WO2015046374A1

WO2015046374A1 - Liquid crystal aligning agent and liquid crystal display element using same

Info

Publication number: WO2015046374A1
Application number: PCT/JP2014/075516
Authority: WO
Inventors: 尚士鉄谷; 宏之桜井; 保坂　和義
Original assignee: 日産化学工業株式会社
Priority date: 2013-09-26
Filing date: 2014-09-25
Publication date: 2015-04-02
Also published as: TW201527846A; CN105765453B; KR20160060733A; JPWO2015046374A1; JP6501073B2; KR102255769B1; CN105765453A; TWI673548B

Abstract

A liquid crystal aligning agent which contains the component (A) and the component (B) described below. Component (A): a polymer containing at least one material selected from among polyimides and polyimide precursors having a structure having a nitrogen atom Component (B): a polymer containing at least one material selected from among polyimides and polyimide precursors having a urea structure or a thiourea structure In this connection, the polymer of the component (A) and/or the polymer of the component (B) contains a specific side chain structure.

Description

Liquid crystal aligning agent and liquid crystal display device using the same

The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

Liquid crystal display elements are now widely used as display devices that are thin and light. Usually, in this liquid crystal display element, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal.

As one of the characteristics required for the liquid crystal alignment film, there is control of the so-called pretilt angle of the liquid crystal, which maintains the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Among the techniques for controlling the pretilt angle depending on the structure of the polyimide, the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle (see, for example, Patent Document 1). In addition, the diamine component for increasing the pretilt angle of the liquid crystal has been studied for improving the stability and process dependency of the pretilt angle, and the side chain structure used here is phenyl. Those containing a ring structure such as a group or a cyclohexyl group have been proposed (see, for example, Patent Document 2).

In addition, as liquid crystal display elements are becoming higher in definition, liquid crystal alignment films used in the liquid crystal alignment films used in the liquid crystal display elements have a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing contrast reduction and afterimage phenomenon. The characteristic that the accumulated charge when applied is small or the charge accumulated by the DC voltage is quickly relaxed has become increasingly important.

In a polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used as a short time until the afterimage generated by direct current voltage disappears. And a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine having a pyridine skeleton or the like as a raw material (for example, see Patent Document 4). In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (for example, Patent Document 5) is known.

JP-A-2-282726 JP-A-9-278724 JP-A-9-316200 JP-A-10-104633 JP-A-8-76128

The liquid crystal alignment film is also used for controlling the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. In particular, in the VA (Vertical Alignment) mode and the PSA (Polymer Sustained Alignment) mode, the liquid crystal needs to be aligned vertically, so the liquid crystal alignment film has the ability to align the liquid crystal vertically (vertical alignment and high pretilt). Called corners). Furthermore, the liquid crystal alignment film has become important not only for high vertical alignment but also for its stability. In particular, liquid crystal display elements that use a backlight that generates a large amount of heat and has a large amount of light to obtain high brightness, such as car navigation systems and large televisions, are exposed to high temperatures and light for a long time. There are cases where it is used or left in a dark environment. Under such severe conditions, when the vertical alignment property is deteriorated, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.

Furthermore, regarding the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element, high stability under the above severe conditions is also required. That is, if the voltage holding ratio is reduced by light irradiation from the backlight, a burn-in defect (also referred to as line burn-in), which is one of display defects of the liquid crystal display element, is likely to occur. A high liquid crystal display element cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time. Furthermore, there is a need for a liquid crystal alignment film that can quickly relieve residual charges accumulated by a direct current voltage by light irradiation from a backlight, even for another surface burn-in that is a poor image burn-in.

Therefore, an object of the present invention is to provide a liquid crystal aligning agent having the above characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, an object of the present invention is to provide a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio even after being exposed to light irradiation for a long time and quickly relaxes residual charges accumulated by a DC voltage.

In addition, another object of the present invention is to provide a liquid crystal display element having the above liquid crystal alignment film and a liquid crystal alignment treatment agent that can provide the above liquid crystal alignment film.

Furthermore, an object of the present invention is to provide a liquid crystal display element provided with a liquid crystal alignment film that meets the above-mentioned requirements.

As a result of intensive studies, the present inventor has found that a liquid crystal alignment treatment agent having two polymers having a specific structure is extremely effective for achieving the above object, and completes the present invention. It came.

That is, the present invention has the following gist.
(1) Liquid crystal aligning agent containing the following (A) component and (B) component.
(A) Component: A polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and polyimide.
(B) Component: A polymer containing at least one selected from a polyimide precursor having a structure represented by the following formula [2] and a polyimide.
In addition, at least one of the polymer of the component (A) and the component (B) contains a structure represented by the following formula [3].

