a material for reflecting light such as aluminum can also be used.

The application method of the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, or ink jet printing is generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.

After the liquid crystal aligning agent is applied onto the BOA substrate or the BCS-adhered substrate, the polymer film can be formed by evaporating the solvent at 50 to 300 deg. C, preferably 80 to 250 deg. C, by a heating means such as a hot plate. When the thickness of the polymer film after firing is too large, the power consumption of the liquid crystal display element is deteriorated. When the thickness of the polymer film is too thin, the reliability of the liquid crystal display element is deteriorated. Therefore, the thickness is preferably 5 to 300 nm, Is 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the polymer film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In a vertical alignment type liquid crystal display device, a photo-polymerizable compound is added in advance to a liquid crystal composition and used together with a vertically oriented film such as polyimide to irradiate ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell, A PSA (Polymer sustained alignment) device capable of controlling the alignment of liquid crystals and improving the response speed of liquid crystals by polymerizing a polymer compound is known and reported in JP-A-2003-307720 and the like.

Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal can not be controlled. When the amount is larger than 10 parts by mass, unreacted polymerizable compounds are increased, .

On the other hand, K. Hanaoka, SID 04 DIGEST, and P.1200-SC-PVA type liquid crystal displays (SC-PVA type liquid crystal displays) that the response speed of a liquid crystal display element is increased even by adding a photopolymerizable compound not in a liquid crystal composition but in a liquid crystal alignment film. 1202 and the like.

Example

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

The abbreviations are as follows.

(Acid anhydride)

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride, CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, PMDA: fatigue Melitic acid dianhydride, TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4,2,3-2 anhydride

(Diamine)

PDA: p-phenylenediamine, DDM: 4,4'-methylenedianiline, DBA: 3,5-diaminobenzoic acid,

Nitrogen diamines represented by the following formulas DA-N1 to DA-N7

[Chemical Formula 45]

(46)

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

(47)

The photosensitive diamine represented by the following formula DA-1

(48)

<Solvent>

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

<Additives>

3AMP: 3-Picolylamine

<Cross-linking agent>

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

(49)

(Conditions for measuring molecular weight of polyimide)

(Column: KD-803, KD-805), column temperature: 50 占 폚, eluent: N, N'-dimethyl (GPC) 30 mmol / l of lithium bromide monohydrate (LiBr.H ₂ O), 30 mmol / l of phosphoric acid anhydrous crystal (o-phosphoric acid) and 10 ml / l of tetrahydrofuran (THF) as an additive, (Molecular weight: about 9,000,000, 150,000, 100,000, and 30,000) and polyethylene glycol (molecular weight about 12,000, 4,000, and 100,000) manufactured by Polymer Laboratories Co., 1,000).

(Imidization ratio of polyimide)

20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard 5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, . This solution was subjected to proton NMR measurement at 500 MHz using an NMR meter (JNW-ECA500) manufactured by Nippon DATUM Co., A proton originating from a structure which does not change before and after imidization is defined as a reference proton and the proton peak integrated value derived from the NH group of the amic acid appearing at about 9.5 to 10.0 ppm near the proton peak value By using the following formula. In the following formulas, x is the proton peak integrated value derived from the NH group of amic acid, y is the peak integrated value of the reference proton, and? Is the NH of amic acid in the case of polyamic acid (0% imidization rate) Is the ratio of the number of reference protons to one proton of the group.

Imidization ratio (%) = (1 -? X / y) x 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 141.5 g of NMP, reacted at 80 ° C for 5 hours, 4.71 g, 24.0 mmol) and NMP (47.2 g) were added and reacted at 40 DEG C for 10 hours to obtain a polyamic acid solution.

To this polyamic acid solution (200 g) was added NMP and diluted to 6.5 mass%. Acetic anhydride (43.1 g) and pyridine (13.4 g) were added as imidation catalysts and reacted at 100 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A). The polyimide had an imidization rate of 78%, a number average molecular weight of 22,000, and a weight average molecular weight of 56,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was stirred and dissolved at 70 占 폚 for 20 hours. 6.0 g of 3AMP (1 mass% NMP solution), 4.0 g of NMP and 40.0 g of BC were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent A1.

