KR20170029022A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

(식 [1] 중, Y¹ 은 단결합 등을 나타내고, Y² 는 단결합 또는 -(CH₂)_b- (b 는 1 ∼ 15 의 정수이다) 를 나타내고, Y³ 은 단결합 등을 나타내고, Y⁴ 는 2 가의 고리형기를 나타내고, Y⁵ 는 2 가의 고리형기를 나타내고, n 은 0 ∼ 4 의 정수를 나타내고, Y⁶ 은 탄소수 1 ∼ 18 의 알킬기 등을 나타낸다).A liquid crystal alignment treatment agent comprising the following components (A) and (B).
Component (A): Propylene glycol monobutyl ether. Component (B): At least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component having a structure represented by the following formula [1] with a tetracarboxylic acid component.

(Wherein, Y ¹ represents a single bond, Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ represents a single bond or the like , Y ⁴ represents a bivalent cyclic group, Y ⁵ represents a bivalent cyclic group, n represents an integer of 0 to 4, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

The present invention relates to a liquid crystal alignment treatment agent used in manufacturing a liquid crystal alignment film and a liquid crystal display device using the same.

2. Description of the Related Art In recent years, liquid crystal display devices have been widely used in mobile applications (digital cameras and mobile phones) of large-screen liquid crystal televisions and fixed screens. . Also in such a situation, it has been demanded that a liquid crystal alignment film is uniformly coated on a large substrate or step in terms of display characteristics. When a liquid crystal alignment treatment agent (also referred to as a coating solution) of a polyamic acid or a solvent-soluble polyimide (also referred to as a resin), which is a polyimide precursor, is applied to a substrate in the manufacturing process of the liquid crystal alignment film, Or by an ink-jet coating method or the like. At this time, in order to improve the film uniformity of the liquid crystal alignment film, in addition to N-methyl-2-pyrrolidone or? -Butyrolactone, which is a solvent excellent in solubility of the resin (also referred to as good solvent) Butylcellosolve, which is a low-solubility solvent (also referred to as a poor solvent), and the like (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 02-037324

A liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain tends to lower the film uniformity of the liquid crystal alignment film. Particularly, when a uniform film property can not be obtained, that is, when cratering or pinholes are generated, this portion becomes a display defect when used as a liquid crystal display element. Therefore, it is necessary to increase the introduction amount of the poor solvent having high wettability of the coating solution to the substrate. However, the poor solvent has an inferior ability to dissolve polyamic acid or polyimide, so that there is a problem that precipitation of the resin occurs when mixed in a large amount.

In recent years, liquid crystal display devices have been used for mobile applications such as smart phones and tablet PCs. In these applications, a sealant used for bonding between the substrates of the liquid crystal display element exists at a position close to the end of the liquid crystal alignment film, in order to secure as much display surface as possible. Therefore, when the film property of the end portion of the liquid crystal alignment film is deteriorated, that is, when the end portion of the liquid crystal alignment film is not straight or the end portion is mounted, the adhesive effect of the sealant between the substrates deteriorates , The reliability of the liquid crystal display element is lowered.

The present invention has been made in view of the above circumstances. That is, a problem to be solved by the present invention is to provide a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain, And a liquid crystal alignment film excellent in the film property of an end portion of the liquid crystal alignment film.

It is another object of the present invention to provide a liquid crystal display element having the above-described liquid crystal alignment film.

It is another object of the present invention to provide a liquid crystal alignment treatment agent capable of providing the above-mentioned liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treating agent using a solvent having a specific structure and a polymer having a side chain of a specific structure is very effective for achieving the above object, and has completed the present invention.

That is, the present invention has the following points.

(1) A liquid crystal alignment treatment agent containing the following components (A) and (B).

Component (A): Propylene glycol monobutyl ether.

Component (B): At least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component having a structure represented by the following formula [1] with a tetracarboxylic acid component.

[Chemical Formula 1]

(Wherein, in the formula [1], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- , Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ represents a single bond, - (CH ₂ ) _c - , -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent cyclic group having 12 to 25 carbon atoms and a steroid skeleton An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms And Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, And Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

(2) The liquid crystal alignment treatment agent according to (1), wherein the diamine component in the polymer of the component (B) comprises a diamine compound having a structure represented by the following formula (1a).

(2)

(In the formula [1a], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- , Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ represents a single bond, - (CH ₂ ) _c - , -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent cyclic group having 12 to 25 carbon atoms and a steroid skeleton An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms atoms and optionally substituted, Y ⁵ represents a divalent cyclic group selected from benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen on these cyclic group An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and m represents an integer of 1 to 4) .

(3) The liquid crystal alignment treatment agent according to the above item (1) or (2), wherein the diamine component in the polymer of the component (B) comprises a diamine compound having a structure represented by the following formula .

(3)

(In the formula [2], X represents a substituent of a structure selected from the following formula [2a], formula [2b], formula [2c] or formula [2d], and m represents an integer of 1-4.

[Chemical Formula 4]

(2a), a represents an integer of 0 to 4, b in the formula [2b] represents an integer of 0 to 4, and X ¹ and X ² in the formula [2c] To 12 carbon atoms, and in the formula [2d], X ³ represents an alkyl group having 1 to 5 carbon atoms.

(4) The method according to any one of (1) to (3) above, wherein the tetracarboxylic acid component in the polymer of the component (B) comprises a compound represented by the following formula [3] Liquid crystal alignment treatment agent.

[Chemical Formula 5]

(In the formula [3], Z ¹ is a group of a structure selected from the following formulas [3a] to [3j]).

[Chemical Formula 6]

(Formula [3a] of, Z ² ~ Z ⁵ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may respectively be the same or different compounds of formula [3g], Z ⁶ and Z ⁷ represents a hydrogen atom or a methyl group And may be the same or different.

(5) As the component (C), any one of the above-mentioned (1) to (4) containing a solvent of N-methyl-2-pyrrolidone, N- The liquid crystal alignment treatment agent described in one.

(6) The liquid crystal alignment liquid crystal display according to any one of (1) to (5) above, which contains, as the component (D), a solvent selected from the solvents represented by the following formulas [D- Treatment agent.

(7)

(D-1), D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² in the formula [D-2] represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

(7) The positive resist composition as described in any one of (1) to (6) above, which contains, as the component (E), a solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2- propanediol or ethylene glycol monobutyl ether (6) above.

(8) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (7).

(9) A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent according to any one of (1) to (7).

(10) A liquid crystal display element having the liquid crystal alignment film according to (8) or (9) above.

(11) A liquid crystal display device comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing at least one of active energy rays and heat between at least one substrate of the pair of substrates and the liquid crystal layer (8) or (9), wherein the liquid crystal composition is used for a liquid crystal display device manufactured by a process of arranging a liquid crystal composition containing a polymerizable compound and polymerizing the polymerizable compound while applying a voltage between the electrodes. Alignment layer.

(12) A liquid crystal display element having the liquid crystal alignment film according to (11).

(13) A liquid crystal display device comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group which is polymerized by at least one of active energy rays and heat between at least one substrate of the pair of substrates and the liquid crystal layer The liquid crystal alignment film according to (8) or (9) above, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured by a process of arranging a liquid crystal alignment film which is formed by polymerizing the polymerizable group while applying a voltage between the electrodes.

(14) A liquid crystal display element having the liquid crystal alignment layer according to (13) above.

By using the liquid crystal alignment treatment agent comprising the solvent of the specific structure of the present invention and the polymer having the side chains of the specific structure, the wetting property of the coating solution to the substrate is high, and the uniform film property can be obtained, It is possible to provide a liquid crystal alignment film excellent in uniform film property at the end portion of the liquid crystal alignment film. Particularly, a liquid crystal alignment film excellent in these properties can be provided even with a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain. In addition, it is possible to provide a liquid crystal display element having the liquid crystal alignment film as described above, and a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for showing a criterion for evaluating the linearity of the end portion of a liquid crystal alignment film. Fig.
2 is a view for showing a standard of mounting evaluation of an end portion of a liquid crystal alignment film.