(In Formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R ¹ ) — (R ¹ is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R ² ) — (R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R ³ ) CO— (R ³ represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH ₂ O—, —COO— and —OCO—, wherein Y ² and Y ⁶ are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y ⁴ represents an oxygen atom or a sulfur atom).

(In the formula [3], B ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. B ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), B ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or —OCO—, wherein B ⁴ is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton A divalent organic group having 17 to 51, wherein any hydrogen atom on the cyclic group contains an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or fluorine having 1 to 3 carbon atoms May be substituted with an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom , B ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, having 1 to 3 carbon atoms May be substituted with an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom, n represents an integer of 0 to 4, and B ⁶ represents the number of carbon atoms An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).

(2) The liquid crystal alignment according to (1), wherein the structure having a nitrogen atom in the component (B) is at least one structure selected from the structures represented by the following formulas [1a] to [1c]: Processing agent.

(In the formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X ² represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms, 1b], X ³ and X ⁷ each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X ⁴ and X ⁶ are each independently Represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X ⁵ represents an alkylene group or biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and in formula [1c], X ⁸ And X ¹⁰ each independently represents at least one structure selected from the structures represented by the following formulas [1c-a] and [1c-b], and X ⁹ represents an alkylene group having 1 to 5 carbon atoms. Or a benzene ring).

(3) In the above (1) or (2), the polymer of the component (A) is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material. The liquid crystal aligning agent of description.

(In Formula [1-1], X ^A represents an organic group having at least one structure selected from the structures represented by Formula [1a] to Formula [1c], and A ¹ and A ² are each independently selected. A hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(4) The liquid crystal according to (3), wherein the diamine compound is a polymer obtained by using a diamine compound represented by the following formulas [1a-1] to [1c-1] as a part of the raw material Alignment treatment agent.

(In the formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X ² represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms, In the formula [1b-1], X ³ and X ⁷ each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X ⁴ and X ⁶ are Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X ⁵ represents an alkylene group or biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and the formula [1c- 1], X ⁸ and X ¹⁰ each independently represent at least one structure selected from the structures represented by the formulas [1c-a] and [1c-b], and X ⁹ has 1 carbon atom Represents an alkylene group or a benzene ring represented by formulas [1a-1] to In [1c-1], A ¹ to A ⁶ each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

(5) The liquid crystal aligning agent according to (4), wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [1-1a] to [1-4a]: .

(In the formula [1-3a], R ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. In the formula [1-4a], n represents an integer of 1 to 10, and the formula [1-1a] In Formula [1-4a], A ¹ to A ⁸ each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

(6) The above-mentioned (1) to (5), wherein the polymer of the component (B) is a polymer obtained by using a diamine compound represented by the following formula [2-1] as a part of the raw material. The liquid-crystal aligning agent in any one.

(In Formula [2-1], Y ^A represents an organic group having the structure represented by Formula [2], and A ¹ and A ² are each independently a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Showing).

(7) The liquid-crystal aligning agent as described in said (6) whose said diamine compound is a polymer obtained by using the diamine compound shown by following formula [2a] for some raw materials. *

(In Formula [2a], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R ¹ ) — (R ¹ is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R ² ) — (R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R ³ ) CO— (R ³ represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH ₂ O—, —COO— and —OCO—, wherein Y ² and Y ⁶ are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, Y ⁴ represents an oxygen atom or a sulfur atom, and A ¹ and A 5 ² each independently represent a hydrogen atom or a C 1-5 It represents an alkylene group).

(8) The liquid crystal aligning agent according to (7), wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [2-1a] to [2-3a]: .

(In the formulas [2-1a] to [2-3a], A ¹ to A ⁶ each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(9) The above (1) to (8) wherein a diamine compound represented by the following formula [3a] is used as a part of the raw material for at least one of the (A) component and the (B) polymer. ) The liquid crystal aligning agent according to any one of

(In the formula [3a], B represents the above formula [3], A ¹ and A ² each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and m represents an integer of 1 to 4. Show).

(10) The polymer of the component (A) and the polymer of the component (B) are at least one selected from a polyimide precursor obtained by using a tetracarboxylic acid component represented by the following formula [4] and a polyimide. The liquid crystal aligning agent according to any one of (1) to (9) above, which is a polymer of

(In the formula [4], Z represents at least one structure selected from structures represented by the following formulas [4a] to [4k]).

(In the formula [4a], Z ¹ to Z ⁴ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [4g] Z ⁵ and Z ⁶ each represent a hydrogen atom or a methyl group, and may be the same or different.

(11) The tetracarboxylic acid component is a tetracarboxylic acid having at least one structure selected from the structures represented by the formulas [4a] and [4e] to [4g], wherein Z in the formula [4] The liquid-crystal aligning agent as described in said (10) which is a component.

