WO2008010528A1

WO2008010528A1 - Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same

Info

Publication number: WO2008010528A1
Application number: PCT/JP2007/064207
Authority: WO
Inventors: Kimiaki Tsutsui; Hirobumi Shida; Mariko Yamada; Kosuke Takazawa
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-07-18
Filing date: 2007-07-18
Publication date: 2008-01-24
Also published as: TW200819509A; JP5428336B2; JPWO2008010528A1; KR101426100B1; KR20090031737A; CN101490188A; TWI439519B; CN101490188B

Abstract

It is intended to provide a liquid crystal oriented film in which deposition of resin component due to moisture absorption is inhibited, and which has stable printability and also has characteristics such as rubbing resistance and ease of removing stored charge. An application liquid, characterized by containing (A) component: an imidized polymer soluble in a solvent obtained from at least one type of amine compound selected from the group consisting of a tetracarboxylic dianhydride, a diamine compound, an amine compound (a), an amine compound (b), and an amine compound (c) described below, and (B) component: polyamic acid. Amine compound (a): an amine compound having in its molecule, one primary amino group selected from the formula [K1] and the formula [K2], and at least one imino group selected from the formula [K3] and the formula [K4]. In the formula [K3] and the formula [K4], the coupling direction of -CH2-NH- is opposite to each other. Amine compound (b): an amine compound having in its molecule, at least two primary amino groups selected from the formula [K1] and the formula [K2]. Amine compound (c): an amine compound having in its molecule, at least one primary amino group selected from the formula [K1] and the formula [K2], and at least one imino group selected from the formula [K3] and the formula [K4].

Description

Specification

LIQUID CRYSTAL ALIGNANT, LIQUID CRYSTAL ALIGNING FILM AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME

The present invention relates to a coating liquid suitable as a liquid crystal aligning agent, and further relates to a liquid crystal alignment film and a liquid crystal display element obtained using this coating liquid.

Background art

[0002] Currently, a liquid crystal alignment film used in a liquid crystal display element or the like is generally made of polyimide, and is usually manufactured by applying a solution called a liquid crystal alignment agent and baking it. Yes. In this case, the liquid crystal aligning agent is generally a solution containing a polyimide precursor such as polyamic acid or a solvent-soluble polyimide, but contains both a polyamic acid and a solvent-soluble polyimide (see Patent Document 1). Also proposed are polyamic acids and those containing two or more types of imidopolymers having different imidication ratios obtained by dehydrating and ring-closing polyamic acids (see Patent Document 2). Thus, the liquid crystal aligning power which contains several kinds of resin components The obtained liquid crystal aligning film has several required properties such as liquid crystal orientation, liquid crystal pretilt angle, and various electric characteristics of the liquid crystal cell. It is known that can be realized simultaneously.

[0003] In order to industrially produce a liquid crystal alignment film, a method of applying a liquid crystal alignment agent by flexographic printing using a printing machine is currently the mainstream, but the film is uniformly printed for a long time. In some cases, the printing performance deteriorates and printing defects occur. One of the reasons for this is that the liquid crystal orientation agent staying on the printing press is concentrated by volatilization of the solvent and further absorbs moisture, causing aggregation and precipitation of the resin component in the solution. Therefore, this phenomenon becomes significant when a main solvent is a highly hygroscopic solvent such as an amide solvent. In addition, the detailed cause has been elucidated! However, in the case of the liquid crystal aligning agent containing both polyamic acid and soluble polyimide, the above-mentioned printing failure is likely to occur. In response to this phenomenon, it has been proposed to use a compound having a biphenyl-diamine skeleton as a diamine component for obtaining a soluble polyimide (see Patent Document 3).

[0004] Patent Document 1: Japanese Patent Laid-Open No. 8-220541 Patent Document 2: Japanese Patent Laid-Open No. 9-2937312

Patent Document 3: International Publication No. 2004Z090016 pamphlet

Disclosure of the invention

Problems to be solved by the invention

[0005] The problem to be solved by the present invention is to improve the stability during moisture absorption with respect to a coating solution containing both a polyamic acid and an imidized polymer soluble in a solvent.

An object of the present invention is to provide a coating liquid suitable as a liquid crystal aligning agent, to provide a high-quality liquid crystal alignment film, and to provide a high-quality liquid crystal display element.

Means for solving the problem

[0006] As a result of intensive studies to solve the above problems, the present inventors have made a specific amine compound react with a solvent-soluble polyimide, or a raw material for producing a solvent-soluble polyimide. It has been found that the use of a specific amine compound improves the hygroscopic stability of the mixed solution with the polyamic acid, and the present invention has been completed. That is, the present invention has the following features.

[0007] (1) Component (A): tetracarboxylic dianhydride, diamine compound, aminic compound (a), aminic compound (b) and aminic compound (c) A coating solution comprising: an imidized polymer that is soluble in the obtained solvent and at least one selected amine compound strength; and (B) component: polyamic acid.

Amine compound (a): In the molecule, at least one primary amino group selected from formula [K1] and formula [K2] and at least an imino group selected from formula [K3] and formula [K4] One amine compound. In the formulas [K3] and [K4], the bonding direction of —CH—NH— is opposite.

2

Amine compound (b): an amine compound having at least two primary amino groups selected from the above formulas [K1] and [K2] in the molecule.

Amine compound (c): At least one primary amino group of formula [K1] and formula [K2] force in the molecule and an imino group of formula [K3] and formula [K4] Amine compound having at least one.

[0008] [Chemical 1] H ₂ N-CH ₂ — H ₂ N-CH—

[Kl] [K2]

— CH ₂ -NH— — NH— CH ₂ ―

[K3] [K4]

(2) The component (A) is composed of at least one of a side chain and a molecular end of a solvent-soluble polyimide obtained by the ability of a tetracarboxylic dianhydride and a diamine compound, and the amine compound (a) and The coating solution according to the above (1), which is an imidized polymer soluble in a solvent obtained by binding an amine compound (b) with at least one amine compound that also has a selected force.

(3) The component (A) is at least one selected from the amine compound (a) and the amine compound (b) as a solvent-soluble polyimide obtained by combining tetracarboxylic dianhydride and diamine compound. The coating solution according to (1) above, which is a product obtained by reacting an amine compound.

(4) The component (A) is a solvent-soluble imido compound obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine compound containing an amine compound (c). The coating solution according to (1) above, which is a soot polymer.

(5) The component (A) is a solvent obtained by using, as the amine compound (a), at least one amine compound selected from amine compounds represented by the following formulas (i) and (ii): The coating solution according to the above (1), which is an imidized polymer soluble in water.

[Chemical 2]

H ₂ N— R ¹ — X ¹ -CH N ~ X ² (i)

H

H ₂ N— R ¹ — X ¹ — N-CH ₂ -X ² (ϋ)

H

[However, R ¹ in the formula is CH CH (CH) or one CH (CH CH) —

2 3 2 3 represents alkylene or an aliphatic ring, X ¹ represents a single bond or an aliphatic hydrocarbon having 120 carbon atoms, and —NH 2 may be contained in the aliphatic hydrocarbon. X ² represents an organic group having 120 carbon atoms, an alkyl group having 120 carbon atoms, and a cyclic aliphatic group. Organic group consisting of a group, aromatic group, heterocyclic group, carboxyl group and combinations thereof, and unsaturated bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), An amino bond (one NH 3), an amine bond (one N), a silyl bond (one Si—), a siloxane bond (SiO 2), and the like may be included. Furthermore, even if the alkyl group of X ² forms a heterocyclic structure with any of —R ¹ , X ¹ —, —CH 1, and NH

2

Good. ]

(6) The component (A) is at least one amine compound selected from amine compounds represented by the following formulas (m) to (V) as the amine compound (b): The coating solution according to (1) above, which is an imidized polymer soluble in the obtained solvent.

[0011] [Chemical 3]

H ₂ N— R ¹ — X ³ -R ¹ — NH ₂ (iii)

H ₂ N— R— X ⁴ — NH— X ⁵ — R ¹ — NH ₂ (iv)

H ₂ N— R ¹ — X ⁶ -NH— X ⁷ -NH— X ⁸ -R ¹ — NH ₂ (v)

[However, R ¹ in the formula is CH —, one CH (CH 2) one, or one CH (CH 2 CH 2) —

2 3 2 3 Represents lucylene or an aliphatic ring, and H? ^ 1 ^-and -1 ^? << 1 R ¹ are the same or different

twenty two

May be. X ³ represents a single bond or an organic group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an aliphatic ring, an aromatic ring, a heterocyclic ring, and an organic group having a combination force thereof, and , Unsaturated bond, ether bond (one 0—), ketone bond (one CO), ester bond (COO), thioether bond (one S), silyl bond (one Si—), siloxane bond (one SiO), etc. May be included. x ⁴ , x ⁵ , X ⁶ , X ⁷ and X ⁸ each independently represent an aliphatic hydrocarbon having 1 to 20 carbon atoms, and may be the same or different. ]

(7) The component (A) is at least one amine compound selected from amine compounds represented by the following formulas (i), (ii), Gv) and (V) as the amine compound (c): The coating solution according to (1) above, which is an imidopolymer soluble in a solvent obtained by using the product.

[0012] [Chemical 4] H ₂ N— R ¹ — X ¹ -CH ₂ — N ~ X ² (i)

H

H ₂ N— R ¹ — X ¹ — N-CH ₂ -X ² (ϋ)

H

[0013] [Chemical 5]

H ₂ N— R ^ -X ⁴ — NH— X ⁵ — R ¹ — NH ₂ (iv) H ₂ N— R ¹ — X ⁶ -NH— X ⁷ — NH— X ⁸ -R ¹ — NH ₂ (v )

(8) Ratio power of imidized polymer of component (A) and polyamic acid of component (B) In the total mass of component (A) and component (B), the ratio of polyamic acid of component (B) is The coating solution according to any one of (1), (2), and (4) to (7), which is 20 to 99% by mass.

(9) The component (A) is composed of tetracarboxylic dianhydride and diamine compound, and the solvent-soluble polyimide obtained is 100 parts by mass with respect to the amine compound (a) and amine compound (b). The coating liquid according to (3) above, which is a product obtained by reacting 1 to 15 parts by mass of at least one amine compound selected from

(10) The component (A) is soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride and a diamine containing the amine compound (c) represented above. The above-mentioned (4) or (7), wherein the amount of the amine compound (c) is 1 mol% to 15 mol% in the total amount of the diamine and the amine compound (c) combined with the imidized polymer. ).