Hereinafter, the present invention will be described in detail.

The present invention relates to a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and furthermore, a liquid crystal display device having the liquid crystal alignment film.

Component (A): Propylene glycol monobutyl ether (also referred to as a specific solvent).

(B): at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component having a structure represented by the following formula [1] (also referred to as a specific side chain structure) with a tetracarboxylic acid component (Also referred to as a specific polymer).

[Chemical Formula 8]

(Wherein, in the formula [1], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- , Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ represents a single bond, - (CH ₂ ) _c - , -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent cyclic group having 12 to 25 carbon atoms and a steroid skeleton An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms And Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, And Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

The specific solvent of the present invention can be used as a poor solvent used for increasing the film-forming property of the liquid crystal alignment film. Since the specific solvent of the present invention has a high wetting property of the coating solution on the substrate as compared with the case where ethylene glycol monobutyl ether (also referred to as butyl cellosolve or BCS) used as a poor solvent is used, It is possible to obtain a liquid crystal alignment film excellent in film-forming property in which cratering or pinholes are not easily generated. Further, since the wetting property of the coating solution is enhanced, the linearity of the end portion of the liquid crystal alignment film is increased, and the mounting of the end portion can be suppressed.

The component (B) of the present invention is at least one polymer selected from a polyimide precursor or polyimide. Among them, when the composition of the present invention is used in a liquid crystal alignment film as a liquid crystal aligning agent, it is preferable to use a specific polymer having a specific side chain structure represented by the above formula [1].

The specific side chain structure of the present invention has a benzene ring, a cyclohexyl ring or a heterocyclic ring in the side chain moiety, or a divalent organic group having 12 to 25 carbon atoms and a steroid skeleton. These benzene rings, cyclohexyl rings, heterocyclic rings, or divalent organic groups having 12 to 25 carbon atoms and a steroid skeleton exhibit a rigid structure as compared with the long chain alkyl groups of the prior art. This improves the stability of the side chain portion against heat and ultraviolet rays, and can provide a liquid crystal alignment film in which the pretilt angle is stable with respect to heat or light.

In view of the above, the liquid crystal alignment treatment agent containing the specific solvent and the specific polymer of the present invention can form a liquid crystal alignment film excellent in film film property. Further, the liquid crystal alignment treatment agent containing the specific solvent and the specific polymer of the present invention becomes a liquid crystal alignment film which does not change the pretilt angle even when exposed to high temperature and light irradiation for a long time. Further, by using this liquid crystal alignment film, a liquid crystal display device having excellent display characteristics and high reliability can be provided.

<Specific solvent>

A particular solvent of the present invention is propylene glycol monobutyl ether.

The specific solvent of the present invention is preferably 5 to 70% by mass of the entire organic solvent contained in the liquid crystal alignment treatment agent in order to enhance the effect of increasing the wettability of the coating solution to the above-described substrate. Among these, 10 to 70 mass% is preferable. And more preferably 10 to 60% by mass.

The effect of the present invention, that is, the wettability of the coating solution onto the substrate is enhanced, the liquid crystal alignment film having excellent film uniformity can be obtained as the amount of the specific solvent of the present invention in the entire organic solvent in the liquid crystal alignment treatment agent is increased .

&Lt; Specific polymer &

The specific polymer as the component (B) of the present invention is a polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor has a structure represented by the following formula [A].

[Chemical Formula 9]

(In the formula [A], R ¹ is a divalent organic group having a carboxyl group and R ² is a divalent organic group having a carboxyl group, A ¹ and A ^{2 each} represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A ³ and A ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different, and n represents a positive integer.

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule. As the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a dicarboxylic acid dihalide compound , A dicarboxylic acid dialkyl ester compound, or a dialkyl ester dihalide compound.

The specific polymer of the present invention can be obtained by using the tetracarboxylic acid dianhydride represented by the following formula [B] and the diamine compound represented by the following formula [C] And a polyimide obtained by imidizing the polyamic acid is preferable.

[Chemical formula 10]

(In the formulas [B] and [C], R ¹ and R ² have the same meanings as defined in formula [A]).

(11)

(In the formula [D], R ¹ and R ² have the same meanings as defined in formula [A]).

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

<Specific side chain structure>

The specific polymer of the present invention is at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a tetracarboxylic acid component with a diamine component having a specific side chain structure represented by the following formula [1].

[Chemical Formula 12]

In formula [1], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable in view of availability of raw materials and ease of synthesis desirable. More preferred is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [1], Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

In the formula [1], Y ³ represents a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [1], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ is a divalent organic group selected from organic groups having 12 to 25 carbon atoms and a steroid skeleton. Among them, a benzene ring, a cyclohexane ring, or a divalent organic group having 12 to 25 carbon atoms and a steroid skeleton are preferable from the viewpoint of ease of synthesis.

In formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom of these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In the formula [1], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials and easiness of synthesis, 0 to 3 is preferable. More preferred is 0 to 2.

In the formula [1], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. And particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

&Lt; Specific side chain type diamine compound &gt;

As a method of introducing a specific side chain structure into a specific polymer of the present invention, it is preferable to use a diamine compound having a specific side chain structure as a part of the starting material. It is particularly preferable to use a diamine compound represented by the following formula [1a] (also referred to as a specific side chain type diamine compound).

[Chemical Formula 13]

In formula [1a], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable in view of availability of raw materials and ease of synthesis desirable. More preferred is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [1a], Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

In formula [1a], Y ³ represents a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [1a], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ is a divalent organic group selected from organic groups having 12 to 25 carbon atoms and a steroid skeleton. Among them, a benzene ring, a cyclohexane ring, or a divalent organic group having 12 to 25 carbon atoms and a steroid skeleton are preferable from the viewpoint of ease of synthesis.

In formula [1a], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In the formula [1a], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials and easiness of synthesis, 0 to 3 is preferable. More preferred is 0 to 2.

In formula [1a], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. And particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Formula 13 of ^{[1a] Y 1, Y 2} , Y 3, Y 4, Y 5, Y 6 , and a preferred combination of n, the International Publication No. WO2011 / 132751 (October 27, 2011 publication) in the (2-1) to (2-629) listed in Tables 6 to 47 of Table 34. In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are represented as Y ¹ to Y ⁶ , and Y ¹ to Y ⁶ are read in replacement with Y ¹ to Y ⁶ . Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615). Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), or (2-603) to ) to be.

In the formula [1a], m is an integer of 1 to 4. It is preferably an integer of 1.

Specifically, it is a structure represented by the following formulas [1a-1] to [1a-31], for example.

[Chemical Formula 14]

(Wherein R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² represents A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxy group).

[Chemical Formula 15]

(In the formulas [1a-4] to [1a-6], R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ - or -CH ₂ -, R ⁴ represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, a straight-chain or branched alkoxy group having 1 to 22 carbon atoms A branched or branched fluorine-containing alkyl group or a fluorine-containing alkoxy group).

[Chemical Formula 16]

(In the formulas [1a-7] and [1a-8], R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O- or -NH-, R ⁶ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, Time or hydroxyl group).

[Chemical Formula 17]

(Formula [1a-9] and the formula [1a-10] of, R ⁷ is a linear or branched alkyl group having a carbon number of 3-12, a 1,4-cyclohexylene cis-trans reason respectively trans isomers) .

[Chemical Formula 18]

(In the formulas [1a-11] and [1a-12], R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer. .

[Chemical Formula 19]

(In the formula [1a-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4- , A ₂ is an oxygen atom or -COO- * (provided that the bonding hand to which &quot; * &quot; is bonded is bonded to A ₃ ), A ₁ is an oxygen atom or -COO- * Hand combines with (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

1a-1] to [1a-6], the formula [1a-9] to the formula [1a-13], and the diamine compound of the formula [ Or the formula [1a-22] to the formula [1a-31].

The above-mentioned specific side chain type diamine compound may be used alone or in combination of two or more types, depending on the solubility in a solvent when the specific polymer of the present invention is used, the liquid crystal alignability in the case of a liquid crystal alignment film, the voltage retention rate, May be mixed and used.