(12) In the polymer of the component (A), the diamine compounds represented by the formulas [1a-1] to [1c-1] are 5 mol% to 95 mol% in 100 mol% of all diamine components. The liquid crystal aligning agent according to any one of (4) to (11) above.

(13) In the polymer of the component (B), the diamine compound represented by the formula [2a] is 5 mol% to 95 mol% in 100 mol% of all diamine components. 12) The liquid-crystal aligning agent in any one of.

(14) Any of (1) to (13) above, wherein the polymer of component (B) is 0.5 to 950 parts by mass with respect to 100 parts by mass of polymer of component (A). A liquid crystal alignment treatment agent according to claim 1.

(15) The above (1) to (14) containing at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone as a solvent for the liquid crystal aligning agent The liquid-crystal aligning agent in any one of.

(16) The solvent for the liquid crystal aligning agent is at least selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether. The liquid crystal aligning agent according to any one of (1) to (15) above, which contains one kind of solvent.

(17) At least one substitution selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group in the liquid crystal aligning agent The liquid crystal aligning agent according to any one of (1) to (16) above, comprising at least one crosslinkable compound selected from a crosslinkable compound having a group and a crosslinkable compound having a polymerizable unsaturated bond.

(18) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (17).

(19) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal aligning agent according to any one of (1) to (17).

(20) A liquid crystal display device having the liquid crystal alignment film according to (18) or (19).

(21) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (18) or (19), wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(22) A liquid crystal display element comprising the liquid crystal alignment film according to (21).

(23) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film as described in (18) or (19) above, which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(24) A liquid crystal display device comprising the liquid crystal alignment film according to (23).

The liquid crystal aligning agent containing at least one polymer selected from polyimide precursors or polyimides having a specific structure of the present invention has a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. A liquid crystal alignment film that can be expressed can be obtained. In addition, even after being exposed to light irradiation for a long time, a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

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 a liquid crystal display element having the liquid crystal alignment film. is there.

Liquid crystal aligning agent containing the following (A) component and (B) component.
(A) Component: A polymer (also referred to as a specific polymer (A)) containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and polyimide.
Component (B): a polymer (specific polymer (B)) containing at least one selected from polyimide precursors and polyimides having a structure represented by the following formula [2] (also referred to as specific structure (2)) Also called).

In addition, at least one of the polymers of the component (A) and the component (B) contains a structure represented by the following formula [3] (also referred to as a specific side chain structure).

The reason why the problems of the present invention are solved in the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is not necessarily clear, but is considered as follows.

That is, the specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention has a benzene ring or a cyclohexyl ring at the side chain site. Or a divalent organic group having 17 to 51 carbon atoms having a heterocyclic ring or a steroid skeleton. The side chain structure of these rings and organic groups shows a rigid structure as compared with the side chain structure of long-chain alkyl groups, which is a conventional technique for vertically aligning liquid crystals. As a result, the liquid crystal alignment film obtained from the liquid crystal aligning agent having a specific side chain structure of the present invention has higher and more stable vertical alignment of liquid crystals than the conventional long chain alkyl group side chain structure. Obtainable.

Also, the specific side chain structure of the present invention is more stable to light such as ultraviolet rays than the conventional side chain structure of long-chain alkyl groups. Therefore, the specific side chain structure of the present invention can reduce the voltage holding ratio and suppress the decomposition product of the side chain component that accumulates residual charges due to DC voltage even when exposed to light irradiation for a long time. .

Furthermore, the interaction between the nitrogen atom in the structure containing the nitrogen atom contained in the specific polymer (A) of the present invention and the carboxyl group (COOH group) in the specific polymer (B), and the specific polymer ( It is considered that charge transfer occurs between the nitrogen atom in the formula [2] in B) and the carboxyl group in the specific polymer (A). Accordingly, the accumulated residual charge can be efficiently transferred within or between the molecules of the polymer. That is, it is considered that the residual charge loss due to the DC voltage can be promoted.

In addition, it is considered that the structure having a nitrogen atom in the specific polymer (A) of the present invention can trap an ionic impurity component that is a factor that lowers the voltage holding ratio. That is, the liquid crystal display element can trap ionic impurities that are generated by exposure to light for a long time, and accordingly, a decrease in voltage holding ratio can be suppressed.

From the above points, the liquid crystal aligning agent containing at least one polymer selected from polyimide precursors or polyimides having a specific structure of the present invention, after being exposed to high temperature and light irradiation for a long time, A liquid crystal alignment film capable of exhibiting a stable pretilt angle can be obtained. In addition, even after being exposed to light irradiation for a long time, a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained.

<Structure having nitrogen atom>
The specific polymer (A) of the present invention is a polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and a polyimide.

Specific examples of the structure containing a nitrogen atom include structures represented by the following formulas [1a] to [1c].