(Synthesis Example 2)

(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 And the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (200 g), diluted to 6.5 mass%, acetic anhydride (46.3 g) and pyridine (14.3 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The polyimide had an imidization rate of 76%, a number average molecular weight of 13,000, and a weight average molecular weight of 32,000.

A liquid crystal aligning agent (B1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (B) (6.0 g) was used.

(Synthesis Example 3)

(7.24 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) And the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (200 g), diluted to 6.5 mass%, acetic anhydride (44.5 g) and pyridine (13.8 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (C). The polyimide had an imidization rate of 79%, a number average molecular weight of 21,000, and a weight average molecular weight of 49,000.

A liquid crystal aligning agent (C1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (C) (6.0 g) was used.

(Synthesis Example 4)

(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) The reaction was carried out at 60 DEG C for 10 hours to obtain a polyamic acid solution.

To this polyamic acid solution (200 g) was added NMP and diluted to 6.5 mass%. Acetic anhydride (37.6 g) and pyridine (11.6 g) were added as an imidation catalyst and reacted at 110 ° C for 4 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (D). The imidization ratio of the polyimide was 68%, the number average molecular weight was 11,000, and the weight average molecular weight was 25,000.

A liquid crystal aligning agent (D1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (D) (6.0 g) was used.

(Synthesis Example 5)

(19.7 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 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.

NMP was added to the polyamic acid solution (200 g), diluted to 6.5 mass%, acetic anhydride (35.5 g) and pyridine (11.0 g) were added as imidation catalysts and reacted at 100 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (E). The imidization ratio of the polyimide was 75%, the number average molecular weight was 16,000, and the weight average molecular weight was 39000.

A liquid crystal aligning agent (E5) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (E) (6.0 g) was used.

(Synthesis Example 6)

(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 reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (200 g), diluted to 6.5 mass%, acetic anhydride (38.8 g) and pyridine (12.0 g) were added as an imidization catalyst and reacted at 100 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (F). The imidization ratio of the polyimide was 57%, the number average molecular weight was 10,000, and the weight average molecular weight was 24,000.

A liquid crystal aligning agent (F1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (F) (6.0 g) was used.

(Synthesis Example 7)

(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 reacting at 60 DEG C for 3 hours, CBDA (9.51 g, 48.5 mmol) and NMP (41.11 g) were added and reacted at 40 DEG C for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (180 g), diluted to 6.5 mass%, acetic anhydride (36.6 g) and pyridine (11.4 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 80 캜 to obtain a polyimide powder (G). The imidization ratio of the polyimide was 73%, the number average molecular weight was 17,000, and the weight average molecular weight was 38000.

A liquid crystal aligning agent (G1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (G) (6.0 g) was used.

(Comparative Synthesis Example 1)

S1 (19.03 g, 50.0 mmol) was dissolved in NMP (192.2 g) and reacted at 60 占 폚 for 3 hours. Then, PMDA (4.36 g, 48.5 mmol), CBDA (9.61 g, 49.0 mmol) and NMP (38.4 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (200 g), diluted to 6.5 mass%, acetic anhydride (35.3 g) and pyridine (10.9 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (H). The imidization ratio of the polyimide was 73%, the number average molecular weight was 17,000, and the weight average molecular weight was 48,000.

A liquid crystal aligning agent (H1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (H) (6.0 g) was used.

(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), reacted at 60 ° C for 3 hours, 9.41 g, 48.0 mmol) and NMP (37.7 g) were added and reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution.

To this polyamic acid solution (200 g), NMP was added and diluted to 6.5 mass%. Acetic anhydride (43.7 g) and pyridine (13.5 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (2700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (I). This polyimide had an imidization rate of 72%, a number average molecular weight of 13,000, and a weight average molecular weight of 25,000.