It is also preferable to use a diamine compound represented by the following formula [2] as a diamine component for producing the specific type of polymer as the component (B) of the present invention.

(25)

In the formula [2], X represents a substituent of the structure selected from the following formula [2a], formula [2b], formula [2c] or formula [2d].

In the formula [2], m represents an integer of 1 to 4.

(26)

In formula [2a], a represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

In the formula [2b], b represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

In the formula [2c], X ¹ and X ² each independently represent a hydrocarbon group of 1 to 12 carbon atoms.

In the formula [2d], X ³ represents an alkyl group having 1 to 5 carbon atoms.

The specific structure of the diamine compound represented by the formula [2] of the present invention is shown below, but it is not limited to these examples.

Namely, examples of the diamine compound represented by the formula [2] include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5- , 5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5- , Diamine compounds having structures represented by the following formulas [2-1] to [2-6] can be exemplified.

(27)

(28)

Among them, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4 -Diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, the diamine compound represented by the formula [2-1], the formula [2-2] or the formula [2-3] Particularly preferred are 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, the formula [2-1] ].

The diamine compound represented by the above formula [2] is preferably one kind or two or more kinds of the diamine compound represented by the formula [2], depending on the solubility and coating properties of the specific polymer of the present invention, Or a mixture of two or more of them may be used.

As the diamine component for producing the specific polymer which is the component (B) of the present invention, a diamine compound other than the diamine compound represented by the formula [1a] and the formula [2] (also referred to as another diamine compound) have. Specific examples of the other diamine compounds are shown below, but the present invention is not limited to these examples.

For example, there may be mentioned m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'- 3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3 Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3'- , 4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldi aniline, 3,3 ' (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis Phenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'- thiodianiline, 4,4'- diaminodiphenylamine, Aminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diamino di (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'- diaminobenzophenone, Diaminobenzoquinone, 4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, Diaminonaphthalene, 2,6-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ) Ethane, 1,2-bis (3-aminophenyl) ethane, 1, (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, - [1,4 - phenylenebis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ (Methylene)] dianiline, 3,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,3' - [1,4-phenylenebis Phenylene bis [(3-aminophenyl) methane], 1,4-phenylenebis [(methylene)] dianiline, Phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-amino Benzoate), 1,4-phenyl Bis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ' , N, N '- (1, 3-phenylene) bis (3-aminobenzamide), N, N' (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'- N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis Bis [4- (4-aminophenoxy) phenyl] hexafluoro (2-hydroxyphenyl) Propane, 2,2'-bis (4- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'- Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4- Bis (4-aminophenoxy) pentane, 1,6-bis (3-aminophenoxy) pentane, Bis (4-aminophenoxy) heptane, 1,7-bis (4-aminophenoxy) heptane, (Aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis , 10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, Diminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. .

As other diamine compounds, those having an alkyl group, a fluorine-containing alkyl group, or a heterocyclic ring in the diamine side chain may also be used.

Specifically, the diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.

[Chemical Formula 29]

(In the formula [DA1] ~ formula [DA4], A ¹ represents an alkyl group or a fluorine-containing alkyl group having a carbon number of 1 to 22).

(30)

(31)

(32)

(Wherein [DA5] ~ formula [DA10] of, A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - represents, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(33)

(In the formula [DA11], p represents an integer of 1 to 10).

As the other diamine compounds, diamine compounds represented by the following formulas [DA12] to [DA13] may be used as long as the effects of the present invention are not impaired.

(34)

(35)

(In the formula [DA14], m represents an integer of 0 to 3, and in the formula [DA17], n represents an integer of 1 to 5).

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA18] to [DA21] may be used.

(36)

(Wherein [DA18] of, A ¹ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O -, -CO-, -NH-, -N ( CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3 during or -N (CH ₃₎ represents a CO-, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² is an integer of 1-4, formula [DA19], -) m ³ and m ⁴ each represent an integer of 1 to 5, and in the formula [DA20], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, DA21] of, A ³ is a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, -O-, - _{CO-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N (CH ₃ ) CO-, and m ⁶ represents an integer of 1 to 4).

In addition, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA22] may be used.

(37)

(Wherein [DA22] of, A ¹ is _{-O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3) - or -N (CH ₃ ) CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ³ is a divalent organic group selected from -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) Or -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.

In addition, as other diamine compounds, diamine compounds represented by the following formulas [DA23] and [DA24] may be used.

(38)

The other diamine compounds may be mixed with one kind or two or more kinds depending on the solubility of the specific polymer of the present invention in the solvent, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, .

&Lt; Tetracarboxylic acid component &gt;

Examples of the tetracarboxylic acid component for producing the specific polymer which is the component (B) of the present invention include tetracarboxylic acid dianhydride represented by the following formula [3], tetracarboxylic acid derivatives thereof, tetracarboxylic acid, tetra A carboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (all collectively referred to as a specific tetracarboxylic acid component) is preferably used.

[Chemical Formula 39]

In the formula [3], Z ¹ is a group of a structure selected from the following formulas [3a] to [3j].

(40)

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ each represent a hydrogen atom or a methyl group, and may be the same or different.

Among the structures represented by the formula [3], which is a specific tetracarboxylic acid component of the present invention, Z ¹ is preferably a tetracarboxylic acid represented by the formula [3a], the formula [3c] , The formula [3d], the formula [3e], the formula [3f] or the formula [3g]. More preferred is a structure represented by Formula [3a], Formula [3e], Formula [3f] or Formula [3g], and particularly preferred is Formula [3e], Formula [3f] or Formula [3g].

The specific tetracarboxylic acid component of the present invention is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, particularly preferably 10 mol% or more.

When the specific tetracarboxylic acid component having the structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic acid component to be used is 20 mol% or more of the total tetracarboxylic acid component, Is obtained. Preferably, it is at least 30 mol%. Further, the tetracarboxylic acid component may all be a tetracarboxylic acid component having the structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer of the present invention, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used as long as the effect of the present invention is not impaired.

Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds shown below have.

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,6- Naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid Bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis Bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,5-pyridine tetracarboxylic acid, 2,6- Perylene tetracarboxylic acid or 1,3-di Carbonyl-1,2,3,4-cycloalkyl may be mentioned butane tetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component are preferably used in combination with the solvent of the specific polymer of the present invention and the liquid crystal alignment layer in accordance with the characteristics of the liquid crystal alignment, One kind or two or more kinds may be mixed and used.

&Lt; Process for producing specific polymer &

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, a method of dehydrating polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound, A method of obtaining an acid or a method of polycondensing a dicarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid is used.

The polyamide acid alkyl ester can be obtained by polycondensation of a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a method of polycondensing a dicarboxylic acid dihalide obtained by converting a carboxylic acid group into a dialkyl ester And a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above-mentioned polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples of the organic solvent used in the reaction are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone, N, Dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- 3], and the like.

(41)

(D-1), D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² in the formula [D-2] represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

These may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. Furthermore, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, it is preferable to use an organic solvent which is dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred and a tetracarboxylic acid component is added as it is or dispersed or dissolved in an organic solvent , A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, and the like. May be used. When a plurality of diamine components or tetracarboxylic acid components are used for the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted You can. The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, a polymer having a high molecular weight can not be obtained well. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by ring closure of the above polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amidic acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

Examples of the method for imidizing the polyimide precursor include a heat imidization for directly heating the solution of the polyimide precursor or a catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Of these, pyridine is preferred because it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or the polyimide is recovered from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. Further, by repeating the operation of re-dissolving the polymer recovered and precipitated in the organic solvent and re-precipitating and recovering the polymer solution 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones or hydrocarbons can be exemplified, and when three or more solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the specific polymer of the present invention is preferably 5,000 to 1,000,000 in terms of the weight average molecular weight measured by GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of film formation, And more preferably from 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film, and is a coating solution containing a specific solvent and a specific polymer.