In the formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

In the formula [1a], X ² represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.

In the formula [1a], when X ² is a hydrogen atom, X ¹ represents a nitrogen-containing aromatic heterocyclic ring, and X ² is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms. , X ¹ represents a benzene ring.

In the formula [1b], X ³ and X ⁷ each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.

In the formula [1b], X ⁴ and X ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

In the formula [1b], X ⁵ represents an alkylene group having 2 to 5 carbon atoms or a biphenyl group.

In the formula [1b], m represents an integer of 0 or 1.

In the formula [1c], X ⁸ and X ¹⁰ each independently represent at least one structure selected from structures represented by the following formulas [1c-a] and [1c-b].

In the formula [1c], X ⁹ represents an alkylene group having 1 to 5 carbon atoms or a benzene ring.

<Specific structure (2)>
The specific polymer (B) of the present invention is a polymer containing at least one selected from a polyimide precursor having a specific structure represented by the following formula [2] and a polyimide.

In the formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —S—, —N (R ¹ ) — (R ¹ is a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), —CON (R ² ) — (wherein R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R ³ ) CO— (R ³ Represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), and represents at least one organic group selected from —CH ₂ O—, —COO— and —OCO—. Of these, a single bond, —O—, —S—, —OCO— or —COO— is preferable. More preferred is a single bond, —O— or —S— from the viewpoint of liquid crystal alignment properties and film hardness of the liquid crystal alignment film.

In the formula [2], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among these, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either linear or branched. Specifically, from the viewpoint of liquid crystal alignment properties and film hardness of the liquid crystal alignment film, a methylene group (—CH ₂ —), ethylene group (—CH ₂ CH ₂ ) having a structure having a free rotation portion and small steric hindrance. -), A propylene group (-(CH ₂ ) _3- ) or an isopropyl group (-C (CH ₂ ) _2- ) is preferred.

In formula [2], Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

In the formula [2], Y ⁴ represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferred from the viewpoint of the film hardness of the liquid crystal alignment film.

<Specific side chain structure>
The specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention is a structure represented by the following formula [3]. is there.

In the formula [3], B ¹ represents a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO -Is preferred. 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 [3], B ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.

In the formula [3], B ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Of these, 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 ease of synthesis. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In the formula [3], B ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Further, B ⁴ may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among these, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

In the formula [3], B 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 is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

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

In the formula [3], B ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferred combinations of B ¹ to B ⁶ and n in Formula [3] are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27) (2 -1) to (2-629) are the same combinations. In each table of the International Publication, B ¹ to B ⁶ in the present invention are indicated as Y 1 to Y ^6, but Y 1 to Y ⁶ should be read as B ¹ to B ⁶ . Further, in (2-605) to (2-629) listed in each table of the International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton. An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

<Specific polymer (A) / Specific polymer (B)>
The specific polymer (A) and the specific polymer (B) of the present invention are at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer). Especially, it is preferable that the polyimide-type polymer of this invention is a polyimide precursor or a polyimide obtained by making a diamine component and a tetracarboxylic acid component react.

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

(In the formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² are each independently a hydrogen atom or an alkylene having 1 to 5 carbon atoms. A ³ and A ⁴ each independently represents a hydrogen atom, an alkylene group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer).

Examples of the diamine component include diamine compounds having two primary or secondary amino groups in the molecule.

In addition, examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound.

In order to obtain a polyamic acid in which A ¹ and A ² in the formula [A] are hydrogen atoms, a diamine compound having two primary or secondary amino groups in the molecule, a tetracarboxylic acid compound or tetra It can be obtained by reacting with a carboxylic anhydride.

In order to obtain a polyamic acid alkyl ester in which A ¹ and A ² in the formula [A] are an alkylene group having 1 to 5 carbon atoms, the diamine compound, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or It can be obtained by reacting with a tetracarboxylic acid dialkyl ester dihalide compound. Further, an alkylene group having 1 to 5 carbon atoms of A ¹ and A ^{2 represented by} the formula [A] can be introduced into the polyamic acid obtained by the above method.

The specific polymer (A) of the present invention is a polymer having a structure containing a nitrogen atom. In particular, the structure represented by the formula [1a] to the formula [1c] is preferable.

The method for introducing a structure containing a nitrogen atom into the specific polymer (A) is not particularly limited, but a diamine compound having a structure represented by the above formulas [1a] to [1c] is used as a part of the raw material. It is preferable.

Specifically, it is preferable to use a diamine compound represented by the following formula [1-1] (also referred to as a specific diamine compound (1)).

In the formula [1-1], X ^A represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by the formulas [1a] to [1c].

In the formula [1-1], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

More specifically, diamine compounds represented by the following formulas [1a-1] to [1c-1] are preferably used.