(11) A liquid crystal aligning agent comprising the coating liquid according to any one of (1) to (10) above.

(12) The liquid crystal aligning agent according to the above (11), wherein the amide solvent is contained in the coating solution in an amount of 50% by mass or more.

(13) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to (11) or (12).

(14) A liquid crystal display device using the liquid crystal alignment film according to (13).

The invention's effect

[0015] According to the coating liquid of the present invention, precipitation of the resin component due to moisture absorption is suppressed, stable printability can be obtained, and it can be suitably used as a liquid crystal aligning agent. In addition, the coating of the present invention Since the liquid crystal alignment film obtained using the cloth liquid has improved rubbing resistance and improved ease of stored charge release, a liquid crystal display element of higher quality than before can be obtained.

Brief Description of Drawings

[0016] FIG. 1 is a graph showing a comparison of the ease of escape of accumulated charges in a liquid crystal cell using a liquid crystal aligning agent having a coating solution force of Example 4 or Comparative Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] In a coating solution containing both a solvent-soluble imidopolymer and a polyamic acid, the solvent-soluble imidized polymer component is particularly suitable for forming a liquid crystal alignment film at a low firing temperature. In addition, it contributes to the voltage holding ratio of the liquid crystal cell, etc., and the polyamic acid component contributes to printability, adhesion to the substrate, reduction of charge accumulation and ease of charge removal when used as a liquid crystal alignment film. . In addition, it is said that after the coating film is formed, the concentration of soluble polyimide and polyamic acid in the film thickness direction has a gradient, which makes it difficult to obtain with a single resin component.

However, as described above, the liquid crystal aligning agent staying on the printing press is concentrated by volatilization of the solvent and further absorbs moisture as described above. The aggregation and precipitation of the fat component is thought to be one of the causes of printing defects. Therefore, the present inventors have moderately suppressed this phase separation by the action of a specific amine compound, so that the advantage of containing both the solvent-soluble polyimide and the polyamic acid is not lost. As a result, the present invention has been completed.

That is, the present invention relates to a solvent obtained from tetracarboxylic dianhydride, diamine compound, and an amine compound (a) and amine compound (b) represented by the following formula: A coating solution containing a component (A) of a soluble imidopolymer and a component (B) of a polyamic acid.

In the present invention, a preferred embodiment of the component (A) is that the solvent-soluble polyimide obtained from tetracarboxylic dianhydride and a diamine compound includes a specific amine compound (a) and an amine compound. (b) An imidyl polymer that is soluble in a solvent obtained by binding at least one amine compound, the force of which is selected, as at least one of a side chain and a molecular end.

[0019] Specifically, the following amine compound (a) and amine compound (b) are added to {1} solvent-soluble polyimide. Or a force that contains an imidized polymer that is soluble in a solvent, which is a product obtained by reacting at least one selected amine compound, and a polyamic acid, or {2} tetracarboxylic acid It contains a polyimide precursor soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting an anhydride with a diamine containing the following amine compound (c), and a polyamic acid. . In {1} and {2}, the polyamic acid is the same.

The amine compound (a) has one primary amino group selected from the formula [K1] and formula [K2] and an imino group selected from the formula [K3] and formula [K4] in the molecule. An amine compound having at least one,

[0020] [Chemical 6]

H ₂ N-CH ₂ — H ₂ N-CH— [Kl] [2]

— CH ₂ -NH— — NH-CH ₂ —

[K3j [K4] Amine compound (b) is an amine compound having at least two primary amino groups selected from the formulas [K1] and [K2] in the molecule.

[0021] It should be noted that in the formulas [K3] and [K4], for example, the CH—NH bonding directions are reversed as in the relations of X ¹ and X ² in formulas (i) and (ii) described later. In relation,

2

In addition, the amine compound (c) has at least one primary amino group having the formula [K1] and formula [K2] forces selected in the molecule and an imino group selected from the formula [K3] and formula [K4]. It is an amine compound with at least one.

[0022] The amine compound (c) is the same as the amine compound (a) when it has one primary amino group represented by the formula [K1] or the formula [K2]. And having at least two primary amino groups selected from the formulas [K1] and [K2] are compounds contained in the amine compound (b).

Preferably, the amine compound (a) has the following formula —I ^ NH (R ¹ is CH —, —CH (CH

2 2 3

1) an amino group represented by CH (CH 2 CH 3) — or an aliphatic ring) and

twenty three

An amine compound having at least one imino group represented by —R ² —NH—R ³ — (R ² and R ³ are divalent organic groups, at least one of which is methylene). [0023] Preferably, the amine compound (b) is represented by the following formula: —I ^ —NH (R ¹ is —CH—, —CH

twenty two

(CH 3) —, —CH 2 (CH 2 CH 3) —, or an aliphatic ring)

3 2 3

Is also an amine compound.

Further, preferably, the amine compound (c) has the following formula —I ^ —NH (R ¹ is —CH—, —C

twenty two

H (CH 3) —, —CH 2 (CH 2 CH 3) —, or an aliphatic ring)

3 2 3

And at least one imino group represented by the following formula: —R ² —NH—R ³ — (R ² and R ³ are divalent organic groups, at least one of which is methylene) It is an amine compound having

As a specific example of the coating solution of {1}, a predetermined amount of the amine compound (a) or amine compound (b) is added to a polyimide solution, and the solution is heated at room temperature or under heating conditions. It is a solution obtained by mixing the imidyl polymer soluble in the solvent of the reaction product obtained by stirring and the polyamic acid solution in an arbitrary ratio.

Further, as a specific example of the coating solution of {2}, an imidyl polymer solution obtained by imidizing a polyimide precursor obtained by reacting tetracarboxylic dianhydride, diamine and the above amine compound (c) And a solution obtained by mixing a polyamic acid solution in an arbitrary ratio.

The specific amine compound (a) and amine compound (b) used in the present invention have at least two action points. One is a site chemically bonded to the solvent-soluble polyimide, and the other is a site that forms a hydrogen bond or salt formation with the polyamic acid. This improves the compatibility between the imidopolymer and polyamic acid that are soluble in the solvent reacted with the specific amine compound, and suppresses phase separation when the coating solution is concentrated.

In the amine compound (a) or the amine compound (b), the primary amino group represented by the formula [K1] and the formula [K2] is an aliphatic amino group, and the imide carbonyl group in the polyimide is When the imidization ratio of the polyimide is less than 100% as described later, in addition to the reaction described above, the carboxyl group or amic acid ester group of the amic acid group It binds to the carboxyester group by a reaction involving elimination of water or alcohol.

Included in the amine compound (a) or the amine compound (b) that is preferred as described above — R ¹ — NH In the amino group represented by R ¹ , R ¹ represents one CH CH (CH) CH (CH CH)

2 2 3 2 3

-Or an aliphatic ring. Aliphatic rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and cyclododecane.

, Adamantane, decahydronaphthalene, norobornane and the like.

These amino groups are aliphatic amino groups and exhibit the characteristics as described above. Therefore, R ^{1 of} this amino group is most preferably methylene because it increases the nucleophilicity of the amino group and has less steric hindrance. Among the aliphatic rings, cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like are preferable.

On the other hand, it is represented by CH—NH or NH—CH— contained in the amine compound (a).

twenty two

The imino group acts with the carboxyl group in polyamic acid, such as hydrogen bonding and salt formation.

. In the amine compound (a), it is represented by —CH—NH or NH—CH—.

twenty two

One or more imino groups may be contained, but 1 to 4 is suitable from the viewpoint of availability and stability of the compound, and 1 to 2 is particularly preferable.

Similarly, the imino group represented by —R ² —NH—R ³ contained in the amine compound (a) described above has a function of forming a hydrogen bond or salt formation with the carboxyl group in the polyamic acid. . Therefore, R ² and R ³ of this imino group need to have at least one of R ² and R ³ methylene because it is necessary to give the nitrogen atom of the imino group a certain electron density. When a one month ^ styrene, structures of the other is not particularly limited, for example, exemplified in ^{R 1 - CH -, - CH} (CH) -, - CH (CH CH) -, aliphatic ring, or off

2 3 2 3

Ehren etc. Among these, methylene or an aliphatic ring is preferable. More preferably, both R ² and R ³ are styrene. In the amine compound (a), it is sufficient that at least one imino group represented by R ² —NH—R ³ is present, but 1 to 4 is appropriate from the viewpoint of availability and stability of the compound. There are 1 to 2 pieces, especially.

[0026] The amine compound (b) has at least two primary amino groups selected from the formulas [K1] and [K2]. In the case of such an amine compound, when the first primary amino group reacts with the solvent-soluble polyimide, the migration of the amine compound is suppressed, so the remaining amino group reacts with another solvent-soluble polyimide. It becomes difficult. As a result, the amino group not reacting with the solvent-soluble polyimide has the same action as the imino group contained in the amine compound (a). It becomes.

[0027] In the amine compound (b), there are 2 or more primary amino groups as described above, but 2 to 5 from the viewpoint of availability and stability of the compound. Is suitable, and 2 to 3 is particularly preferable. In addition, it is preferable that the amine compound (b) further has one or more imino groups selected from the formulas [K3] and [K4] because the compatibility with the polyamic acid becomes higher. This imino group is preferably an imino group represented by R ² —NH—R ³ as in the amine compound (a). The definitions of R ² and R ³ are the same as in the amine compound (a).

[0028] In the coating solution of {2}, at the time of producing the soluble imidized polymer of component (A), at least one of the formula [K1] and formula [K2] forces possessed by the amine compound (c) is also selected. The primary amino group reacts with tetracarboxylic dianhydride, so that the amine compound (c) is taken into the polyimide. One or more amino groups may be contained in the molecule, but 1 to 5 is suitable from the viewpoint of availability and stability of the compound, and 1 to 2 is particularly preferable. Since the amine compound (c) with one amino group is located at either the side chain or the terminal of the polymer molecule, it has less steric hindrance when it forms a hydrogen bond or salt with the polyamic acid. Most preferred for reasons. If the number of amino groups is 3 or more, the resulting soluble polyimide has a three-dimensional structure. When this coating solution is used as a liquid crystal alignment film, the reason for obtaining uniform orientation of the liquid crystal is preferred to have less branching of the main chain. Therefore, two or less amino groups are preferred.

This amino group, like the amine compound (a), is an amino group represented by R ¹ —NH.

2

Are preferred. The definition of R ¹ is the same as the amine compound (a).