In the liquid crystal alignment treatment agent of the present invention, all of the polymer components may be the specific polymer of the present invention, or other polymers may be mixed. At that time, the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass of the specific polymer of the present invention. Examples of the other polymer include a diamine compound represented by the formula [1a], a diamine compound represented by the formula [2], and a polyimide polymer not using a specific tetracarboxylic acid component. Further, polymers other than the polyimide polymer, specifically acrylic polymer, methacrylic polymer, polystyrene, polyamide or polysiloxane can be mentioned.

The organic solvent in the liquid crystal alignment treatment agent of the present invention preferably has an organic solvent content of 70 to 99.9 mass% from the viewpoint of forming a uniform liquid crystal alignment film by application. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film.

The organic solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is an organic solvent (also referred to as a good solvent) for dissolving a specific polymer. Specific examples of the two solvents are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, D-3], and the like.

Among these two solvents, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone (also referred to as component (C)). When the specific polymer has a high solubility in a solvent, it is preferable to use a solvent represented by the above-mentioned formula (D-1) to formula (D-3) (also referred to as a component (D)).

In the liquid crystal alignment treatment agent of the present invention, it is preferable that both the solvents are 10 to 80% by mass of the total solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 70% by mass is preferable. More preferred is 30 to 60 mass%.

The liquid crystal alignment treatment agent of the present invention is an organic solvent (also referred to as a poor solvent) which improves the film property or surface smoothness of a resin film or a liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, (Propylene glycol monobutyl ether). In order to enhance the effect of the present invention, the specific solvent is preferably 5 to 70% by mass of the entire organic solvent contained in the liquid crystal alignment treatment agent. Among these, 10 to 70 mass% is preferable. And more preferably 10 to 60% by mass.

Further, in the liquid crystal alignment treatment agent of the present invention, a poor solvent (other poor solvent) other than the specific solvent may be used together as long as the effect of the present invention is not impaired. Specific examples of the other poor solvent include, but are not limited to, these examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Butylene glycol monomethyl ether, ethylene glycol mono isoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1- Acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monome Ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- Propylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Propyl methoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-ethoxypropionate, , Butyl 3-methoxypropionate, methyl lactate, Acid ethyl ester, lactic acid n- propyl ester, lactic acid n- butyl ester, the lactic acid and the like solvents represented by the isoamyl ester, or the above-mentioned the formula [D-1] ~ formula [D-3].

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol and ethylene glycol monobutyl ether (also referred to as the above component (E)) or the above- ] To [D-3] is preferably used.

These other poor solvents are preferably 1 to 60 mass% of the total amount of the organic solvent contained in the liquid crystal alignment treatment agent. Among them, it is preferably 1 to 50% by mass. More preferred is 5 to 40 mass%.

The liquid crystal alignment treatment agent of the present invention may contain a crosslinking compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group in the group A crosslinkable compound having at least one substituent selected, or a crosslinkable compound having a polymerizable unsaturated bond may be introduced. These substituents and polymerizable unsaturated bonds need to have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene , Tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- Foxy) phenyl) -1- (4- ( 1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

(42)

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].

(43)

(In the formula [4-1], n represents an integer of 1 to 3).

(44)

[Chemical Formula 45]

(46)

(4-7), n represents an integer of 1 to 3, and n in the formula [4-8] represents an integer of 1 to 3, and n in the formula [4-9] Lt; / RTI &gt;

(47)

(In the formula [4-11], n represents an integer of 1 to 10).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

(48)

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(In the formula [5-24], n represents an integer of 1 to 10, and in the formula [5-25], n represents an integer of 1 to 10).

(61)

(62)

(63)

&Lt; EMI ID =

(65)

(In the formula [5-36], n represents an integer of 1 to 100, and in the formula [5-37], n represents an integer of 1 to 10).

Also, a polysiloxane having at least one structure represented by the following formulas [5-38] to [5-40] may be used.

(66)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, a carbon number An alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring, and at least one of them represents a structure represented by the formula [5].

More specifically, the compounds of the following formulas [5-41] and [5-42] can be mentioned.

(67)

(In the formula [5-42], n represents an integer of 1 to 10).

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group include amino resins having a hydroxyl group or an alkoxy group such as melamine resin, urea resin, guanamine Resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, or a benzoguanamine derivative or glycoluril can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. They preferably have 3 to 6, on average, methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co., Ltd.) or methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , 254 and the like, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated melamines such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as benzoguanamine, Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, And anamine (manufactured by Mitsui Cyanamid Co., Ltd.). Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174 and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 4-bis (sec-butoxymethyl) benzene, or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed in International Patent Publication No. WO2011 / 132751 (published on October 27, 2011) .

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Acryloyloxyethoxy trimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate, and also crosslinkable compounds having three polymerizable unsaturated groups in the molecule, such as ethylene glycol di (meth) acrylate, di Acrylates such as ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol di (Meth) acrylate such as di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl Rate, 2- (me (Meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide may be cited as a crosslinking compound having one polymerizable unsaturated group in its molecule.

In addition, a compound represented by the following formula [7] may be used.

(68)

(Wherein E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring) And E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

(69)

The compound is an example of a crosslinking compound, but is not limited thereto. The crosslinkable compound used in the liquid crystal alignment treatment agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components, in order for the crosslinking reaction to proceed to exhibit the intended effect.

As a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge leakage of the liquid crystal cell using the liquid crystal alignment film when the liquid crystal alignment treatment agent of the present invention is used as a liquid crystal alignment film, It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156], which is disclosed in paragraphs 69 to 73 of the above-mentioned publication. The amine compound may be directly added to the composition, but it is preferable to add the amine compound in a suitable solvent at a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. This solvent is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer.

As long as the effect of the present invention is not impaired, the liquid crystal alignment treatment agent of the present invention can use a compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate may be used.

Examples of the compound that further improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic-based surfactant.

More specifically, for example, EF301, EF303 and EF352 (manufactured by Tohchem Products Corporation), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC430 and FC431 SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.)), and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

Specific examples of the compound improving the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane or N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound which adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain, in addition to the above-mentioned other poor solvent, the compound which further improves the uniformity of the film thickness of the crosslinkable compound and the liquid crystal alignment film or the surface smoothness, A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. Further, in a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used only for a substrate on one side, and as the electrode in this case, a material for reflecting light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, or inkjet printing are generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it is heated to 30 to 300 占 폚, preferably 30 to 300 占 폚, depending on the solvent used for the liquid crystal alignment treatment agent by a heating means such as a hot plate, a heat- The liquid crystal alignment layer can be formed by evaporating the solvent at a temperature of 30 to 250 ° C. When the thickness of the liquid crystal alignment film after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm, Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired liquid crystal alignment film is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention is formed by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on a liquid crystal alignment film of a substrate of one substrate, the substrates of the other substrate are laminated so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and a method in which liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed and a method in which a substrate is bonded by sealing is performed.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having a liquid crystal layer between a pair of substrates provided with an electrode and is characterized in that polymerization is carried out by at least one of active energy rays and heat between at least one substrate and a liquid crystal layer of a pair of substrates To a liquid crystal display element produced by a process of polymerizing a polymerizable compound by at least one of irradiation of an active energy ray and heating while applying a voltage between the electrodes and arranging the liquid crystal composition containing the polymerizable compound do. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed in a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. Further, in the PSA system, since the rubbing treatment is not required, it is suitable for forming a vertical alignment type liquid crystal layer which is difficult to control the pretilt by the rubbing treatment.

That is, the liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, preparing a liquid crystal cell, The orientation of the liquid crystal molecules can be controlled.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped onto a surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed to effect a sealing.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound will not polymerize and the alignment of the liquid crystal can not be controlled. If more than 10 parts by mass, unreacted polymerizable compound increases, .

After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and at least one of active energy rays and heat between at least one substrate of the pair of substrates and the liquid crystal layer It is preferably used for a liquid crystal display device manufactured by arranging a liquid crystal alignment film containing a polymerizable group to be polymerized and applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerizing from at least one of the active energy ray and heat, a method of adding a compound containing the polymerizable group to the liquid crystal alignment treatment agent or a method of using a polymer component containing a polymerizable group . Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation of ultraviolet rays and heating have.