In the formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

In the formula [1a-1], X ² represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms.

In the formula [1a-1], when X ² is a hydrogen atom, X ¹ represents a nitrogen-containing aromatic heterocyclic ring, and X ² is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms. In this case, X ¹ represents a benzene ring.

In the formula [1b-1], X ³ and X ⁷ each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.

In the formula [1b-1], X ⁴ and X ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

In the formula [1b-1], X ⁵ represents an alkylene group having 2 to 5 carbon atoms or a biphenyl group.

In the formula [1b-1], m represents an integer of 0 or 1.

In formula [1c-1], X ⁸ and X ¹⁰ each independently represent at least one structure selected from structures represented by the following formulas [1c-a] and [1c-b].

In the formula [1c-1], X ⁹ represents an alkylene group having 1 to 5 carbon atoms or a benzene ring.

Specific examples of the diamine compound (1) of the present invention include diamine compounds represented by the following formulas [1-1a] to [1-4a].

In the formula [1-3a], R ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

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

In the formulas [1-1a] to [1-4a], A ¹ to A ⁸ each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

Among them, it is preferable to use a diamine compound represented by the formula [1-3a] or the formula [1-4a].

The specific diamine compound (1) in the specific polymer (A) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.

The specific diamine compound (1) of the present invention includes the solubility of the specific polymer (A) of the present invention in the solvent, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment property when the liquid crystal alignment film is formed, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.

The specific polymer (B) of the present invention is a polymer having a specific structure (2).

The method for introducing the specific structure (2) of the present invention into the specific polymer (B) is not particularly limited, but a diamine compound having the specific structure (2) is preferably used as the diamine component. It is particularly preferable to use a diamine compound having a structure represented by the formula [2].

Specifically, it is preferable to use a diamine compound represented by the following formula [2-1] (also referred to as a specific diamine compound (2)).

In Formula [2-1], Y ^A represents an organic group having a structure represented by Formula [2].

In formula [2-1], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

More specifically, it is preferable to use a diamine compound represented by the following formula [2a].

In the formula [2a], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —S—, —N (R ¹ ) — (R ¹ is a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), —CON (R ² ) — (wherein R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R ³ ) CO— (R ³ Represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), and represents at least one organic group selected from —CH ₂ O—, —COO— and —OCO—. Of these, a single bond, —O—, —S—, —OCO— or —COO— is preferable. More preferred is a single bond, —O— or —S—, which is a structure that is as flexible as possible and has as little steric hindrance in terms of liquid crystal orientation and film hardness.

In the formula [2a], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among these, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure thereof may be either linear or branched. Specifically, from the viewpoint of liquid crystal alignment properties and film hardness of the liquid crystal alignment film, a methylene group (—CH ₂ —), ethylene group (—CH ₂ CH ₂ ) having a structure having a free rotation portion and small steric hindrance. -), A propylene group (-(CH ₂ ) _3- ) or an isopropyl group (-C (CH ₂ ) _2- ) is preferred.

In the formula [2a], Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

In formula [2a], Y ⁴ represents an oxygen atom or a sulfur atom. Of these, oxygen atoms are preferred from the viewpoint of the film hardness of the liquid crystal alignment film.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ^{7 in} the formula [2a] are as shown in Table 1 below.

Among these, the combinations represented by the formula [2-1a], the formula [2-2a], the formula [2-4a], the formula [2-5a], the formula [2-7a], and the formula [2-8a] are preferable. .

In the formula [2a], A ¹ and A ² each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

Specific examples of the diamine compound (2) of the present invention include diamine compounds represented by the following formulas [2-1a] to [2-3a].

The specific diamine compound (2) in the specific polymer (B) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.

The specific diamine compound (2) of the present invention has the solubility in the solvent of the specific polymer (B) of the present invention, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment property when it is used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.

At least one of the specific polymer (A) and the specific polymer (B) of the present invention contains a specific side chain structure.

The method for introducing the specific side chain structure of the present invention into the specific polymer (A) or the specific polymer (B) is not particularly limited, but a diamine compound having a specific side chain structure is preferably used as the diamine component. .

Specifically, it is preferable to use a diamine compound represented by the following formula [3a] (also referred to as a specific side chain diamine compound).

In the formula [3a], B represents the formula [3]. The preferred combinations of B ¹ to B ⁶ and n in the formula [3] are as described above.

In the formula [3a], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkylene group having 1 or 2 carbon atoms is preferable.

In the formula [3a], m represents an integer of 1 to 4. Of these, 1 is preferable.

Specific examples of the specific side chain diamine compound of the present invention include, for example, diamine compounds represented by the following formulas [3a-1] to [3a-31], and these amino groups are secondary amino groups. A certain diamine compound is mentioned.