[0029] On the other hand, the imino group selected from the formula [K3] and the formula [K4] contained in the amine compound (c) is the above-mentioned amine compound (a) with regard to its constitution, action and preferred form. It is the same as the imino group contained in. That - R ² - NH-R ³ in the preferred instrument R ² be an imino group represented,

The definition of R ³ is the same as in the amine compound (a).

More specifically, as the amine compound (a) in the present invention, for example, amine compounds represented by the following formulas (i) and (ii) can be exemplified.

[0030] [Chemical 7] H ₂ N— R ¹ — X -CH ₂ -N— X ² (i)

H

H ₂ N— R ¹ — X ¹ — N-CH ₂ -X ² (ϋ)

H where R ¹ is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —

2 3 2 3 represents an alkylene or an aliphatic ring, X ¹ represents a single bond or a divalent organic group, and specific examples of the divalent organic group include an alkylene, an aliphatic ring, an aromatic ring, Heterocycles and organic groups that combine these, and unsaturated bonds, ether bonds (one O—), ketone bonds (one CO), ester bonds (one COO), thioether bonds (one S— ), Amino bonds (one NH), amide bonds (one CONH), silyl bonds (one Si—), siloxane bonds (SiO 2), and the like.

[0031] X ² is a monovalent organic group, and specific examples thereof include an alkyl group, an alkoxy group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and an organic group having a combination force thereof. , Unsaturated bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), thioether bond (one S), amino bond (one NH), amide bond (one CON H), silyl bond (One Si—), a siloxane bond (one SiO 2), and the like may be included.

[0032] In addition, X ² is ^{^{- R 1 -, - X 1}} -, -CH-, and - double and one selected from NH

2

Form an elemental ring structure.

In the above examples, examples of the aliphatic ring or cycloaliphatic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, decahydronaphthalene, and norobornane. A ring structure. Examples of the aromatic ring or aromatic group include ring structures such as benzene and naphthalene. Examples of the heterocyclic ring or heterocyclic group include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine. Examples of the alkyl group, alkoxy group, and alkylene include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and alkylene.

[0033] X ¹ and X ² may have a substituent! /. Specific examples of the substituent include alkyl Group, alkoxy group, hydroxyl group, carboxyl group, and the like.

As the amine compound (b) in the present invention, for example, amine compounds represented by the following formulas (m) to (V) can be exemplified.

[0034] [Chemical 8]

H ₂ N— R ¹ — X ³ -R ¹ — NH ₂ (iii)

H ₂ N— R ^ X ⁴ — NH— X ⁵ — R ¹ — NH ₂ (iv)

H ₂ N— R ¹ — X ⁶ -NH— X ⁷ — NH— X ⁸ -R ¹ — NH ₂ (v)

However, R ¹ in the formula is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —

2 3 2 3 represents an alkylene or an aliphatic ring, and H ¹ — R ¹ — and — R ¹ — NH have the same or different R ¹

twenty two

It may be.

[0035] X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ represent a single bond or a divalent organic group, and specific examples of the divalent organic group include alkylene, an aliphatic ring, Organic groups consisting of aromatic rings, heterocycles, and combinations of these include unsaturated bonds, ether bonds (one o-), ketone bonds (one CO), ester bonds (one COO), thioethers. A bond (one S—), an amino bond (NH), an amide bond (one CONH), a silyl bond (one Si—), a siloxane bond (one SiO—), and the like may be included.

In the above examples, as the aliphatic ring or cycloaliphatic group, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, deca And ring structures such as hydronaphthalene and norobornane. Examples of the aromatic ring or aromatic group include ring structures such as benzene and naphthalene. Examples of the heterocyclic ring or heterocyclic group include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine. Examples of the alkylene include alkylene having 1 to 20 carbon atoms.

X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ may have a substituent. Specific examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, and a carboxyl group. Examples of the amine compound (c) in the present invention include amine compounds represented by the following formulas (i), (ii), (iv) and (V).

[0037] [Chemical 9]

H ₂ N— R ¹ to X ¹ -CH ₂ — N to X ² (i)

H

H ₂ N— R ¹ — X ¹ — N-CH ₂ -X ² (ϋ)

H

[0038] [Chemical 10]

H ₂ N— R ^ -X ⁴ — NH— X ⁵ — R ¹ — NH ₂ (iv) H ₂ N— R ¹ — X ⁶ -NH— X ⁷ — NH— X ⁸ -R ¹ — NH ₂ (v ) However, R ¹ in the formula is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —

twenty two

It may be.

[0039] X ¹ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ represent a single bond or a divalent organic group, and specific examples of the divalent organic group include alkylene, an aliphatic ring, Organic groups consisting of aromatic rings, heterocycles, and combinations of these include unsaturated bonds, ether bonds (one o-), ketone bonds (one CO), ester bonds (one COO), thioethers. A bond (one S—), an amino bond (NH), an amide bond (one CONH), a silyl bond (one Si—), a siloxane bond (one SiO—), and the like may be included.

X ² is a monovalent organic group, and specific examples thereof include an alkyl group, an alkoxy group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and an organic group having a combination force thereof. Bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), thioether bond (one S), amino bond (one NH), amide bond (one CON H), silyl bond (Si) , Including siloxane bonds (SiO 2), etc.

[0040] In addition, the formula (i), the X ² of ^{(ii) - R 1 -,} - X 1 -, -CH-, and - any force NH and double

2

Form an elemental ring structure. In the above examples, examples of the aliphatic ring or cycloaliphatic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, decahydronaphthalene, and norobornane. A ring structure. Examples of the aromatic ring or aromatic group include ring structures such as benzene and naphthalene. Examples of the heterocyclic ring or heterocyclic group include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine. Examples of the alkyl group, alkoxy group, and alkylene include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and alkylene.

[0041] X ¹ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ may have a substituent! /. Specific examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, and a carboxyl group. From the viewpoint that the amine compound (a), the amine compound (b) or the amine compound (c) does not deteriorate the physical properties of the polyimide even in the film, the molecular weight of the compound is preferably 1000 or less. Preferably it is 500 or less, Especially preferably, it is 300 or less.

Specific examples of the amine compound (a) or the amine compound (b) include the following, but are not limited thereto. Two or more amine compounds may be used in combination.

[0042] [Table 1]

2]

3]

Four]

Five]

[0047] Specific examples of the amine compound (c) include No. 1 to No. 50, No. 71 to No. 76, No. 93 to N ο.102, and Νο.106 to Νο.108. It is not limited to these. Two or more amine compounds may be used in combination.

In the coating liquids {1} and {2} of the present invention, the solvent-soluble polyimide and the imidyl polymer soluble in the solvent are polymers having an imide bond in the repeating unit, and an organic solvent. It refers to what can be dissolved.

[0048] A solvent-soluble polyimide used in the present invention and a solvent-soluble imide include those in which a part of the imide group contained in the repeating unit is ring-opened to form an amic acid group or an amic acid ester group. Included in the category of chemical polymers. Imi contained in polymers having these imide bonds The ratio of dodo groups can be expressed as an imidization rate as shown in the following formula.

Imide ratio = number of imide groups ÷ (number of imide groups + number of amide acid groups + number of amide acid ester groups) These imidation rates are determined by dissolving the polyimide in d-DMSO (dimethylsulfoxide d).

6 6 Dissolved and measured by ¹ H-NMR, derived from the above-mentioned amic acid group and amic acid ester group based on the integrated value of the proton peak derived from the structure that does not change even when the imide group is opened. This can be confirmed by comparing the integrated values of NH proton peaks.

[0049] The imidation ratio of the solvent-soluble polyimide used in the coating solution of the present invention and the imidized polymer soluble in the solvent is not particularly limited. Usually, the higher the imidization rate, the lower the solubility of the polyimide in the solvent. As a result, if the solution cannot be dissolved at the required concentration, the imidization rate may be lowered appropriately. In view of the purpose of using a polymer that has been imidized in advance, the imidization rate is preferably 10% or more. In addition, when used as a liquid crystal aligning agent, the reason for obtaining good liquid crystal alignment or good electrical properties. The imidity ratio is preferably 40% or more, more preferably 60% or more. Particularly preferably, it is 80% or more.

[0050] The molecular weight of the solvent-soluble polyimide and the solvent-soluble imidopolymer is not particularly limited, but it is 2 in terms of weight average molecular weight from the viewpoints of handling and stability of characteristics when a film is formed. 000 to 200,000 force, more preferably 4,000 to 50,000. The molecular weight is determined by GPC (gel permeation chromatography).

The structure of the solvent-soluble polyimide used in the coating solution of {1} of the present invention is not particularly limited, but can be obtained relatively easily by using tetracarboxylic dianhydride and diamine as raw materials. For this reason, a polyimide having a repeating unit represented by the following formula (I) is preferred.

[0051] Also, the imidized polymer soluble in the solvent used in the coating solution of {2} of the present invention is a reaction between tetraforce rubonic acid dianhydride and diamine containing an amine compound (c). The force obtained by imidizing the polyimide precursor obtained is obtained using diamine as a main raw material, and the polyimide having a repeating unit represented by the following formula (I) is used as a basic structure in the same manner as {1}. Yes.

[0052] Further, the imidized polymer soluble in the solvent used in the coating solution of {1} of the present invention is a specific amine polymer in a part of the polyimide having a repeating unit represented by the following formula (I). Compound (a) and The amine group represented by —R ¹ —NH of the amine compound in which the biamine compound (b) force is also selected,

2

If the polyimide has a structure bonded to the imide carbonyl group by a reaction involving ring opening of the imide group, or the polyimide has an imido ratio of less than 100%, the carboxyl group or amide acid of the amide acid group It has a structure in which the ester group is bonded to the carboxyester group.

[0053] Further, the imidyl polymer soluble in the solvent used in the coating solution of {2} is selected from a specific amine compound (c) force on a polyimide having a repeating unit represented by the following formula (I). Amino group represented by —R ¹ — NH of the amine compound to be reacted with tetracarboxylic dianhydride

2

The force taken into the imide as a molecular end, a bonded state in which a part of the polyimide having the repeating unit represented by the formula (I) is ring-opened to the imide carbonyl group, or the amide acid group It has a structure bonded to a carboxyl group of a carboxyl group or an amic acid ester group.

[0054] [Chemical 11]

[0055] In the above formula (I), A represents a tetravalent organic group, and B represents a divalent organic group.

In the above formula (I), the structure of A is not particularly limited. In addition, the structure of A may be one type, or multiple types may be mixed. Specific examples of A are as follows.