For example, a pair of substrates on which liquid crystal alignment films are formed are prepared, spacers are scattered on the liquid crystal alignment films of the substrates of the individual substrates, the substrates of the other substrates are bonded so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed and a substrate is then subjected to sealing to perform sealing.

After the liquid crystal cell is fabricated, the alignment of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

As described above, the liquid crystal display element manufactured by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television of a large screen and a large screen.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

&Quot; Synthesis of polyimide precursor and polyimide of the present invention: specific polymer as component (B) of the present invention &quot;

&Lt; Diamine component &gt;

(Specific side chain type diamine compound: diamine compound represented by formula [1a] of the present invention)

A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (diamine compound represented by the following formula [A1]

A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (diamine compound represented by the following formula [A2]

A3: 1,3-Diamino-4- {trans 4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (diamine compound represented by the following formula [A3]

A4: A diamine compound represented by the following formula [A4]

(70)

(71)

(The diamine compound represented by the formula [2] of the present invention)

B1: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [B1]):

B2: a diamine compound represented by the following formula [B2]

(72)

(Other diamine compounds)

C1: p-phenylenediamine (diamine compound represented by the following formula [C1]):

C2: 4,4'-diaminodiphenylamine (diamine compound represented by the following formula [C2]):

C3: 1,3-Diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [C3]):

(73)

&Lt; Tetracarboxylic acid component &gt;

D1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D1]):

D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D2]

D3: tetracarboxylic acid dianhydride represented by the following formula [D3]

D4: tetracarboxylic acid dianhydride represented by the following formula [D4]

&Lt; EMI ID =

<Organic solvent>

(Organic solvent which is the component (A) of the present invention)

PB: Propylene glycol monobutyl ether

(Organic solvent as component (C) of the present invention)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

(Organic solvent as component (D) of the present invention)

PGME: Propylene glycol monomethyl ether

PCS: Ethylene glycol monopropyl ether

DEEE: diethylene glycol monoethyl ether

(Organic solvent of component (E) of the present invention)

BCS: ethylene glycol monobutyl ether

<Molecular weight measurement of polyimide precursor and polyimide>

The molecular weights of the polyimide precursor and the polyimide in the synthetic examples were measured using a gel permeation chromatograph (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) Manufactured by Toshiba Machine Co., Ltd.).

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ (L), phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, 10 ml / l of tetrahydrofuran (THF)

Flow rate: 1.0 ml / min

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

&Lt; Measurement of imidization rate of polyimide &

The imidization rate of the polyimide in the synthesis example was measured as follows. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) mixture was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, (0.53 ml) was added, and completely dissolved by adding ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Dental Electronics Co., Ltd.). A proton originating from a structure which does not change before and after the imidization is determined as a reference proton and the peak value of the proton and the proton peak derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm And the total value was obtained by the following formula.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid when the polyamide acid (imidization ratio is 0% The ratio of the number of reference protons to one protopertone.

&Quot; Synthesis of specific polymer and comparative example polymer (B) of the present invention &quot;

&Lt; Synthesis Example 1 &

D1 (9.10 g, 46.4 mmol), Al (8.83 g, 23.2 mmol) and B1 (3.53 g, 23.2 mmol) were mixed in NEP (64.4 g) and reacted at 40 ° C for 6 hours to obtain resin solid concentration To obtain a 25 mass% polyamic acid solution (1). This polyamic acid had a number average molecular weight of 25,200 and a weight average molecular weight of 70,300.

&Lt; Synthesis Example 2 &

A mixture of D2 (6.25 g, 25.0 mmol), A1 (6.79 g, 17.8 mmol), B1 (2.17 g, 14.3 mmol) and C1 (0.39 g, 3.61 mmol) in NMP (29.2 g) (2.10 g, 10.7 mmol) and NMP (23.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass% . The polyamic acid had a number average molecular weight of 23,200 and a weight average molecular weight of 65,300.

&Lt; Synthesis Example 3 &

NMP was added to the polyamic acid solution (2) (40.0 g) obtained in Synthesis Example 2 to dilute it to 6 mass%, acetic anhydride (4.75 g) and pyridine (3.75 g) were added as an imidation catalyst, The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The imidization ratio of the polyimide was 56%, the number average molecular weight was 18,900, and the weight average molecular weight was 45,400.

&Lt; Synthesis Example 4 &

A mixture of D2 (6.10 g, 24.4 mmol), A3 (5.28 g, 12.2 mmol), B1 (2.65 g, 17.4 mmol) and B2 (1.06 g, 5.21 mmol) in NMP (28.3 g) (2.05 g, 10.5 mmol) and NMP (23.1 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (9.00 g) and pyridine (6.50 g) were added as imidation catalysts and reacted at 90 ° C for 3 hours . This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 80%, the number average molecular weight was 17,200, and the weight average molecular weight was 40,900.

&Lt; Synthesis Example 5 &

A mixture of D2 (4.40 g, 17.6 mmol), A1 (6.70 g, 17.6 mmol), B1 (1.07 g, 7.03 mmol) and C2 (2.10 g, 10.5 mmol) in NMP (29.2 g) After reacting for 5 hours at 25 ° C, D1 (3.45 g, 17.6 mmol) and NMP (23.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (4.70 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 55%, the number average molecular weight was 18,800, and the weight average molecular weight was 43,500.

&Lt; Synthesis Example 6 &

(0.41 g, 3.79 mmol) were mixed in NMP (29.1 g) and treated with a solution of 80 (0.61 g, 34.7 mmol), D2 (8.61 g, 34.4 mmol) (0.75 g, 3.82 mmol) and NMP (23.8 g) were added and reacted at 40 DEG C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (4.65 g) and pyridine (3.65 g) were added as an imidation catalyst and the reaction was carried out at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 51%, the number average molecular weight was 14,800, and the weight average molecular weight was 37,300.

&Lt; Synthesis Example 7 &

(2.14 g, 13.9 mmol) and B2 (1.41 g, 6.94 mmol) were mixed in NMP (27.6 g) and treated with 80 (3.40 g, 17.3 mmol) and NMP (22.6 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute it to 6 mass%, acetic anhydride (8.85 g) and pyridine (6.25 g) were added as imidation catalysts and reacted at 90 ° C for 3.5 hours . This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 78%, the number average molecular weight was 18,200, and the weight average molecular weight was 42,500.

&Lt; Synthesis Example 8 &

B1 (2.91 g, 19.1 mmol), B2 (0.78 g, 3.84 mmol) and Cl (0.41 g, 3.79 mmol) were added to a solution of D2 (7.65 g, 30.6 mmol), A3 (4.96 g, 11.5 mmol) (1.50 g, 7.65 mmol) and NMP (24.6 g) were added and reacted at 40 占 폚 for 6 hours to obtain a resin solid concentration of 25 % By mass of a polyamic acid solution.

To the obtained polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.90 g) and pyridine (3.90 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 60%, the number average molecular weight was 17,600, and the weight average molecular weight was 39,900.

&Lt; Synthesis Example 9 &

(0.39 g, 3.61 mmol) were mixed in NMP (52.1 g) and treated with a solution of D3 (8.00 g, 35.7 mmol), A1 (6.79 g, 17.8 mmol), B1 (2.17 g, 14.3 mmol) C for 5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (4.71 g) and pyridine (3.60 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 55%, the number average molecular weight was 17,900, and the weight average molecular weight was 40,100.

&Lt; Synthesis Example 10 &

(5.19 g, 34.1 mmol) and D3 (9.00 g, 40.1 mmol), A4 (2.97 g, 6.03 mmol) and B1 (5.19 g, 34.1 mmol) were mixed in 51.5 g of NMP and reacted at 40 ° C for 8 hours, Of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (4.70 g) and pyridine (3.60 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The imidization ratio of the polyimide was 50%, the number average molecular weight was 16,100, and the weight average molecular weight was 37,900.