A liquid crystal aligning agent (I1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (I) (6.0 g) was used.

(Synthesis Example 8)

6.0 g of the liquid crystal aligning agent (H1) obtained in Comparative Synthesis Example 1 as a first component and 14.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as a second component were mixed and stirred for 1 hour to obtain a liquid crystal aligning agent J1) was prepared.

(Synthesis Example 9)

6.0 g of the liquid crystal aligning agent (I1) obtained in Comparative Synthesis Example 2 as a first component and 14.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as a second component were mixed and stirred for 1 hour to obtain a liquid crystal aligning agent K1) was prepared.

(Synthesis Example 10)

CL-2 was added to 10.0 g of the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 in an amount of 10 wt% of the resin component and stirred at room temperature for 1 hour to prepare a liquid crystal aligning agent (A2).

(Synthesis Example 11)

To 10.0 g of the liquid crystal aligning agent (D1) obtained in Synthesis Example 4, CL-1 was added in an amount of 10 wt% of the resin component and stirred at room temperature for 1 hour to prepare a liquid crystal aligning agent (D2).

(Synthesis Example 12)

To 10.0 g of the liquid crystal aligning agent (K1) obtained in Synthesis Example 9, CL-3 was added in an amount of 10 wt% of the resin component and stirred at room temperature for 1 hour to prepare a liquid crystal aligning agent (K2).

(Synthesis Example 13)

(3.81 g, 10.0 mmol) and DA-N6 (3.97 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 reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution.

To the polyamic acid solution (40 g) was added NMP and diluted to 6.5 mass%. Acetic anhydride (6.68 g) and pyridine (2.07 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (461 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyimide powder (L). The polyimide had an imidization rate of 72%, a number average molecular weight of 15,000, and a weight average molecular weight of 28,000.

A liquid crystal aligning agent (L1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (L) (6.0 g) was used.

(Synthesis Example 14)

(3.41 g, 10.0 mmol), DA-N7 (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 reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution.

To the polyamic acid solution (40 g) was added NMP and diluted to 6.5 mass%. Acetic anhydride (6.99 g) and pyridine (2.17 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (463 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyimide powder (M). The imidization ratio of the polyimide was 70%, the number average molecular weight was 14,000, and the weight average molecular weight was 30000.

A liquid crystal aligning agent (M1) was obtained in the same manner as in Synthesis Example 1, except that the obtained polyimide powder (M) (6.0 g) was used.

(Example 1)

A liquid crystal cell was prepared using the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 according to the following procedure, and the measurement of the pretilt angle and the voltage holding ratio were carried out.

&Lt; Preparation of colored resin composition >

The colored resin composition (a) for a black column spacer (BCS) used in the present invention is a resin composition which is also used as a black matrix material. Resist (VI) described in "0312" to "0314" . &Lt; / RTI &gt;

&Lt; Fabrication of ITO substrate 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 mu m x 300 mu m and a line / space of 5 mu m / 5 mu m was formed, Mu m by spin coating. Thereafter, the substrate was dried in a vacuum drier for 60 seconds, and then dried on a hot plate at 110 DEG C for 2 minutes to obtain a substrate before exposure to which the colored resin composition (a) was adhered.

This pre-exposure substrate was exposed to light at 50 mJ / cm 2 through an ultra-high pressure mercury lamp through a 20 탆 aperture photomask having an aperture of 20 탆 and then developed using a KOH aqueous solution at a temperature of 25 캜 and a concentration of 0.05% by mass. Thereafter, the substrate with the resist (VI) was fired at 230 DEG C for 30 minutes using a hot air circulating oven to obtain an ITO substrate with a BCS.

&Lt; Production of liquid crystal cell &

A liquid crystal cell was produced in the following manner by using the liquid crystal aligning agent (A1). The liquid crystal aligning agent A1 was spin-coated on the ITO surface of the ITO substrate with BCS and dried for 90 seconds on a hot plate at 80 DEG C and then fired in a hot air circulating oven at 200 DEG C for 30 minutes to obtain a film 100 Nm liquid crystal alignment film was formed.