[0056] [Table 6]

[0058] Of these, A-6, A-16, A-18 to A-22, and A-25 are preferable because they have high solubility even with polyimide having a high imidization rate.

In addition, when it has an alicyclic structure or an aliphatic structure such as a force of -1 to -25, the voltage holding ratio of the liquid crystal cell is improved when it is used as a liquid crystal alignment film. Good.

In the formula (I), the structure of B is not particularly limited. In addition, the structure of B may be one type or a mixture of multiple types. Specific examples of B are as follows.

[0059] [Table 8]

[Οΐ 挲] [Ϊ900]

L0ZP90IL00Zdt / L3d 93 8 0 Difficult 00Z OAV

11]

12]

[0064] Of these, when part or all of B is B-80 to B-101, the pretilt angle of the liquid crystal can be increased when the liquid crystal alignment film is formed.

The polyimide having the repeating unit represented by the above formula (I) corresponds to the tetracarboxylic dianhydride having the corresponding structure of A as represented by the following formula (II) and the following formula (III) according to a conventional method. It can be obtained by reacting with a diamine having the structure of B to obtain a polyimide precursor, which is dehydrated and cyclized.

[0065] [Chemical 12]

[0066] [Chemical 13]

[0067] Also, in the case of obtaining an imidopolymer soluble in the solvent used in the coating solution of {2}, the above formula

It can be obtained by reacting the tetracarboxylic dianhydride of (II), the diamine of the above formula (III) and the amine compound () to form a polyimide precursor, which is dehydrated and cyclized. If the amount of the amine compound (c) used is too small, the effect of the moisture absorption stability of the coating solution will not be sufficiently exerted, so lmol% in the total amount of the diamine of formula (III) and the amine compound (c) More preferably, the amount is 2 mol% Amine compound (c) containing one primary amino group in the molecule limits the molecular weight of the imidyl polymer soluble in the resulting solvent. 15 mol% or less is preferable, more preferably 10 mol% or less, particularly preferably 5 mol% or less, and the amine compound (c) having 2 or more primary amino groups contained in the molecule is Since it plays the role of diamine of formula (III), di of formula (III) Be replaced by Min and Amini 匕合 was the total amount of (c) in this,.

The reaction for obtaining the polyimide precursor is usually carried out in an organic solvent at −20 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 80 ° C.

[0068] At this time, the proportion of tetracarboxylic dianhydride and diamine used is such that the acid anhydride group contained in tetracarboxylic dianhydride is 0.5 to 1 equivalent of amino group contained in diamine. It is preferable that it is -1.5 equivalent, More preferably, it is 0.8-1.2 equivalent. In the case of reacting the amine compound (c), the acid anhydride contained in the tetracarboxylic dianhydride with respect to the amino group obtained by combining the amino group contained in the diamine and the amino group contained in the amine compound. It is the ratio of the physical group.

[0069] As the organic solvent used in the above reaction, a polyimide precursor to be generated is dissolved. That is not particularly limited. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ —Butyloraton. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use an organic solvent that has been dehydrated and dried as much as possible.

Common methods for dehydrating and ring-closing polyimide precursors include thermal imidization by heating the polyimide precursor solution as it is, and chemical imidization by adding a catalyst to the polyimide precursor solution, but imidization at a relatively low temperature. Chemical imidization, in which the reaction proceeds, is preferred because the molecular weight of the resulting polyimide is less likely to decrease.

[0070] Chemical imidization can be performed by stirring a polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is 20 to 250 ° C, preferably 0 to 180 ° C. Higher reaction temperature Force of S-imide is too high. If it is too high, the molecular weight of the polyimide may decrease. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction. Examples of the basic catalyst to be used include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. As the organic solvent, the solvent used in the polyamic acid polymerization reaction described above can be used. The imidity ratio due to chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0071] Since the added catalyst remains in the solution of the polyimide solution obtained in this way, it is preferable to throw this polyimide solution into a stirring poor solvent and recover the precipitate. Yes. Although it does not specifically limit as a poor solvent used for the precipitation collection | recovery of a polyimide, Methanol, acetone, hexane, a butyl cellosolve, a heptane, a methyl ethyl ketone, a methyl isobutyl ketone, ethanol, toluene, benzene etc. can be illustrated. The polyimide precipitated by adding it to a poor solvent can be recovered by filtration and washing, and then dried at normal temperature or under reduced pressure at room temperature or by heating.

The reaction between the solvent-soluble polyimide and the amine compound (a) or the amine compound (b) can be performed as follows in the coating solution of {1}.

First, solvent-soluble polyimide is dissolved in an organic solvent to obtain a solution. At this time, if the polyimide is difficult to dissolve, it may be heated. If the heating temperature is too high, the molecular weight of the polyimide may decrease, so 30-100 ° C is preferred.

[0072] The concentration of the polyimide solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, because the polyimide and the amine compound can be reacted efficiently and uniformly. Preferably it is 3-10 mass%. Also, the amine compound is represented by —R ¹ —NH.

2 If there are two or more amino groups, if the polyimide concentration is too high, the polyimides may form a three-dimensional structure with the amine compound and the solubility may be reduced. It is preferable to be less than mass%.

[0073] The solvent is not particularly limited as long as the resin is completely dissolved within the above concentration range. Specific examples include N, N dimethylformamide, N, N dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, 2-pyrrolidone, N-ethylpyrrolidone, N vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea. , Pyridine, dimethylsulfone, hexamethylsulfoxide, y-butyrolatatone, 1,3 dimethylimidazolidinone. Two or more of these solvents may be used in combination. However, since Lataton solvents such as y-petit-mouthed rataton react easily with aliphatic amino groups and may consume amine compounds, N, N dimethylformamide is N-methyl 2-pyrrolidone, etc. It is preferable to use the solvent. If you want to use a rataton solvent such as y-petit-mouth rataton as the main solvent, first react the amine compound with the polyimide using a solvent other than the rataton solvent, and then put this solution into an appropriate poor solvent for recovery. Then, it may be dissolved again in the rataton solvent. As a poor solvent at this time, Examples include butanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. The polyimide precipitated by pouring into a poor solvent can be recovered by filtration, washing, and drying at normal temperature or reduced pressure at room temperature or by heating.

Next, an amine compound selected from the amine compound (a) and the amine compound (b) is added to the polyimide solution, and the mixture is stirred at room temperature or under heating conditions.

If the amount of the amine compound added is too small, the effect of the moisture absorption stability of the coating solution will not be sufficiently exerted, and if it is too large, for example, in the liquid crystal alignment film, the orientation of the liquid crystal will be reduced. 1 to 15 parts by mass is more preferable, and 2 to 5 parts by mass is particularly preferable, with respect to 100 parts by mass of the solvent-soluble polyimide, because the characteristics are deteriorated. The amine compound may be added directly to the solvent-soluble polyimide solution, but it is preferable to add the aminey compound after making a solution with a concentration of 0.1 to 10% by mass with an appropriate solvent. Examples of the solvent include the solvent of the solvent-soluble polyimide described above. In this case as well, _latonic solvents such as petit _latatotone may react with the aliphatic amino group and consume the aminic compound immediately. Therefore, solvents such as Ν, ジメチル dimethylformamide 等 methyl-2-pyrrolidone, etc. Preferred to use.

[0075] The temperature during the reaction is preferably 25 to 150 ° C, more preferably 30 to 100 ° C, because the polyimide and the amine compound react efficiently and side reactions do not easily occur. It is particularly preferably 40 to 80 ° C. If the temperature is too high, the soluble polyimide may be hydrolyzed.

The reaction time varies depending on the reactivity between the solvent-soluble polyimide and the amine compound and the temperature at which the reaction is carried out. To give a standard example, it is 6 to 48 hours at 40 to 80 ° C. The structure of the polyamic acid used in the coating solution is not particularly limited, but is represented by the following formula (IV) because it can be obtained relatively easily by using tetraforce rubonic acid dianhydride and diamine as raw materials. Preferable is a polyamic acid having a repeating unit.

[0076] [Chemical 14]

[0077] In the above formula (IV), A 'represents a tetravalent organic group, and B' represents a divalent organic group.

The polyamic acid having a repeating unit represented by the above formula (IV) is a tetracarboxylic acid having the structure of A ′, as shown in the method for synthesizing a polyimide precursor for obtaining the solvent-soluble polyimide described above. It can be obtained by reacting a dianhydride and a diamine having the structure of B ′ in an organic solvent.

[0078] The molecular weight of the polyamic acid is not particularly limited, but a weight average molecular weight of 2,000 to 200,000 is more preferable and 5 is more preferable from the viewpoints of handling and stability of characteristics when a film is formed. , 00000 to 100,000. The molecular weight was determined by GPC (gel permeation chromatography).

In the above formula (IV), the structure of A ′ is not particularly limited. Further, the structure of A ′ may be one type, or may have different A ′ structures and a plurality of different types of repeating units may be mixed. As a specific example of A ′, the structure exemplified in the above A can be mentioned. In the formula (IV), the structure of B ′ is not particularly limited. Further, the structure of B ′ may be one type, or may have a different B ′ structure, and a plurality of different types may be mixed as a repeating unit. If the specific example of B 'is given, the structure illustrated by said B will be mentioned.

[0079] In order to obtain the coating solution of the present invention, it is soluble in a solvent of a product obtained by reacting a solvent-soluble polyimide with an amine compound selected from amine compounds (a) and (b). What is necessary is just to mix the solution of an imidyl polymer (henceforth a specific product) and the solution of a polyamic acid in arbitrary ratios. In addition, an imidyl polymer (hereinafter referred to as a specific polyimide) soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride and a diamine containing an amine compound (c). And a solution of polyamic acid may be mixed at an arbitrary ratio. [0080] Even if the solution of the specific product is used as it is as the reaction solution of the specific product, the reaction solution is put into an appropriate poor solvent, and after the specific product is recovered, it is dissolved in the solvent and used again. May be. Examples of the poor solvent at this time include water, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. Solvents for re-dissolution include N, N dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, 2-pyrididone, N ethylpyrrolidone, N bull pyrrolidone Dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolacton, 1,3 dimethylimidazolidinone, and the like. These redissolving solvents can also be used as solvents for dissolving the specific polyimide.

[0081] In the coating liquid of the present invention, the specific product and the specific polyimide may be used in combination. The ratio of the specific product, specific polyimide, and polyamic acid is arbitrary. Because a liquid crystal alignment film with good characteristics can be obtained, the polyamic mass in the mass of the specific product, the specific polyimide, and the polyamic acid is combined. The acid ratio is more preferably 20 to 99% by mass, more preferably 40 to 95% by mass, and particularly preferably 60 to 90% by mass.