&Lt; Synthesis Example 11 &

A mixture of D4 (5.97 g, 19.9 mmol), A2 (5.23 g, 13.3 mmol), B1 (2.02 g, 13.3 mmol) and C2 (1.32 g, 6.62 mmol) in NMP (28.3 g) (2.60 g, 13.3 mmol) and NMP (23.1 g) were added and reacted at 40 占 폚 for 5 hours to obtain a polyamic acid solution 11 having a resin solid content concentration of 25 mass% &Lt; / RTI &gt; This polyamic acid had a number average molecular weight of 24,500 and a weight average molecular weight of 69,900.

&Lt; Synthesis Example 12 &

To the polyamic acid solution (11) (40.0 g) obtained in Synthesis Example 11, NMP was added and diluted to 6% by mass, acetic anhydride (4.85 g) and pyridine (3.75 g) were added as an imidation catalyst, Followed by reaction at 80 ° C for 4.5 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (12). The imidization ratio of the polyimide was 61%, the number average molecular weight was 18,500, and the weight average molecular weight was 42,200.

&Lt; Synthesis Example 13 &

(4.49 g, 11.4 mmol), B1 (1.49 g, 9.79 mmol) and B2 (2.32 g, 11.4 mmol) were mixed in NMP (27.8 g) After reacting for 5 hours at room temperature, D1 (3.20 g, 16.3 mmol) and NMP (22.8 g) were added and reacted at 40 占 폚 for 5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (8.90 g) and pyridine (6.50 g) were added as imidation catalysts and reacted at 90 ° C for 3.5 hours . This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (13). The imidization ratio of the polyimide was 80%, the number average molecular weight was 16,400, and the weight average molecular weight was 38,500.

&Lt; Synthesis Example 14 &

C (0.41 g, 3.79 mmol) and C3 (7.20 g, 19.1 mmol) were mixed in NMP (31.2 g) and treated with a solution of D2 (6.70 g, 26.8 mmol), B1 (2.33 g, 15.3 mmol) (2.25 g, 11.5 mmol) and NMP (25.5 g) were added and reacted at 40 占 폚 for 5 hours to obtain a polyamic acid solution 14 having a resin solid content concentration of 25 mass% . This polyamic acid had a number average molecular weight of 25,100 and a weight average molecular weight of 68,900.

&Lt; Synthesis Example 15 &

To the polyamic acid solution (14) (40.0 g) obtained in Synthesis Example 14, NMP was added and diluted to 6% by mass, acetic anhydride (4.70 g) and pyridine (3.70 g) were added as an imidation catalyst, The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (15). The imidization ratio of the polyimide was 55%, the number average molecular weight was 19,500, and the weight average molecular weight was 47,900.

The specific polymers of the present invention and the comparative polymers are shown in Table 1.

1: Polyamide acid.

&Quot; Production of liquid crystal alignment treatment agent of the present invention &quot;

In the following Examples 1 to 22 and Comparative Examples 1 to 5, production examples of a liquid crystal alignment treatment agent are described.

The liquid crystal alignment treatment agents of the present invention are shown in Tables 2 to 4.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;, &quot; Evaluation of liquid crystal alignment property and evaluation of liquid crystal alignment property ), Evaluation of the pretilt angle (normal cell) and production of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) were performed. The conditions are as follows.

&Quot; Evaluation of printability of liquid crystal alignment treatment agent &quot;

The liquid crystal alignment treatment agents obtained in Examples and Comparative Examples of the present invention were pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉 to perform printing evaluation. For the printing machine, a simple printer S15 type (manufactured by Nihon Photo Printing Co., Ltd.) was used. The printing was carried out in such a manner that a printing area of 80 mm x 80 mm, an applied pressure of 0.2 mm, five sheets of discarded substrates, a time from printing to drying of 90 seconds, Lt; 0 &gt; C for 5 minutes.

Evaluation of the pinhole of the liquid crystal alignment film, evaluation of the linearity of the end portion of the liquid crystal alignment film, and evaluation of the mounting of the end portion of the liquid crystal alignment film were performed on the obtained liquid crystal alignment film.

The evaluation of the pinhole of the liquid crystal alignment film was carried out by visually observing the liquid crystal alignment film under a sodium lamp. Specifically, the number of pinholes identified on the liquid crystal alignment film was counted, and the smaller the number of pinholes, the better the evaluation was.

The evaluation of the linearity of the end portion of the liquid crystal alignment film was carried out by observing the liquid crystal alignment film at the right end portion with respect to the printing direction by an optical microscope. Specifically, the difference between (1) and (2) in FIG. 1 of the liquid crystal alignment film image obtained by observing the magnification of the optical microscope at 25 times, that is, the length of A in FIG. 1, was measured. At that time, images of all liquid crystal alignment films were obtained at the same magnification. The shorter the length of A, the better the linearity of the end portion of the liquid crystal alignment film.

Mounting of the end portion of the liquid crystal alignment film was evaluated by observing the liquid crystal alignment film at the right end portion with respect to the printing direction by an optical microscope. Specifically, the length of B in Fig. 2 of the liquid crystal alignment film image obtained by observing the magnification of the optical microscope at 25 times was measured. At that time, all liquid crystal alignment film images were obtained at the same magnification. The shorter the length of B, the better the mounting of the end portion of the liquid crystal alignment film.

Tables 5 to 7 show the number of pinholes, the length of A and the length of B in the liquid crystal alignment film obtained in Examples and Comparative Examples.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

The liquid crystal alignment treatment agent 6 obtained in Example 6 of the present invention, the liquid crystal alignment treatment agent 12 obtained in Example 12, the liquid crystal alignment treatment agent 20 obtained in Example 20 and the liquid crystal alignment treatment agent 21 obtained in Example 21, Was subjected to pressure filtration with a membrane filter having a pore diameter of 1 占 퐉 to evaluate the inkjet applicability. For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on an ITO (indium tin oxide) -evaporated substrate cleaned with pure water and IPA (isopropyl alcohol) with a coating area of 70 x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 Mm / sec, the time from application to drying was 60 seconds, and drying was carried out on a hot plate at 70 DEG C for 5 minutes.

The evaluation of the pinhole of the obtained liquid crystal alignment film was carried out under the same conditions as in &quot; evaluation of printability of liquid crystal alignment treatment agent &quot;.

Table 5 and Table 6 show the number of pinholes of the liquid crystal alignment film obtained in the examples.

&Quot; Production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot;

The liquid crystal alignment treatment agent obtained in Examples and Comparative Examples of the present invention was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell. This solution was spin-coated on an ITO surface of a substrate (40 mm long × 30 mm wide, 0.7 mm thick) on which a 30 × 40 mm ITO electrode cleaned with pure water and IPA had been formed and heat treated on a hot plate at 100 ° C. for 5 minutes To obtain an ITO substrate on which a polyimide liquid crystal alignment film having a thickness of 100 nm was formed. The coated surface of the ITO substrate was rubbed with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation rate of 1000 rpm, a roll advancing speed of 50 mm / sec and an indentation amount of 0.1 mm.

Two sheets of the ITO substrates on which the obtained liquid crystal alignment films were formed were prepared, and the liquid crystal alignment film faces were set inside with spacers of 6 mu m interposed therebetween, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals) was printed. Subsequently, the other substrate and the liquid crystal alignment film were faced to each other with facing each other, and then the sealant was cured by heat treatment at 120 ° C for 90 minutes in a thermocycling type clean oven to prepare empty cells. A liquid crystal was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell (ordinary cell). Nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was used for the liquid crystal at that time.

Using the liquid crystal cell obtained above, evaluation of liquid crystal alignability was carried out. The liquid crystal alignability was determined by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation) to determine whether there was an alignment defect. Concretely, it was determined that the evaluation was excellent in the case where alignment defects could not be seen (indicated as good in Tables 8 to 10).

Tables 8 to 10 show the results of the liquid crystal alignment properties obtained in the examples and comparative examples.

Evaluation of Pretilt Angle (Normal Cell)

Evaluation of the pretilt angle was carried out by using the liquid crystal cell obtained in the above-mentioned &quot; Production of liquid crystal cell and evaluation of liquid crystal orientation (normal cell) &quot;. The pretilt angle was measured after heat treatment at 95 ° C for 5 minutes, after heat treatment at 120 ° C for 5 hours, after injecting the liquid crystal. After the liquid crystal injection, the liquid crystal cell after heat treatment at 95 캜 for 5 minutes was irradiated with ultraviolet rays of 10 J / cm 2 in terms of 365 nm, and then measured.