(In the formulas [3a-1] to [3a-3], R ¹ , R ³ and R ⁵ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, wherein R ² , R ⁴ and R ⁶ are each independently a linear or branched alkylene having 1 to 22 carbon atoms in the formulas [3a-1] to [3a-3] Group, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group or fluorine-containing alkoxyl group having 1 to 22 carbon atoms).

(In the formulas [3a-4] to [3a-6], R ¹ , R ³ and R ⁵ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ — _{_{, -CH 2 OCO -, - CH}} 2 O -, - OCH 2 - or -CH ₂ - indicates, wherein [3a-4] ~ formula ^{[3a-6], R 2} , R 4 and ^{R 6} each Independently, a linear or branched alkylene group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms Or a fluorine-containing alkoxyl group).

(In the formulas [3a-7] and [3a-8], R ¹ and R ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O— or —NH—, wherein R ² and R ⁴ are each independently a fluorine group, a cyano group, a trifluoromethane group Nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group).

(In the formulas [3a-9] and [3a-10], R ¹ and R ² each independently represents a linear or branched alkylene group having 3 to 12 carbon atoms, and 1,4-cyclohexylene. The cis-trans isomerism of each is the trans isomer).

(In the formulas [3a-11] and [3a-12], R ¹ and R ² each independently represents a linear or branched alkylene group having 3 to 12 carbon atoms, and 1,4-cyclohexylene. The cis-trans isomerism of each is the trans isomer).

(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, and A ₃ is a 1,4-cyclohexylene group or A ₂ -phenylene group, A ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (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.

Among the above formulas [3a-1] to [3a-31], particularly preferred diamine compounds have the formulas [3a-1] to [3a-6] and [3a-9] to [3a-13]. Or they are the formula [3a-22] to the formula [3a-31].

The specific side chain diamine compound of the present invention may be used in at least one of the specific polymer (A) and the specific polymer (B), or may be used in both specific polymers. Especially, it is preferable to use for a specific polymer (A).

The specific side chain type diamine compound in the specific polymer (A) and / or the specific polymer (B) of the present invention is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.

The specific side chain type diamine compound of the present invention is a liquid crystal in the case where the specific polymer (A) and the specific polymer (B) of the present invention are soluble in a solvent, coating property of a liquid crystal aligning agent, and a liquid crystal alignment film. One kind or a mixture of two or more kinds can be used depending on the orientation, voltage holding ratio, accumulated charge and the like.

As the diamine component of the specific polymer (A) and the specific polymer (B) of the present invention, the specific diamine compound (1), the specific diamine compound (2) and the specific side chain type are used as long as the effects of the present invention are not impaired. Other diamine compounds other than the diamine compound (also referred to as other diamine compounds) can be used.

Specifically, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4, 4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2 , 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, , 4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2 '-Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl -Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine , 3,4'-diaminodiphe Ruamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl (4,4′-diaminodiphenyl) amine, N-methyl (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, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1 , 7-Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, , 3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane Bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4- Aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′ [1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3 , 4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] dianiline, 3,3 '-[1,3-phenylenebis (methylene) ] Dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone] 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-amino Benzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4 -Aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamide), N, N'-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N '-Bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4 -Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (4-amino) Phenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4 -Aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenol) ) Propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3 -Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6- Bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1, 8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-a Nophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) ) Dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane, and further diamine compounds in which these amino groups are secondary amino groups Can be mentioned.

Furthermore, a diamine compound having a carboxyl group (COOH group) or a hydroxyl group (OH group) can also be used in the diamine compound.

Specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, Mention may be made of 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid. Of these, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable. Further, diamine compounds represented by the following formulas [3b-1] to [3b-4] and diamine compounds in which these amino groups are secondary amino groups can also be used.

(In the formula [3b-1], A ¹ 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—, each of m ¹ and m ² independently represents an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, In [3b-2], m ³ and m ⁴ each independently represents an integer of 1 to 5, and in formula [3b-3], A ² represents a linear or branched alkylene group having 1 to 5 carbon atoms. indicates, ^{m 5} represents an integer of 1 to 5, wherein [3b-4], ^{a 3} and ^{a 4} are each independently 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- indicates, ^{m 6} is an integer of 1 to 4) .

In addition, a diamine compound having a nitrogen-containing heterocyclic ring represented by the following formula [3c] and a diamine compound in which these amino groups are secondary amino groups can also be used in the diamine compound.

In the formula [3c], D ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) —. Or —N (CH ₃ ) CO—. Among them, —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— represents a diamine compound. It is preferable because it is easy to synthesize. More preferred is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCO— or —CON (CH ₃ ) —. Particularly preferred is —O—, —CONH— or —CH ₂ O—.

In the formula [3c], D ² represents a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Of these, an alkylene group having 1 to 10 carbon atoms is preferable.