That is, the ratio of the polyamic acid in the mass of the specific product and the soot or the specific polyimide and the polyamic acid is preferably 20 to 99% by mass, more preferably 40 to 95% by mass, and particularly preferably. Is 60-90% by mass.

[0082] The concentration of the solid component in the coating solution can be appropriately changed depending on the thickness of the coating film to be formed. To obtain a uniform coating film, 0.1 is required. From the viewpoint of storage stability that is preferably at least 30% by mass, it is preferably at most 30% by mass. In addition, 1 to 10% by mass is preferable because a coating film having an appropriate thickness can be obtained as a liquid crystal alignment film.

[0083] The solvent contained in the coating solution of the present invention may contain a solvent for improving the printability in addition to the above-described re-dissolving solvent for the specific product. Specific examples thereof include ethinorecerosonolev, butinorecellosonoleb, ethinorecanorebitonore, butinorecanolebitonore, ethenorecarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-etoxy-2- Propanol, 1-butoxy 2-propanol, 1-phenoxy 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene Lopyleneglycol 1 Monomethylolate 2—Acetate, Propylene glycol 1 —Monoethyl ether—2-Acetate, Dipropylene glycol, 2- (2-Ethoxypropyloxy) propanol, Lactic acid methyl ester, Lactic acid ethyl ester, Lactic acid Examples thereof include solvents having low surface tension such as n-propyl pill ester, lactic acid n butyl ester, and lactyl isoamyl ester. It is known that the coating film uniformity is improved at the time of application to the substrate by mixing these appropriately, and it is also suitably used in the coating liquid of the present invention.

[0084] When the coating liquid of the present invention is used as a liquid crystal aligning agent, an amide solvent such as N, N dimethylformamide N-methyl-2pyrrolidone is contained in an amount of 50% by mass or more of the coating liquid. When the thin film is formed by a printing method such as flexographic printing, the film thickness uniformity is improved, which is preferable.

The liquid crystal aligning agent of the present invention comprises the above coating solution, and an additive such as a silane coupling agent may be added to improve the adhesion of the liquid crystal aligning film to the substrate. In addition, since the liquid crystal aligning agent needs to form a thin film of 300 nm or less on the substrate, when using the coating liquid as the liquid crystal aligning agent, it is filtered with a membrane filter having a pore diameter of 0.1 m to l μm. U prefer that.

[0085] The liquid crystal aligning agent of the present invention increases the entanglement of the polymer by appropriately suppressing the phase separation between the imidyl copolymer soluble in the solvent and the polyamic acid when formed into a coating film. In addition, it has the effect of being sharpened against the rubbing process. Furthermore, compared with the case where no amine compound is used, the electrical characteristics of the liquid crystal display element, such as the ease of draining the stored charge and the voltage holding ratio, tend to be improved.

The liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking, and is used for aligning liquid crystals in a predetermined direction. .

The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used. Use of a substrate on which is formed is also preferable from the viewpoint of simplifying the process. In addition, the reflective liquid crystal display element can be used with an opaque object such as a silicon wafer as long as it is only on one side of the substrate. Can also use materials that reflect light, such as aluminum.

[0087] Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, and ink jet. Industrially, transfer printing such as flexographic printing is widely used from the viewpoint of productivity. The liquid crystal aligning agent of the present invention is also preferably used.

The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is constant for each substrate, or is not baked immediately after coating! It is preferable to include a drying step. The drying means is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed due to transport of the substrate or the like. As a specific example, a method of drying on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes is used.

The substrate coated with the liquid crystal aligning agent can be baked at any temperature of 100 to 350 ° C, preferably 150 ° C to 300 ° C, more preferably 180 ° C to 250 ° C. It is. Also, it is more preferable to fire at a temperature of 10 ° C or higher than the heat treatment temperature required for the liquid crystal cell manufacturing process, such as curing the sealant.

[0088] If the thickness of the coating film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm. , More preferably 10: LOOnm.

When the liquid crystal is aligned horizontally or tilted, the fired coating film is treated with rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a liquid crystal alignment agent-powered substrate with a liquid crystal alignment film of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

[0089] To give an example of liquid crystal cell production, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and sealed by injecting liquid crystal under reduced pressure, or after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacer is dispersed, the substrate is bonded and sealed. The method etc. which perform can be illustrated. The thickness of the spacer at this time is preferably 1 to 30 m, more preferably 2 to 10 μm. The liquid crystal display element of the present invention includes a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an OCB liquid crystal display element, a horizontal electric field type liquid crystal display element, and a vertical alignment type liquid crystal display. It is suitably used for display elements of various methods using nematic liquid crystal such as elements. Further, by selecting the liquid crystal to be used, it can also be used for a ferroelectric and antiferroelectric liquid crystal display element.

The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

Example

[0091] In Synthesis Examples 1, the abbreviations and structures of tetracarboxylic dianhydride and diamine used for the synthesis of solvent-soluble polyimide, solvent-soluble imidized polymer, or polyamic acid are shown below. Show.

[0092] [Chemical 15]

[0093] [Chemical 16]

[0094] [Chemical 17]

[0095] [Chemical 18]

DA12 DA13

[0096] Abbreviations of organic solvents used in Synthesis Examples, Examples, etc. are as follows.

NMP: N-methyl 2-pyrrolidone

BCS: Butinorecero Sorelev

GBL: _ΎButiro Lataton

The abbreviations of the amine compounds used in the examples are as follows. (No. in parenthesis is the number of the amine compound shown in the specification.)

ΑΜ1: (Νο.94) Triethylenetetraamine

AM2: (No.37) (Aminoethylaminomethyl) phenethyltrimethoxysilane

AM3: (No.32) N- (2-aminoethyl) -3-aminominotrimethoxysilane

AM4: (No. 47) (3-Trimethoxysilylpropyl) diethylenetriamine

AM5: (No.34) N- (2-aminoethyl) -3-amino

AM6: (No.35) N- (2-aminoethyl) -3-amino AM7: (No.95): Ν, Ν, -bis (2-aminoethinole) -1,3-propanediamin

ΑΜ8: (Νο.36): Ν- (2-Aminoethyl) -11-aminoundecyltrimethoxysilane

ΑΜ9: (Νο.38): Ν- (6-Aminohexyl) aminopropyltrimethoxysilane

AM10 (No 55): 1,6-Diaminohexane

AM11 (No 71): Diethylenetriamine

AM12 (No 73): Dipropylenetriamine

AM13 (No 11): n-propyl-1,3-propanedia

AM14 (No 51): Ethylenediamine

AM15 (No 56): 1,12-Diaminododecane

AM16 (No 65): p-Xylylenediamine

AM17 (No 27): 1- (2-Aminoethyl) piperazine

The molecular weights of the solvent-soluble polyimide, the solvent-soluble imidopolymer, and the polyamic acid in the synthesis examples are as follows: Shodex's room temperature gel permeation chromatography (GPC) apparatus (GPC-101), Shodex's column ( Measurement was performed as follows using KD-803 and KD-805).

Column temperature: 50 ° C

Eluent: Ν, Ν-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr'H2 0) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) force S30 mmol / L, tetrahydrofuran ( (THF) is 10ml / L)

Flow rate: l.OmLZ min

Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.

[0098] <Measurement of imidization ratio>

The imido ratio of the solvent-soluble polyimide in the synthesis example and the imido polymer soluble in the solvent was measured as follows. Add 20 mg of polyimide powder to the NMR sample tube (N MR sampling tube standard φ5 manufactured by Kusano Kagakusha) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d, 0.05% TMS (tetramethylsilane) mixture) Hesitate and apply ultrasound It was completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA 500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and the proton peak integrated value derived from the NH group of amic acid that appears in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using and.

Imidi ratio (%) = (l-a -x / y) X 100

In the above formula, X is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and a is one NH group proton of the amic acid in the case of polyamic acid (imido ratio is 0%). Is the number ratio of the reference proton to.

[0099] (Synthesis Example 1)

A polyamic acid solution was prepared by reacting 150.14 g (0.5 mol) of TDA, 48.67 g (0.45 mol) of DA1, and 18.83 g (0.05 mol) of DA2 in 1233 g of NMP at 50 ° C. for 24 hours. This polyamic acid solution was diluted to 5% by mass with NMP, and 237.9 g of pyridine and 510.6 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 17.4 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white polyimide powder.

The obtained solvent-soluble polyimide had a number average molecular weight of 9,273 and a weight average molecular weight of 18,815. The imidization ratio was 84%.

[0100] (Synthesis example 2)

CBDA 98.05 g (0.5 mol), PMDA 95.98 g (0.44 mol) and DA3 198.27 g (1.0 mol) were reacted in a mixed solvent of NMP lll lg and GBL lll lg at room temperature for 5 hours to polyamic. An acid solution was prepared. This polyamic acid had a number average molecular weight of 11,067 and a weight average molecular weight of 26,270.

[0101] {Example 1}

3 g of the polyimide powder obtained in Synthesis Example 1 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours. To this solution was added 3.0 g (0.15 g as an amine compound) of 5 mass ⁰ / oNMP solution of triethylenetetraamine (No. 94 amine compound), and the polyimide concentration in this solution was 6 mass. the NMP 9.5 g so that the ^_0/0 Ka卩E and 20h stirred at 50 ° C. At this time, the addition amount of the amine compound is 5 parts by mass with respect to 100 parts by mass of the polyimide. NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid power of 3% by mass, NMP of 59% by mass, GBL of 20% by mass and BCS of 15% by mass.

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is NMPZGBLZBCS = 66Z16Z12 by mass ratio.

[0102] (Synthesis Example 3)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA and 19.83 g (0.1 mol) of DA3 in 283 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.1 g of pyridine and 15.4 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered and dried to obtain a white polyimide powder. The solvent-soluble polyimide obtained had a number average molecular weight of 13,651 and a weight average molecular weight of 48,092. The imidation ratio was 81%.

[0103] {Example 2}

A coating solution of the present invention was obtained in the same manner as in Example 1 except that the polyimide powder obtained in Synthesis Example 3 was used.

{Examples 3 to 29}

A coating solution of the present invention was obtained in the same manner as in Example 1 except that the addition amount or type of the amine compound was changed as follows. When 3 parts by mass of the amine compound is added, a 3% by weight NMP solution of the amine compound is added. When 2 parts by mass is added, the same 2% by weight NMP solution is added. When 1 part by mass of the mass% NMP solution was added, the same 1 mass% NMP solution was added.