The smaller the change in the pretilt angle after the heat treatment at 120 ° C for 5 hours or after the ultraviolet ray irradiation, the higher the stability of the pretilt angle with respect to heat or ultraviolet ray, relative to the pretilt angle after heat treatment at 95 ° C for 5 minutes Respectively.

The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). In addition, UV irradiation was performed using a table-top UV curing apparatus (HCT3B28HEX-1) (manufactured by Sen Wright).

Tables 8 to 10 show the results of the pretilt angles obtained in Examples and Comparative Examples.

&Quot; Production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;

The liquid crystal alignment treatment agent (5) obtained in Example 5 and the liquid crystal alignment treatment agent (19) obtained in Example 19 were pressure-filtered with a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell and evaluate the liquid crystal alignment properties. This solution was coated on a substrate (40 mm long × 30 mm wide, 0.7 mm thick) on which ITO electrodes with a pattern interval of 20 μm were formed with 10 × 10 mm in the center, cleaned with pure water and IPA and a 10 × 40 mm ITO electrode Was spin-coated on the ITO surface of a substrate (40 mm long x 30 mm wide, 0.7 mm thick) formed thereon, and heat treatment was performed on a hot plate at 100 DEG C for 5 minutes to obtain a polyimide coating film having a thickness of 100 nm. After the coating film surface was cleaned with pure water, the substrate was heat-treated at 100 ° C for 15 minutes in a thermocycling type clean oven to obtain a substrate having a liquid crystal alignment film formed thereon.

The substrate on which the liquid crystal alignment film was formed was assembled with spacers of 6 占 퐉 interposed therebetween with the liquid crystal alignment film surface on the inner side and bonded to the periphery with a sealant to prepare empty cells. The polymerizable compound (1) represented by the following formula was dissolved in 100 ml of a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) A liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) relative to the mass% was injected, and the injection port was sealed to obtain a liquid crystal cell.

(75)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying an AC voltage of 5 V to the obtained liquid crystal cell and irradiated with ultraviolet light of 20 J / cm 2 in terms of 365 nm, (PSA cell) in which the alignment direction of the liquid crystal cell was controlled. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

It was confirmed that the PSA cell obtained in the Example had a higher response speed of the liquid crystal cell after the ultraviolet ray irradiation than the liquid crystal cell before the ultraviolet ray irradiation, so that the alignment direction of the liquid crystal was controlled. Also, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) for all the liquid crystal cells.

&Lt; Example 1 &gt;

NEP (18.9 g) and PB (14.4 g) were added to polyamic acid solution (1) (10.5 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 1 and stirred at 25 캜 for 3 hours To obtain a liquid crystal alignment treatment agent (1). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent (1), and it was confirmed that the solution was a homogeneous solution. Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 1 under the above- Cell) &quot;.

&Lt; Example 2 &gt;

NMP (16.0 g) and PB (15.7 g) were added to polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 2 and stirred at 25 캜 for 3 hours Thereby obtaining a liquid crystal alignment treating agent (2). No abnormality such as occurrence of turbidity or precipitates was observed in the liquid crystal alignment treatment agent (2), and it was confirmed that the solution was a homogeneous solution. Evaluation of printability of a liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal alignment properties (normal cell) &quot; and evaluation of a pretilt angle (normal (normal)) were carried out by using the obtained liquid crystal alignment treatment agent 2 under the above- Cell) &quot;.

&Lt; Example 3 &gt;

NMP (14.0 g), PB (11.8 g) and BCS (5.90 g) were added to a polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 2, C for 3 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent (3), and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal alignment property (normal cell) &quot;, and evaluation of the pretilt angle (normal (normal)) were carried out by using the obtained liquid crystal alignment treatment agent 3 under the above- Cell) &quot;.

<Example 4>

NMP (17.6 g) was added to the polyimide powder (3) (2.50 g) obtained by the synthetic method of Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (21.5 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (4). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent (4), and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal cell alignment and evaluation of liquid crystal orientation (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) were carried out using the obtained liquid crystal alignment treatment agent (4) Cell) &quot;.

&Lt; Example 5 &gt;

NMP (8.00 g) and NEP (12.0 g) were added to the polyimide powder (3) (2.55 g) obtained by the synthetic method of Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (16.0 g) and BCS (4.00 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 5, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal orientation property (normal cell) &quot;, &quot; evaluation of pretilt angle (normal (Production of liquid crystal cell and evaluation of liquid crystal alignment property (PSA cell) &quot;).

&Lt; Example 6 &gt;

NMP (8.56 g) and NEP (12.8 g) were added to the polyimide powder (3) (1.55 g) obtained by the synthetic method of Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (17.1 g) and BCS (4.30 g) were added and stirred at 40 占 폚 for 6 hours to obtain liquid crystal alignment treatment agent (6). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 6, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (6), &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was carried out under the above-described conditions.

&Lt; Example 7 &gt;

NMP (19.6 g) was added to the polyimide powder (4) (2.50 g) obtained by the synthetic method of Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (3.90 g), PCS (7.80 g) and BCS (7.80 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 7, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 7 under the above- Cell) &quot;.

&Lt; Example 8 &gt;

? -BL (18.0 g) was added to the polyimide powder (5) (2.56 g) obtained by the synthetic method of Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (16.0 g) and PGME (6.00 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment processing agent (8). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 8, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) were carried out under the above- Cell) &quot;.

&Lt; Example 9 &gt;

NEP (22.0 g) was added to the polyimide powder (6) (2.55 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (8.00 g) and BCS (10.0 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 9, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of a liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal alignment properties (normal cell) &quot; and evaluation of a pretilt angle (normal) were conducted under the above-described conditions using the obtained liquid crystal alignment treatment agent 9 Cell) &quot;.

&Lt; Example 10 &gt;

NMP (6.00 g) and NEP (12.0 g) were added to the polyimide powder (7) (2.55 g) obtained by the synthetic method of Synthetic Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (16.0 g) and DEEE (6.00 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (10). No abnormality such as generation of turbidity or precipitates was observed in this liquid crystal alignment treatment agent 10, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were conducted under the above- Cell) &quot;.

&Lt; Example 11 &gt;

NEP (19.6 g) was added to the polyimide powder (7) (2.50 g) obtained by the synthetic method of Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (19.6 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (11). No abnormality such as turbidity or generation of precipitates was observed in this liquid crystal alignment treatment agent 11, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out under the above- Cell) &quot;.

&Lt; Example 12 &gt;

NEP (20.7 g) was added to the polyimide powder (7) (1.50 g) obtained by the synthetic method of Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (20.7 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 12, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 12, &quot; evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was carried out under the above-described conditions.

&Lt; Example 13 &gt;

NMP (20.0 g) was added to the polyimide powder (8) (2.55 g) obtained by the synthetic method of Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (8.00 g), PCS (8.00 g) and BCS (4.00 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 13, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal cell alignment and evaluation of liquid crystal orientation (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out using the obtained liquid crystal alignment treatment agent 13 under the above- Cell) &quot;.

&Lt; Example 14 &gt;

? -BL (20.1 g) was added to the polyimide powder (8) (2.57 g) obtained by the synthetic method of Synthetic Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (16.1 g) and DEEE (4.00 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (14). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 14, and it was confirmed that the solution was a homogeneous solution.

Evaluation of liquid crystal alignment treatment agent (evaluation of liquid crystal alignment property (normal cell) &quot; and evaluation of &quot; pretilt angle (normal) evaluation of liquid crystal alignment treatment agent &quot; Cell) &quot;.

&Lt; Example 15 &gt;

NMP (5.94 g) and NEP (15.9 g) were added to the polyimide powder (9) (2.53 g) obtained by the synthetic method of Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (17.8 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 15, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal cell alignment and evaluation of liquid crystal orientation (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out under the above- Cell) &quot;.