The liquid crystal aligning agent A1 was spin-coated on an ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 占 폚 and fired in a hot air circulating oven at 200 占 폚 for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.

A thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the two substrates. Subsequently, the other side of the substrate on which the liquid crystal alignment film was formed was inwardly bonded to the previous substrate, and then the sealing agent was cured to prepare an empty cell. A liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Inc., alkenyl-based liquid crystal) containing a polymerizable compound for PSA was injected into this vacancy cell by a low 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 in which a DC voltage of 15 V was applied to the liquid crystal cell, UV light having passed through a band-pass filter of 365 nm from the outside of the liquid crystal cell was irradiated with 10 J / cm 2 (also referred to as primary PSA treatment). The UV illuminance was measured using UV-MO3A (attachment: UV-35) manufactured by ORC. Thereafter, in order to deactivate the unreacted polymerizable compound remaining in the liquid crystal cell, the UV (FL lamp: FLR40SUV32 / A (UV lamp: UV lamp: -1) was irradiated for 30 minutes (also referred to as secondary PSA treatment). Thereafter, the cell subjected to the UV irradiation was measured for the pretilt angle of the pixel portion and the voltage holding ratio was measured.

&Quot; Measurement of the pretilt angle &quot;

Was measured using an LCD analyzer LCA-LUV42A (manufactured by Meier Technology).

Evaluation of voltage holding ratio &quot;

A voltage of 1 V was applied for 60 seconds in a hot air circulating oven at 60 DEG C, and a voltage after 1667 milliseconds was measured, and the degree of voltage maintenance was calculated as a voltage holding ratio. VHR-1 manufactured by Toyo Technica Co., Ltd. was used for measurement of the voltage holding ratio.

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

The same operation as in Example 1 was carried out except that the liquid crystal aligning agent (A1) used in Example 1 was changed to liquid crystal aligning agents (B1) to (M1), (A2), (D2) Tilt angle and voltage holding ratio were measured.

(Example 1 ')

A liquid crystal cell was prepared using the substrate with an ITO electrode to which BCS was not attached in the same operation as in Example 1, and the pretilt angle and the voltage holding ratio were measured. In addition, to keep the cell gap, a 4 μm bead spacer was used instead of the black column spacer and was scattered on the liquid crystal alignment film.

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

The same operation as in Example 1 'was carried out except that the liquid crystal aligning agent (A1) used in Example 1' was changed to liquid crystal aligning agents (B1) to (M1), (A2), (D2) , Measurement of the pretilt angle and measurement of the voltage holding ratio were carried out.

Examples 1 to 7, 13 and 14 and Examples 1 'to 7', 13 'and 14', as compared with Comparative Examples 1 and 2 and Comparative Examples 1 'and 2' It was confirmed that even when used, high VHR characteristics were exhibited.

Further, as can be seen from Examples 8 and 9 and Examples 8 'and 9', a combination of a polymer having no diamine containing a carboxyl group or nitrogen-containing structure as a monomer unit and a polymer having the diamine as a monomer unit It was confirmed that high VHR characteristics can be exhibited. Further, as shown in Examples 10 to 12 and Examples 10 'to 12', even when a BCS-attached substrate is used, even if a crosslinking agent is added to a polymer exhibiting high VHR characteristics, high VHR characteristics It was confirmed that it could.

Also, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2016-118281 filed on June 14, 2016 are incorporated herein by reference and are incorporated herein by reference.