Example No Amine compound Addition amount (parts by mass)

1 AMI 0.15g (5)

3 AMI 0.09g (3)

4 AMI 0.06g (2)

5 AM2 0.09g (3)

6 AM2 0.15g (5) 7 AM2 0.30g (10)

8 AM3 0.15g (5)

9 AM3 0.30g (10)

10 AM4 0.15g (5)

11 AM4 0.30g (10)

12 AM5 0.09g (3)

13 AM5 0.15g (5)

14 AM5 0.30g (10)

15 AM6 0.15g (5)

16 AM6 0.30g (10)

17 AM7 0.15g (5)

18 AM8 0.15g (5)

19 AM8 0.30g (10)

20 AM9 0.15g (5)

21 AM10 0.15g: 5)

22 AM11 0.03 g: 1)

23 AM11 0.09g: 3)

24 AM12 0.09g: 3)

25 AM13 0.15g: 5)

26 AM 14 0.15g: 5)

27 AM15 0.15g: 5)

28 AM16 0.15g: 5)

29 AM17 0.15g: 5)

{Comparative Example 1}

In Example 1, except that the amine compound was not added to the solvent-soluble polyimide solution and diluted to 6% by mass with NMP, and this was mixed with the dilute solution of polyamic acid. A coating solution for comparison was obtained in the same manner as in 1.

{Comparative Example 2} A coating solution for comparison was obtained in the same manner as in Example 1, except that 3-aminopropylmethyljetoxysilane was used as the amine compound in Example 1.

{Comparative Example 3}

A coating solution for comparison was obtained in the same manner as in Example 1 except that 2- (4-aminophenol) ethylamine was used as the amine compound in Example 1.

{Comparative Example 4}

A coating solution for comparison was obtained in the same manner as in Example 1 except that bis (trimethoxysilylpropyl) amine was used as the amine compound in Example 1.

{Comparative Example 5}

A coating solution for comparison was obtained in the same manner as in Example 1 except that N-methylaminopropyltrimethoxysilane was used as the amine compound in Example 1.

About 0.1 ml of each of the coating solutions prepared in the above examples or comparative examples was dropped on a Cr film-formed glass substrate (chromium-deposited glass substrate) and left in an environment at a temperature of 23 ° C. and a humidity of 50%. The vicinity of the edge and the center of the droplet were observed with a microscope every hour. The observation was performed at 100x magnification near the edge of the droplet and at 50x magnification near the center of the droplet.

As a result, in the coating liquids of Examples 1 to 29, no agglomerates were observed even after 6 hours. Aggregates were observed near the center.

{Example 30}

In Example 1, except that the dilute solution of polyamic acid to be mixed was prepared so that polyamic acid was 6% by mass, NMP was 39.5% by mass, GBL was 39.5% by mass, and BCS was 15% by mass. Similarly, the coating liquid of the present invention was obtained. The solvent composition of this coating solution is NMP / GBL / BCS = 50.3 / 31.6,12 by mass ratio.

{Example 31}

In Example 1, the dilute solution of polyamic acid to be mixed was prepared in the same manner as in Example 1 except that the polyamic acid was adjusted to 6% by mass, NMP 20% by mass, GBL 59% by mass, and BCS 15% by mass. Similarly, the coating liquid of the present invention was obtained. The solvent composition of this coating solution is N MP / GBL / BCS = 34.7 / 7 / 47.2,12.

[0106] {Example 32}

3 g of the polyimide powder obtained in Synthesis Example 1 was dissolved in 34.5 g of GBL by stirring at 50 ° C. for 20 hours. To this solution, add 3 mass ⁰ / oGBL solution of triethylenetetraamine (No.94 amine compound) 3. Og (0.15 g as amine compound), and then add polyimide concentration in this solution GBL (9.5 g) was added so that the amount was 6 mass%, and the mixture was stirred at 50 ° C for 20 hours. The amount of the amine compound added at this time is 5 parts by mass with respect to 100 parts by mass of the polyimide.

NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid strength of 3% by mass, NMP of 20% by mass, GBL of 59% by mass and BCS of 15% by mass.

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is NMPZGBLZBCS = 16Z66Z12 by mass ratio.

[0107] {Examples 33 to 36}

A coating solution of the present invention was obtained in the same manner as in Example 30, except that the type of amine compound was changed as follows.

Example No. Aminy compound

33 AM2

34 AM5

35 AM7

36 AM10

[0108] {Examples 37 to 39}

A coating solution of the present invention was obtained in the same manner as in Example 31 except that the type of amine compound was changed as follows.

Example No. Aminy compound

37 AM2

38 AM5

39 AM7 [0109] {Examples 40 to 46}

A coating solution of the present invention was obtained in the same manner as in Example 32 except that the type of amine compound was changed as follows.

Example No. Aminy compound

40 AM2

41 AM3

42 AM4

43 AM5

44 AM6

45 AM7

46 AM10

(Synthesis Example 4)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.46 g (0.0875 mol) of DA1, and 4.71 g (0.0125 mol) of DA2 in 251 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.1 g of pyridine and 17.3 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,195 and a weight average molecular weight of 19,235. The imidation ratio was 83%.

[0110] (Synthesis Example 5)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.65 g (0.015 mol) of DA2 in 254 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17. lg of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,324 and a weight average molecular weight of 19,244. The imidation ratio was 83%.

[0111] (Synthesis Example 6) A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DAI, and 5.23 g (0.015 mol) of DA4 in 252 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and further 8.0 g of pyridine and 17.2 g of acetic anhydride were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,834 and a weight average molecular weight of 21,659. The imidation ratio was 83%.

[0112] (Synthesis Example 7)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 8.56 g (0.08 mol) of DA1, and 5.85 g (0.02 mol) of DA5 in NMP 252 g at 50 ° C for 24 hours. . 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and further 8.0 g of pyridine and 17.2 g of anhydrous acetic acid were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,111 and a weight average molecular weight of 18,045. Further, the imido ratio was 83%.

[0113] (Synthesis Example 8)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 8.65 g (0.08 mol) of DA1, and 7.61 g (0.02 mol) of DA6 in NMP 185 g at 50 ° C. for 24 hours. . 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, 10.3 g of pyridine and 22. lg of acetic anhydride were further added as an imido catalyst and reacted at 35 ° C. for 3 hours. This solution was put into 0.8 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 6,446 and a weight average molecular weight of 13,971. The imidation ratio was 74%.

[0114] (Synthesis Example 9)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.71 g (0.015 mol) of DA6 in NMP 255 g at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were further added as an imido catalyst and reacted at 35 ° C. for 3 hours. This solution in 0.6 L methanol The precipitate obtained was filtered off and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,943 and a weight average molecular weight of 14,365. The imidation ratio was 76%.

[0115] (Synthesis Example 10)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 6.11 g (0.015 mol) of DA7 in 257 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 16.9 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 5,735 and a weight average molecular weight of 12,670. The imidation ratio was 83%.

[0116] (Synthesis Example 11)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.92 g (0.015 mol) of DA8 in 256 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,495 and a weight average molecular weight of 22,294. The imidization ratio was 84%.

[0117] (Synthesis Example 12)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 6.04 g (0.015 mol) of DA9 in 257 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 16.9 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,775 and a weight average molecular weight of 23,308. The imidization ratio was 84%.

[0118] (Synthesis Example 13) A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DAI, and 5.44 g (0.015 mol) of DA10 in 253 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.0 g of pyridine and 17.1 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,367 and a weight average molecular weight of 18,959. The imidization ratio was 84%.

[Synthesis Example 14]

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.80 g (0.015 mol) of DA11 in NMP 255 g at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,203 and a weight average molecular weight of 18,298. The imidization ratio was 84%.

[0120] (Synthesis Example 15)

A polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 12.26 g (0.09 mol) of DA12, and 3.77 g (0.01 mol) of DA2 in 261 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and further 7.7 g of pyridine and 16.6 g of acetic anhydride were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,634 and a weight average molecular weight of 17,655. The imidation ratio was 81%.

[0121] (Synthesis Example 16)

30.03 g (0.1 mol) of TDA and 19.83 g (0.1 mol) of DA13 were reacted in 329 g of NMP at 50 ° C. for 24 hours to prepare a polyamic acid solution. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 6.1 g of pyridine and 13.1 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was It was filtered and dried to obtain a white polyimide powder. The obtained solvent-soluble polyimide had a number average molecular weight of 18,197 and a weight average molecular weight of 70,609. The imidization rate was 90%.

[0122] (Synthesis Example 17)

A polyamic acid solution was prepared by reacting 19.22 g (0.098 mol) of CBDA, 16.26 g (0.08 mol) of DA14, and 5.85 g (0.02 mol) of DA5 in 234 g of NMP at room temperature for 24 hours. This polyamic Mick acid solution 50g diluted five mass ^_0/0 by NMP, pyridine 2.3 g, acetic anhydride 5.5g added as further imidization catalyst, and reacted for 3 hours at 50 ° C. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 12,988 and a weight average molecular weight of 30,324. The imidation ratio was 94%.

[0123] (Synthesis example 18)

TDA 15.02g (0.05mol), BODA 12.51g (0.05mol), DA1 9.73g (0.09mol), DA2 3.77g (0.01mol) in NMP 164g at 35 ° C 24 A polyamic acid solution was prepared by reacting for a time. 50 g of this polyamic acid solution was diluted to 7% by mass with NMP, and 9.6 g of pyridine and 6.2 g of acetic anhydride were further added as an imidation catalyst, followed by reaction at 100 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The obtained solvent-soluble polyimide had a number average molecular weight of 12,808 and a weight average molecular weight of 32,511. The imidization ratio was 85%.

[0124] (Synthesis Example 19)

A polyamic acid solution was prepared by reacting 18.43 g (0.094 mol) of CBDA and 19.83 g (0.1 mol) of DA3 in a mixed solvent of 108 g of NMP and 108 g of GBL at room temperature for 5 hours. This polyamic acid had a number average molecular weight of 16,951 and a weight average molecular weight of 37,292.

[0125] (Synthesis Example 20)

A polyamic acid solution was prepared by reacting 18.43 g (0.094 mol) of CBDA and 20.02 g (0.1 mol) of DA15 in a mixed solvent of 109 g of NMP and 109 g of GBL at room temperature for 5 hours. This polyamic acid had a number average molecular weight of 15,139 and a weight average molecular weight of 31,565.