&Lt; Example 16 &gt;

NMP (20.0 g) was added to the polyimide powder (10) (2.55 g) obtained by the synthetic method of Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. PB (12.0 g) and PCS (8.00 g) were added to this solution and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (16). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 16, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out under the above- Cell) &quot;.

&Lt; Example 17 &gt;

NMP (11.1 g), NEP (6.92 g) and PB (13.7 g) were added to the polyamide acid solution 11 (10.0 g) having a resin solid content concentration of 25% by mass obtained by the synthetic method of Synthesis Example 11, C for 3 hours to obtain a liquid crystal alignment treatment agent (17). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 17, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal orientation property (normal cell) &quot; and evaluation of & Cell) &quot;.

&Lt; Example 18 &gt;

NMP (16.0 g), PB (5.90 g) and BCS (9.80 g) were added to polyamic acid solution 11 (10.0 g) having a resin solid concentration of 25 mass% obtained by the synthetic method of Synthesis Example 11, C for 3 hours to obtain a liquid crystal alignment treatment agent (18). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 18, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 18 under the above- Cell) &quot;.

&Lt; Example 19 &gt;

NEP (22.1 g) was added to the polyimide powder (12) (2.56 g) obtained by the synthetic method of Synthesis Example 12 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (4.00 g) and BCS (14.0 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (19). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 19, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal cell alignment and liquid crystal alignment properties (normal cell) &quot;, &quot; evaluation of pretilt angle (normal (Production of liquid crystal cell and evaluation of liquid crystal alignment property (PSA cell) &quot;).

&Lt; Example 20 &gt;

NEP (19.2 g) was added to the polyimide powder (12) (1.55 g) obtained by the synthetic method of Synthesis Example 12 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (12.8 g) and BCS (10.7 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (20). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 20, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 20, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was carried out under the above-described conditions.

&Lt; Example 21 &gt;

? -BL (22.7 g) was added to the polyimide powder (12) (1.50 g) obtained by the synthetic method of Synthesis Example 12 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (14.5 g) and PGME (4.10 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (21). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 21, and it was confirmed that the solution was a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent 21, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was carried out under the above-described conditions.

&Lt; Example 22 &gt;

NEP (21.5 g) was added to the polyimide powder (13) (2.50 g) obtained by the synthetic method of Synthesis Example 13 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, PB (11.8 g) and BCS (5.90 g) were added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 22. No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 22, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal orientation property (normal cell) &quot; and evaluation of pretilt angle (normal) were carried out by using the obtained liquid crystal alignment treatment agent 22 under the above- Cell) &quot;.

&Lt; Comparative Example 1 &

NMP (16.0 g) and BCS (15.7 g) were added to polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 2 and stirred at 25 캜 for 3 hours A liquid crystal alignment treatment agent 23 was obtained. No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 23, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal state) of liquid crystal alignment treatment agent "were carried out under the above- Cell) &quot;.

&Lt; Comparative Example 2 &

NMP (39.2 g) was added to the polyimide powder (3) (2.50 g) obtained by the synthetic method of Synthesis Example 3 and stirred at 70 占 폚 for 24 hours to obtain a liquid crystal alignment treating agent (24). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 24, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 24 under the above- Cell) &quot;.

&Lt; Comparative Example 3 &

NMP (17.6 g) was added to the polyimide powder (3) (2.50 g) obtained by the synthetic method of Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, BCS (21.5 g) was added and stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (25). No abnormality such as generation of turbidity or precipitates was observed in the liquid crystal alignment treatment agent 25, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; evaluation of liquid crystal cell alignment and evaluation of liquid crystal orientation (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 25 under the above- Cell) &quot;.

&Lt; Comparative Example 4 &

NMP (17.6 g) and BCS (17.2 g) were added to polyamic acid solution 14 (11.0 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 14 and stirred at 25 캜 for 3 hours A liquid crystal alignment treatment agent 26 was obtained. No abnormality such as turbidity or generation of precipitates was observed in this liquid crystal alignment treatment agent 26, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 26 under the above- Cell) &quot;.

&Lt; Comparative Example 5 &

NMP (18.0 g) was added to the polyimide powder (15) (2.55 g) obtained by the synthetic method of Synthesis Example 15 and dissolved by stirring at 70 占 폚 for 24 hours. BCS (22.0 g) was added to this solution, and the mixture was stirred at 40 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (27). No abnormality such as turbidity or generation of precipitates was observed in the liquid crystal alignment treatment agent 27, and it was confirmed that the solution was a homogeneous solution.

Evaluation of printability of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell and evaluation of liquid crystal alignment property (normal cell) &quot; and &quot; evaluation of pretilt angle (normal) &quot; were carried out by using the obtained liquid crystal alignment treatment agent 27 under the above- Cell) &quot;.

2: represents the proportion of the polymer in the composition (liquid crystal alignment treatment agent).

3: The ratio of the polymer in the composition (liquid crystal alignment treatment agent).

4: Percentage of the polymer in the composition (liquid crystal alignment treatment agent).

5: More than 15 alignment defects due to pinholes were observed.

As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention exhibited a uniform film property without pinhole formation, as compared with the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Further, the linearity of the end portion of the liquid crystal alignment film was high, and the mounting of the end portion of the liquid crystal alignment film was small. Particularly, even when a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using the diamine compound having a specific side chain structure of the present invention, the above-mentioned effect is high.

In the evaluation of the printability of the liquid crystal alignment treatment agent using the same polymer, in the comparison between the example including the specific solvent of the present invention and the comparative example not including the specific solvent, in the comparative example not containing the specific solvent, The linearity of the end portion of the liquid crystal alignment film was low and the mounting of the end portion of the liquid crystal alignment film was large. Specifically, the comparison between Example 2 and Comparative Example 1, and the comparison between Example 4 and Comparative Example 2 and Comparative Example 3 are made.

Further, in the evaluation of the liquid crystal alignment property of the liquid crystal cell of the liquid crystal alignment treatment agent using the same polymer, in the comparison between the example including the specific solvent of the present invention and the comparative example not containing the specific solvent, , Many alignment defects accompanying pinholes were observed. Specifically, the comparison between Example 2 and Comparative Example 1, and the comparison between Example 4 and Comparative Example 2 and Comparative Example 3 are made.

In addition, in the evaluation of the pretilt angle of the liquid crystal cell, in the comparison between the liquid crystal alignment treatment agent containing the specific side chain structure of the present invention and the liquid crystal alignment treatment agent containing no specific side chain structure, The liquid crystal alignment treatment agent had a low stability of the pretilt angle, that is, a large change with respect to heating and ultraviolet rays. Specifically, the comparison between Example 2 and Comparative Example 4 and the comparison between Example 4 and Comparative Example 4 are made. In addition, since the liquid crystal alignment treatment agents of these comparative examples did not contain a specific solvent, many pinholes were generated in the liquid crystal alignment film, the linearity of the end portion of the liquid crystal alignment film was low, and the mounting of the end portions of the liquid crystal alignment film was large. Further, in the evaluation of the liquid crystal alignment property of the liquid crystal cell, many alignment defects accompanying pinholes were observed.

Industrial availability

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film which exhibits uniform film-like properties without pinholes, has a high linearity of the end portion of the liquid crystal alignment film, and has a small amount of mounting at the end portion of the liquid crystal alignment film.

In addition, the liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film which does not cause alignment defects accompanying pinholes. In particular, the same result can be obtained even with a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be preferably used for a liquid crystal television with a large screen and a large screen size, and can be suitably used for a TN device, an STN device, And is useful for a vertically aligned liquid crystal display element.

Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also useful for a liquid crystal display element which needs to irradiate ultraviolet rays when a liquid crystal display element is manufactured. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal display element manufactured through a process of polymerizing the polymerizable compound while applying a voltage between electrodes and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, The present invention is also applicable to a liquid crystal display element manufactured by arranging a liquid crystal alignment film containing a polymerizable group polymerizing at least one of energy rays and heat and polymerizing the polymerizable group while applying a voltage between the electrodes.

Claims (1)

The liquid crystal alignment treatment agent described in the description of the present invention.

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