Specific examples of the non-aromatic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring. Decane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring , Norbornene ring or adamantane ring. Of these, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring is preferred.

Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring. Of these, a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.

Preferred D ² in the formula [3c] is a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, A naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring; Of these, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferable.

In the formula [3c], D ³ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). — Or —N (CH ₃ ) CO—, —O (CH ₂ ) _m — (m is an integer of 1 to 5) is shown. Among these, a single bond, —O—, —COO—, —OCO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5) is preferable. More preferred is a single bond, —O—, —OCO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5).

In the formula [3c], D ⁴ is a nitrogen-containing aromatic heterocyclic ring, which is an aromatic heterocyclic ring containing at least one structure selected from the following formulas [a], [b] and [c]. is there.

(In the formula [c], Z represents an alkylene group having 1 to 5 carbon atoms).

More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring be able to. Of these, a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring are preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

Moreover, D ³ in the formula [3c] can expressions included in the D ⁴ [a], is preferably bonded with a substituent nonadjacent the formula [b] and the formula [c].

In the formula [3c], n is an integer of 1 to 4, and is preferably 1 or 2 from the viewpoint of reactivity with the tetracarboxylic acid component.

Particularly preferred combinations of D ¹ to D ⁴ and n in the formula [3c] are as follows: D ¹ represents —CONH—, D ² represents an alkyl group having 1 to 5 carbon atoms, D ³ represents a single bond, ⁴ is a diamine compound in which ⁴ represents an imidazole ring or a pyridine ring and n represents 1.

The bonding position of the two amino groups (—NH ₂ ) in the formula [3c] is not limited. Specifically, with respect to the linking group (B ¹ ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.

Furthermore, as other diamine compounds, diamine compounds represented by the following formulas [3d-1] to [3d-13] and diamine compounds in which these amino groups are secondary amino groups can also be used.

(In the formulas [3d-1] to [3d-4], A ¹ to A ⁴ each independently represents an alkylene group having 1 to 22 carbon atoms or a fluorine-containing alkylene group).

(In the formula [3d-5], A ¹ and A ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or — indicates NH-, a ² represents a linear or straight-chain or branched fluorine-containing alkylene group having branched alkylene group or a C 1-22 of 1 to 22 carbon atoms, the formula [3d-6] in, and each ^{a 4} and ^{a 6} are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown, ^{a 5} Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

(In the formula [3d-7], A ¹ and A ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or — NH— represents A ² represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, and represented by the formula [3d-8] in, and each ^{a 4} and ^{a 6} are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown, ^{a 5} Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

(In the formula [3d-9], A ¹ and A ³ are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or — indicates NH-, a ² represents a linear or straight-chain or branched fluorine-containing alkylene group having branched alkylene group or a C 1-22 of 1 to 22 carbon atoms, the formula [3d-10] in, and each ^{a 4} and ^{a 6} are independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or -NH- are shown, ^{a 5} Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

(In the formula [3d-11], p represents an integer of 1 to 10).

Other diamine compounds of the present invention include the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment properties when used as a liquid crystal alignment film. One type or a mixture of two or more types can be used depending on characteristics such as voltage holding ratio and accumulated charge.

As the specific polymer (A) and specific polymer (B) of the present invention, that is, the tetracarboxylic acid component for producing these polyimide polymers, tetracarboxylic dianhydride represented by the following formula [4] It is preferable to use a product. At that time, not only the tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester di Halide compounds can also be used (the tetracarboxylic dianhydride represented by the formula [4] and its derivatives are collectively referred to as a specific tetracarboxylic acid component).

In the formula [4a], Z ¹ to Z ⁴ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [4g], Z ⁵ and Z ⁶ each represent a hydrogen atom or a methyl group, and may be the same or different.

Among Z in formula [4], from the viewpoint of ease of synthesis and ease of polymerization reactivity in producing a polymer, formula [4a], formula [4c] to formula [4g] or formula [4k] ] The tetracarboxylic dianhydride of the structure shown by these and its tetracarboxylic acid derivative are preferable. More preferable is the structure represented by the formula [4a] or the formula [4e] to the formula [4g]. Particularly preferred are tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives having the structure represented by [4a], formula [4e] or formula [4f].

The specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.

The specific tetracarboxylic acid component of the present invention includes the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment film. One type or a mixture of two or more types can be used depending on the properties such as orientation, voltage holding ratio, and accumulated charge.

As long as the effects of the present invention are not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic acid component are used for the specific polymer (A) and the polyimide polymer of the specific polymer (B). You can also.

Other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds.

That is, other tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4 ′ -Benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1, 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4 Examples include '-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The other tetracarboxylic acid component of the present invention includes the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, the coating property of a liquid crystal aligning agent, and the liquid crystal alignment film. One type or a mixture of two or more types can be used depending on the properties such as orientation, voltage holding ratio, and accumulated charge.