[Synthesis Example 21] A polyamic acid solution was prepared by reacting 18.04 g (0.092 mol) of CBDA and 19.93 g (0.1 mol) of DA16 in a mixed solvent of NMP 171 g and GBL 17 lg at room temperature for 5 hours. This polyamic acid had a number average molecular weight of 20,821 and a weight average molecular weight of 49,970.

[0127] {Example 47}

3 g of the polyimide powder obtained in Synthesis Example 4 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours. To this solution, 3 wt ⁰ / ^oNMP solution was added (0.09 g as Amini匕合product) to 3.0 g, further polyimide concentration in the solution is 6 mass triethylenetetramine (Amin compound of No.94) the NMP 9.5 g so that the ^_0/0 Ka卩E and 20h stirred at 50 ° C. The added amount of the amine compound at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.

NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid power of 3% by mass, NMP of 59% by mass, GBL of 20% by mass and BCS of 15% by mass.

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is, in mass ratio, Example NoNMPZGBLZBCS = 66Zl6Zl2.

[0128] {Examples 48 to 58}

A coating solution of the present invention was obtained in the same manner as in Example 47 except that the polyimide powder was changed as follows.

Example 48 Polyimide powder obtained in Synthesis Example 5

Example 49 Polyimide powder obtained in Synthesis Example 6

Example 50 Polyimide powder obtained in Synthesis Example 7

Example 51 Polyimide powder obtained in Synthesis Example 8

Example 52 Polyimide powder obtained in Synthesis Example 9

Example 53 Polyimide powder obtained in Synthesis Example 10

Example 54 Polyimide powder obtained in Synthesis Example 11

Example 55 Polyimide powder obtained in Synthesis Example 12

Example 56 Polyimide powder obtained in Synthesis Example 13

Example 57 Polyimide powder obtained in Synthesis Example 14 Example 58 Polyimide powder obtained in Synthesis Example 15

[0129] {Example 59}

3 g of the polyimide powder obtained in Synthesis Example 16 was stirred and dissolved in 34.5 g of GBL at 50 ° C. for 20 hours. To this solution was added 3.0 g (0.15 g as an amine compound) of 3 mass ⁰ / oGBL solution of triethylenetetraamine (No. 94 amine compound), and the polyimide concentration in this solution was 6%. GBL 9.5g was added so that it might become the amount%, and it stirred at 50 degreeC for 20 hours. The amount of the amine compound added at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.

NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 19 to prepare a polyamic acid power of 3% by mass, NMP of 20% by mass, GBL of 59% by mass and BCS of 15% by mass.

[0130] {Example 60}

3 g of the polyimide powder obtained in Synthesis Example 17 was dissolved in 34.5 g of GBL by stirring at 50 ° C. for 20 hours. To this solution was added 3.0 g (0.15 g as an amine compound) of 3 mass ⁰ / oGBL solution of triethylenetetraamine (No. 94 amine compound), and the polyimide concentration in this solution was 6%. GBL 9.5g was added so that it might become the amount%, and it stirred at 50 degreeC for 20 hours. The amount of the amine compound added at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.

NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 20 to prepare a polyamic acid power of 3% by mass, NMP of 20% by mass, GBL of 59% by mass, and BCS of 15% by mass.

[0131] {Example 61}

3 g of the polyimide powder obtained in Synthesis Example 18 was stirred and dissolved in 23.5 g of NMP and 23.5 g of GBL at 50 ° C. for 20 hours. To this solution, (aminoethylaminomethyl) phenethyltrimethoxysilane It was added (0.03 g as Amini匕合). 1 mass ⁰ / OGBL solution 3.0g of (Amin compound of No.37), as further polyimide concentration in the solution becomes 5 mass ^_0/0 GBL 7.0 g was stirred and stirred at 50 ° C. for 20 hours. The amount of the amine compound added at this time is 1 part by mass with respect to 100 parts by mass of the polyimide.

NMP to the polyamic acid solution 40g obtained in Synthesis Example 20, GBL, the BCS was added, the polyamic acid force ^ mass ^_0/0, NMP is 17.75 mass ^_0/0, GBL is 52.25 mass ^_0/0, BCS is 25 mass ⁰ / Prepared to be _zero .

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is NMPZGBLZBCS = 22Z53Z20 by mass ratio.

[0132] {Example 62}

3 g of the polyimide powder obtained in Synthesis Example 1 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours. To this solution was added 3.Og (0.09 g as an amine compound) of 3 mass ⁰ / oNMP solution of triethylenetetraamine (No.94 amin compound), and the polyimide concentration in this solution was 6 NMP 9.5g was added so that it might become mass%, and it stirred at 50 degreeC for 20 hours. At this time, the addition amount of the amine compound is 3 parts by mass with respect to 100 parts by mass of the polyimide.

NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 19 to prepare a polyamic acid power of 3 mass%, NMP of 59 mass%, GBL of 20 mass%, and BCS of 15 mass%.

[0133] {Example 63}

In Example 62, NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 21 as a dilute solution of the polyamic acid to be mixed, and the polyamic acid strength was ¾ mass%, NMP was 39.5 mass%, A coating solution of the present invention was obtained in the same manner as in Example 62 except that GBL was 39.5% by mass and BCS was 15% by mass. The solvent composition of this coating solution is NMP / GBL / BCS = 50.3 / 31.6Z12 by mass ratio. [Synthesis Example 22]

A polyamic acid solution was prepared by reacting 9.81 g (0.05 mol) of CBDA, 9.60 g (0.044 mol) of PMDA, and 19.83 g (0.1 mol) of DA3 in 222 g of NMP at room temperature for 5 hours. This polyamic acid had a number average molecular weight of 10,893 and a weight average molecular weight of 25,972.

[0135] {Example 64}

3 g of the polyimide powder obtained in Synthesis Example 1 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours. 10 masses of (aminoethylaminomethyl) phenethyltrimethoxysilane (No. 37 amine compound) in this solution. / OGBL solution was added (0.30 g as Amini匕合product) and 3.0 g, even more NMP 9.5 g as polyimide concentration becomes 6 mass ^_0/0 of the solution Ka卩E at 50 ° C Stir for 20 h. The amount of the amine compound added at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.

NMP and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 22 to prepare 6 mass% polyamic acid, 79 mass% NMP, and 15 mass% BCS.

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is NMPZBCS = 82Z12 in terms of mass ratio.

[0136] {Example 65}

3 g of the polyimide powder obtained in Synthesis Example 1 was dissolved in 34.5 g of GBL by stirring at 50 ° C. for 20 hours. To this solution, add 2 mass ⁰ / oGBL solution of triethylenetetraamine (No.94 amine compound) 3. Og (0.15 g as amine compound), and then add polyimide concentration in this solution GBL (9.5 g) was added so that the amount was 6 mass%, and the mixture was stirred at 50 ° C for 20 hours. The amount of the amine compound added at this time is 2 parts by mass with respect to 100 parts by mass of the polyimide.

20 g of the reaction solution of polyimide and amine mixture prepared above and 80 g of dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain the coating solution of the present invention. The solvent composition of this coating solution is NMPZGBLZBCS = 16Z66Z12 by mass ratio. [0137] (Synthesis Example 23)

30.03 g (0.1 mol) of TDA, 9.46 g (0.0875 mol) of DAI, 3.77 g (0.01 mol) of DA2, (aminoethylaminomethyl) phenethyltrimethoxysilane (No. 37 ammine) Compound) was reacted with 1.49 g (0.005 mol) in NMP 254 g at room temperature for 24 hours to prepare a polyamic acid solution. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.0 g of pyridine and 17.1 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white polyimide powder. The obtained imidized polymer soluble in the solvent had a number average molecular weight of 5,951 and a weight average molecular weight of 22,992. The imidation ratio was 81%.

[0138] {Example 66}

3 g of the polyimide powder obtained in Synthesis Example 23 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours. Thereafter, 12.5 g of NMP was added and diluted so that the polyimide concentration in the solution was 6% by mass.

20 g of the polyimide solution prepared above and 80 g of a dilute solution of polyamic acid were mixed and stirred at room temperature for 20 hours to obtain a coating solution of the present invention. The solvent composition of this coating solution is NMP ZGBLZBCS = 66Z16Z12 by mass ratio.

[0139] <Evaluation of moisture absorption stability>

Using the coating solutions prepared in Examples 28 to 66, the moisture absorption stability was evaluated in the same manner as described above. As a result, these coating solutions showed no agglomeration even after 6 hours.

(Liquid crystal aligning agent)

The coating liquids prepared in Examples 1 to 66 and Comparative Examples 1 to 5 were pressure filtered through a membrane filter having a pore size of 1 μm to obtain a liquid crystal aligning agent.

[0140] <Evaluation of rubbing resistance>

A liquid crystal aligning agent is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then baked in a hot air circulation oven at 230 ° C for 30 minutes. An Onm coating was formed. This coating surface was rubbed with a rayon cloth with a rubbing machine having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film . The surface of the liquid crystal alignment film was observed with a real-time scanning laser microscope 1LM21D (objective lens 10 ×) manufactured by Lasertec (magnification magnification 340 × on the monitor).

[0141] As a result, the surface of the liquid crystal alignment film obtained using the liquid crystal aligning agent having the coating liquid force of Examples 1 to 64 and Example 66 was strong enough to show no scratches or film peeling. Although peeling of the film was not observed on the surface of the liquid crystal alignment film obtained by using the liquid crystal aligning agent comprising the coating liquids of Comparative Examples 1 to 5, many fine scratches were observed. Further, the surface of the liquid crystal alignment film obtained using the liquid crystal aligning agent having the coating liquid force of Example 65 was observed to have fine scratches although no film peeling was observed. This is because in Example 65, γ-petit-mouth rataton was used as the solvent for reacting the solvent-soluble polyimide and the amine compound, so that the amine compound was consumed by reacting with γ-petit-mouth rataton. It is considered that a sufficient amount of the added amount by mass did not react with the solvent-soluble polyimide.

[0142] <Evaluation of printability>

Examples The liquid crystal aligning agents having the coating liquid power of Examples 30 to 32 were subjected to a printability test by the flexographic printing method as follows.

Printer: Nissha Printing Angstromer S-15

Printed version: 400 mesh APR version

Printing conditions:-The width of the pop was 0.2 mm. The tact time was set to 30 seconds, and printing was first performed on six 100 mm × 100 mm glass substrates, followed by printing on four Cr film-formed glass substrates of the same size. Finally, the printed substrate is dried on a hot plate at 80 ° C for 5 minutes and viewed with a microscope at 50x magnification.