Claims (12)

A polyimide precursor obtained by reacting a diamine component containing a diamine containing a nitrogen or carboxylic acid group and a tetracarboxylic acid dianhydride component in a structure other than two amino groups and a polyimide precursor obtained by imidizing the polyimide precursor Wherein the liquid crystal aligning agent comprises at least one kind of polymer selected from the group consisting of BOA and BCS. The method according to claim 1,
Wherein the diamine has at least one structure selected from the group consisting of the following formulas as a partial structure.
[Chemical 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 portions.) R ₁₄ Is a hydrogen atom, a single bond, a carbonyl group or * -CONH- (provided that the bond to which * is attached is a bond to a piperidine ring), R ₁₅ represents hydrogen or a monovalent organic group, R ₁₈ and And R &lt; ₁₉ &gt; are each independently a hydrogen atom or a single bond. 3. The method according to claim 1 or 2,
Wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulas (1) to (9).
(2)

(Wherein X ¹ represents a single bond, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO- _{, -CON (CH 3) -.} . , or N (CH ₃₎ CO- is X ² is a non-aromatic heterocyclic ring containing a nitrogen atom or an alkyl group having 1 to 5 carbon atoms X ³ is an alkyl group of 1 to 5 carbon atoms And n is an integer of 1 to 4), which is optionally substituted with a halogen atom, a halogen atom,
(3)

(In the 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.)
[Chemical Formula 4]

(In the formula (3), Q ₁ represents an alkylene of 1 to 5 carbon atoms, Cy represents an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine Q ₂ represents a structure of the following formula (3-I) or (3-II): embedded image In the formulas (3-I) and * 1 represents a bond with Q _1, * 2 represents the bonding to the benzene ring. in the formula (3-II) of the R ₁ represents a hydrogen, or a monovalent organic. R _2, R ₃ are monovalent Q and r are each independently an integer of 0 to 4. However, when the sum of q and r is 2 or more, R ₂ and R ₃ are independent of each other.
[Chemical Formula 5]

[Chemical Formula 6]

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

(In the formula (8), R ⁸ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an alkyl group having 7 to 13 carbon atoms or a 1,3-dioxobutyl group.
X ¹¹ is a single bond, a carbonyl group or * -CONH- (provided that the bond to which the "*" is attached bonds with 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, 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 each independently represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH) - Which binds to the piperidine ring).
X ¹⁴ each independently represents a group represented by -O-, -OCO-, a group represented by the following formula (X ¹⁴ -1) (provided that the bonding hands to which "*" is attached and the bonding hands to which the piperidine ring , A methylene group or an alkylene group having 2 to 6 carbon atoms.)
[Chemical Formula 8]

(Formula (X ¹⁴ -1) of, a is an integer of 1 ~ 12. B is an integer of 0-5.)
[Chemical Formula 9]

(9), R ₁₁ represents hydrogen or a monovalent organic group, each R ₁₂ independently represents a single bond or a structure represented by the following formula (9-2), and any hydrogen atom of the benzene ring May be substituted with a monovalent organic group, and n is an integer of 1 to 3.)
[Chemical formula 10]

(In the formula (9-2), R ₁₃ represents a single bond, -O-, -COO-, -OCO-, - (CH ₂ ) _l -, -O (CH ₂ ) _m O-, -CONH-, And -NHCO- (1, m represents an integer of 1 to 5) * ₁ represents a site bonded to the benzene ring in formula (9) * ₂ represents a divalent organic group selected from the group consisting of (9). &Lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS, wherein the diamine component comprises a diamine represented by the following formula (10) or (11).
(11)

(In the formula (10), Y ¹ represents 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. Any hydrogen atom 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom . Y ⁴ is a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. Y ⁴ is preferably an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a steroid skeleton.
Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring. Any hydrogen atom 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom .
n is an integer of 0 to 4;
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms.
and m is an integer of 1 to 4.)
[Chemical Formula 12]