¾πί.

As a result, the liquid crystal aligning agent having the coating solution power of Example 30 was superior in in-plane film thickness uniformity to the other two liquid crystal aligning agents.

[0143] (Production of liquid crystal display element and evaluation of electrical characteristics)

A liquid crystal aligning agent is spin-coated on a glass substrate with a ΙΤΟ electrode, dried on a hot plate at 80 ° C for 5 minutes, and then baked in a hot air circulation oven at 230 ° C for 30 minutes. An Onm coating was formed. The coated surface was rubbed with a rayon cloth using a rubbing machine having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. .

[0144] Prepare two substrates with this liquid crystal alignment film, spray a 6 μm spacer on the surface of one liquid crystal alignment film, and then print another sealant with the upper force. The substrates were laminated so that the liquid crystal alignment film faces each other and the rubbing direction was orthogonal, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. Using the liquid crystal aligning agent having the coating liquid force of Examples 1 to 65 and Comparative Examples 1 to 5, the liquid crystal cells produced as described above were observed under a polarizing microscope. Were uniformly oriented.

[0145] <Evaluation of voltage holding ratio>

The temperature of the liquid crystal cell produced above is 90 using the VHR-1 voltage holding ratio measuring device manufactured by Toyo Tech-Riki. C, voltage: ± 4V, pulse width: 60 μs, flame period: measured at a setting of 16.67ms, voltage holding of how much can be maintained after 16.6ms of voltage force of 4VZ60s at a temperature of 90 ° C Calculated as a rate.

The results are shown below.

[0146] [Table 13]

Coating liquid Voltage holding ratio Voltage holding ratio Coating voltage holding ratio Example 1 94¾ Example 2 6 94¾ Example 5 1 93¾

Example 2 93¾ Example 2 7 94¾ Example 5 2 93¾

Example 3 93% Example 2 8 94% Example 5 3 93¾

Example 4 93¾ Example 2 9 94¾ Example 5 4 93¾

Example 5 93% Example 3 0 94¾ Example 5 5 93¾

Example 6 94¾ Example 3 1 94¾ Example 5 6 93¾

Example 7 95¾ Example 3 2 94¾ Example 5 7 93¾

Example 8 94¾ Example 3 3 94¾ Example 5 8 93%

Example 9 95¾ Example 3 4 94¾ Example 5 9 93¾

Example 1 0 94¾ Example 3 5 94¾ Example 6 0 95¾

Example 1 1 95¾ Example 3 6 94¾ Example 6 1 95¾

Example 1 2 93¾ Example 3 7 94¾ Example 6 2 94¾

Example 1 3 94¾ Example 3 8 94¾ Example 6 3 94¾

Example 1 4 95¾ Example 3 9 94¾ Example 6 4 95¾

Example 1 5 94¾ Example 4 0 94¾ Example 6 5 93¾

Example 1 6 95¾ Example 4 1 94¾ Example 6 6 94X

Example 1 7 94¾ Example 4 2 94¾ Comparative Example 1 93%

Example 8 94¾ Example 4 3 94¾ Comparative Example 2 93%

Example 1 9 95¾ Example 4 4 94¾ Comparative Example 3 93¾

Example 2 0 94¾ Example 4 5 94¾ Comparative Example 4 93¾

Example 2 1 94¾ Example 4 6 94¾ Comparative Example 5 93¾

Example 2 2 93¾ Example 4 7 93¾

Example 2 3 93¾ Example 4 8 94¾

Example 2 4 93¾ Example 4 9 94¾

Example 2 5 94¾ Example 5 0 94¾

[0147] <Evaluation of easy removal of accumulated charge>

Among the above liquid crystal cells, the liquid crystal cell of the liquid crystal aligning agent (liquid crystal display element of the present invention) that is the coating liquid of Example 4 and the liquid crystal cell of the liquid crystal aligning agent that is the coating liquid force of Comparative Example 1 (the liquid for comparison) The crystal display element) was compared with the ease of stored charge release as follows.

After applying a DC voltage of 10V to the liquid crystal cell for 30 minutes and short-circuiting it for 1 second, a change in the potential (accumulated charge) generated in the liquid crystal cell and the V charge (stored charge) Measured using. As a result, in the liquid crystal display element of the present invention, the maximum value of the accumulated charge was smaller than that of the comparative liquid crystal display element, and the decrease in the charge was quick. Figure 1 shows a graph of this potential change.

Industrial applicability

[0148] According to the coating solution of the present invention, precipitation of the rosin component due to moisture absorption can be suppressed, stable printability can be obtained, and it can be suitably used as a liquid crystal aligning agent. In addition, the liquid crystal alignment film of the present invention can provide a liquid crystal display element of higher quality than before, and this liquid crystal display element can be suitably used for various display devices. It should be noted that the entire contents of the specification, claims, drawings and abstract of the Japanese Patent Application No. 2006-195403, filed on July 18, 2006, are hereby incorporated herein by reference. As it is incorporated.

Claims

Claim [1] Component (A): tetracarboxylic dianhydride, diamine compound, amine compound (a), amine compound (b) and amine compound (c) A coating solution comprising: an imidi polymer soluble in a solvent obtained from at least one amine compound, and a component (B): a polyamic acid. Amine compound (a): an amine compound having one primary amino group selected from formula [K1] and formula [K2] and at least one imino group selected from formula [K3] and formula [K4] in the molecule Compound. Note that in the formulas [K3] and [K4], the bonding direction of —CH—NH— is opposite. 2 Amine compound (b): Amine compound having at least two primary amino groups selected from the above formulas [K1] and [K2] in the molecule. Amine compound (c): At least one primary amino group of formula [K1] and formula [K2] force in the molecule and an imino group of formula [K3] and formula [K4] Amine compound having at least one.

[Chemical 1]

H ₂ N-CH ₂ — H ₂ N-CH— [Kl] [K2]

— CH ₂ -NH— — NH-CH ₂ ―

[K3] [4]

[2] The component (ii) is a solvent-soluble polyimide that can also obtain the ability of a tetracarboxylic dianhydride and diamine compound, and at least one of the side chain and molecular end of the polyimide, the amine compound (a), and the amine compound 2. The coating solution according to claim 1, wherein the coating solution is an imidized polymer that is soluble in a solvent obtained by binding (b) at least one amine compound that also has a selected force.

[3] The component (A) is a solvent-soluble polyimide capable of obtaining a compound strength of tetracarboxylic dianhydride and diamine compound, and at least one amine compound selected from the amine compound (a) and amine compound (b). 2. The coating solution according to claim 1, which is a product obtained by reacting the compound.

[4] The component (A) is a diamine compound containing a tetracarboxylic dianhydride and an amine compound (c); 2. The coating solution according to claim 1, wherein the coating solution is an imidopolymer soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting with.

[5] The component (A) is obtained by using at least one amine compound selected from the amine compounds represented by the following formulas (i) and (ii) as the amine compound (a). The coating solution according to claim 1, which is an imidized polymer soluble in a solvent to be obtained.

[Chemical 2]

H ₂ N— R ¹ — X -CHQ-N ~ X ² (i)

H

H ₂ N— R ¹ — X ¹ — N— CH ₂ — X ² (ϋ)

H

[However, R ¹ in the formula is CH CH (CH) or one CH (CH CH) —

2 3 2 3 represents alkylene or an aliphatic ring, X ¹ represents a single bond or an aliphatic hydrocarbon having 1 to 20 carbon atoms, and —NH 2 may be included in the aliphatic hydrocarbon. . X ² represents an organic group having 1 to 20 carbon atoms, and an organic group comprising an alkyl group having 1 to 20 carbon atoms, a cycloaliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, and a combination thereof. And unsaturated bonds, ether bonds (one O), ketone bonds (one CO), ester bonds (one COO), amino bonds (one NH), ammine bonds (one N), silyl bonds (one Si— ), A siloxane bond (SiO 2), or the like. Further, even if the alkyl group of X ² forms a heterocyclic structure with either —R ¹ X ¹ —CH ² or NH 3

2

Good. ]

[6] The component (A) is obtained by using, as the amine compound (b), at least one amine compound selected from the amine compounds represented by the following formulas (m) to (V): 2. The coating solution according to claim 1, which is an imidized polymer soluble in a solvent.

[Chemical 3] H ₂ N— R ¹ — X ³ — R ¹ — NH ₂ (iii)

H ₂ N— RL _X 4— NH— X ⁵ — R ¹ — NH ₂ (iv)

H ₂ N— R ¹ — X ⁶ -NH— X ⁷ -NH— X ⁸ -R ¹ ― NH ₂ (v)

twenty two

[7] The component (A) is at least one amine compound selected from the following formulas (i), (ii), (iv) and (v) as the amine compound (c): 2. The coating solution according to claim 1, which is an imidopolymer soluble in a solvent obtained using the compound.

[Chemical 4]

H ₂ N— R ¹ — X ¹ — N— CH ₂ — X ² (ϋ)

H

[Chemical 5]

H ₂ N— R ^ -X ⁴ — NH— X ⁵ — R ¹ — NH ₂ (iv) H ₂ N— R ¹ — X ⁶ -NH— X ⁷ _NH— X ⁸ -R ¹ — NH ₂ (v)

[8] Ratio power of imidized polymer of component (A) and polyamic acid of component (B) Component (A) and component (B) The coating solution according to any one of claims 1, 2, and 4 to 7, wherein the ratio of the polyamic acid of the component (B) is 20 to 99% by mass in the total mass of the component.

[9] The component (A) is composed of the amine compound (a) and the amine compound (b) with respect to 100 parts by mass of the solvent-soluble polyimide capable of obtaining a tetracarboxylic dianhydride and diamine compound. 4. The coating solution according to claim 3, which is a product obtained by reacting 1 to 15 parts by mass of at least one selected amine compound.

[10] The component (A) can be used as a solvent obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride and a diamine containing the above-described amine compound (c). The amount of the amine compound (c) in the soluble imido polymer is from 1 mol% to 15 mol% in the combined amount of diamine and amine compound (c). The coating liquid as described.

[11] A liquid crystal aligning agent that also has a coating liquid force according to any one of claims 1 to 10.

12. The liquid crystal aligning agent according to claim 11, wherein the amide solvent is contained in the coating solution in an amount of 50% by mass or more.

[13] A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to claim 11 or 12.

14. A liquid crystal display device using the liquid crystal alignment film according to claim 13.