(In the formula (11), Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom.
R ₁ and R ₂ each independently represent an alkyl group, an alkoxy group, a benzyl group or a phenethyl group having 1 to 10 carbon atoms, and in the case of an alkyl group or an alkoxy group, R ₁ and R ₂ may form a ring.
T ₁ and T ₂ each independently represents a single bond or a group selected from the group consisting of -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ) -CON (CH ₃₎ -, or -N (CH ₃₎ a linking group of CO-.
S represents an alkylene group having 1 to 20 carbon atoms (which may be optionally substituted with -CH ₂ - or CF ₂ - in the alkylene group, which is optionally substituted by a single bond or an unsubstituted or fluorine atom, In the case where any of the groups listed below are not adjacent to each other, a group represented by -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring Or a divalent heterocyclic ring).
Q represents the following structure.
[Chemical Formula 13]

(Wherein each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents -CH ₂ -, -NR-, -O- or S-.) 5. The method according to any one of claims 1 to 4,
Wherein the tetracarboxylic acid dianhydride component is at least one tetracarboxylic acid dianhydride selected from the group consisting of the following formulas (12) to (14):
[Chemical Formula 14]

(12), Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. In the formula (13) or the formula (14), j and k is, independently of each other, 0 or 1. X and y are each independently a single bond, a carbonyl, an ester, a phenylene, a sulfonyl or an amide group. 6. The method according to any one of claims 1 to 5,
Wherein the liquid crystal aligning agent comprises a polymer other than the polyimide precursor, or a polymer other than polyimide in which the polyimide precursor is imidized, the liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS. 7. The method according to any one of claims 1 to 6,
Wherein the liquid crystal aligning agent further comprises at least one selected from the group consisting of a liquid crystal aligning agent, an adhesion auxiliary agent, a crosslinking agent, a dielectric, a conductive material and an organic solvent. 8. The method of claim 7,
Wherein the crosslinking agent is at least one compound selected from the following formulas (17), (19) and (21): a liquid crystal aligning agent for coating a BOA substrate or a substrate with a BCS;
[Chemical Formula 15]

(Wherein R ₂₀ , R ₂₁ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkoxy group having 2 to 4 carbon atoms, R ₂₂ and R ₂₄ each independently represent an aromatic ring, and any hydrogen atom in the aromatic ring may have a substituent selected from the group consisting of a hydroxyl group, a hydrocarbon group having 1 to 3 carbon atoms An alkyl group, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group, and R ₂₃ is a saturated or unsaturated, saturated or unsaturated Hydrocarbon group.)
[Chemical Formula 16]

(In the formula (19), R ₂₇ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an organic group having an n-valent containing an aromatic hydrocarbon group, and c is an integer of 2 to 6. R ₂₈ and R ₂₉ are each independently , At least one of R ₂₈ and R ₂₉ 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, , as a substituent having a hydroxy group. in addition, it is substituted by a group represented by R ₂₈ and R at least one dog (20) of ₂₉ is preferred. (20) of, R ₃₀ ~ R ₃₃ are, each independently, A hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.
[Chemical Formula 17]

(In the formula (21), R ₃₄ and R ₃₈ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ₃₅ and R ₃₇ each independently represent an aromatic ring; Any hydrogen atom may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group, R ₃₆ is a single bond, A saturated hydrocarbon group of 1 to 10 carbon atoms which may form a cyclic structure, and any hydrogen atom may be replaced by -NH-, -N (CH ₃ ) - or a group represented by the formula (22) (22), P ₁ and P ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring. In the formula (21), d and f are each independently an integer of 1 to 5, E and g are each independently an integer of 1 to 3.) 9. The method of 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 aligning agent for coating a BOA substrate or a substrate with a BCS.
[Chemical Formula 18]

A liquid crystal display element comprising a BOA substrate or a BCS-attached substrate on which a liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 9 is formed. A process for producing a liquid crystal alignment film on a BOA substrate or a BCS-adhered substrate, wherein the liquid crystal aligning agent according to any one of claims 1 to 9 is applied to a BOA substrate or a substrate with a BCS. A substrate for a liquid crystal display element comprising a BOA substrate or a BCS-attached substrate, and a liquid crystal alignment film formed on the BOA substrate or the BCS-attached substrate using the liquid crystal aligning agent according to any one of claims 1 to 9.