<Method for Producing Specific Polymer (A) / Specific Polymer (B)>
In the present invention, the specific polymer (A) and the specific polymer (B), that is, methods for producing these polyimide polymers are not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydrides and their derivatives is reacted with a diamine component consisting of one or more diamine compounds. And a method of obtaining a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.

In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group, and A method of polycondensation with a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component. The solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.

Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] The indicated solvents can be used.

(In the formula [D-1], D ¹ represents an alkylene group having 1 to 3 carbon atoms. In the formula [D-2], D ² represents an alkylene group having 1 to 3 carbon atoms. ], D ³ represents an alkylene group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydrated and dried solvent.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed or dissolved in the solvent. Methods, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc., and any of these methods May be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer. In this case, the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction can be carried out at a high concentration, and then a solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.

The polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.

When the polyimide precursor is thermally imidized in a solution, the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

The catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can. The amount of the basic catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times of the amic acid groups, and the amount of the acid anhydride is 1 mol times to 50 mol times of the amic acid groups, The amount is preferably 3 mole times to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. Further, when the polymer collected by precipitation is redissolved in a solvent and then re-precipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent. It is a coating solution for forming.

The specific polymer (A) of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid alkyl ester or polyimide is preferable. More preferably, it is a polyimide.

The specific polymer (B) of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid or polyamic acid alkyl ester is preferable. More preferred is polyamic acid.

The ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent of the present invention is 0.5 mass for the specific polymer (B) with respect to 100 mass parts of the specific polymer (A). Part to 950 parts by mass is preferable. Of these, 10 parts by weight to 900 parts by weight is preferable, and 10 parts by weight to 400 parts by weight is more preferable.

All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer (A) and the specific polymer (B) of the present invention, and other polymers are mixed. May be. Examples of other polymers include the polyimide polymer having no tertiary nitrogen atom structure and the polyimide polymer having no specific structure (2). Furthermore, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used. At that time, the content of the other polymer other than that is 0.5 parts by mass with respect to 100 parts by mass of the specific polymer (A) and the specific polymer (B) of the present invention. To 30 parts by mass. Of these, 1 to 20 parts by mass is preferable.

In addition, the content of the solvent in the liquid crystal aligning agent of the present invention is preferably 70% by mass to 99.9% by mass. This content can be appropriately changed depending on the application method of the liquid crystal aligning agent and the film thickness of the target liquid crystal alignment film.

The solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the specific polymer (A) and the specific polymer (B). Although the specific example of a good solvent is given to the following, it is not limited to these examples.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.

Furthermore, when the solubility of the specific polymer (A) and the specific polymer (B) in the solvent is high, it is preferable to use the solvents represented by the formulas [D-1] to [D-3].

The good solvent in the liquid crystal aligning agent of the present invention is preferably 20% by mass to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20% by mass to 90% by mass is preferable. More preferred is 30% by mass to 80% by mass.

The liquid crystal aligning agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied unless the effects of the present invention are impaired. be able to. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-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, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, -Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene Carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1 -(Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, Methyl acetate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, lactate n-propyl ester, lactate n-butyl ester, Examples thereof include lactic acid isoamyl ester and solvents represented by the above formulas [D-1] to [D-3].

Of these, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

These poor solvents are preferably 1% by mass to 80% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 10% by mass to 80% by mass is preferable. More preferred is 20% by mass to 70% by mass.

The liquid crystal aligning agent of the present invention has at least one substituent selected from a crosslinkable 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. It is preferable to introduce a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl , Triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3- Epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2, And 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 [4A].

Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).

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

Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication No. WO2012 / 014898 (published on 2012.2.2). It is done.

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

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated eth Cymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-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] described on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27). Is mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene Cold di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neo A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3- One polymerizable unsaturated group such as chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide in the molecule Examples thereof include crosslinkable compounds.

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

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

The above compound is an example of a crosslinkable compound and is not limited thereto. Moreover, the crosslinkable compound used for the liquid-crystal aligning agent of this invention may be 1 type, and may be combined 2 or more types.

In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.1 parts by mass to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among these, in order for the crosslinking reaction to proceed and to exhibit the desired effect, the amount is preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.

For the liquid crystal alignment treatment agent of the present invention, a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired.

Examples of compounds that improve the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).

The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. ~ 1 part by mass.

Furthermore, in the liquid crystal alignment treatment agent of the present invention, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the element, page 69 of International Publication No. WO2011 / 132751 (published 2011.10.20). It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on page 73. This amine compound may be added directly to the liquid crystal aligning agent, but it is added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable. The solvent is not particularly limited as long as it is a solvent that dissolves the specific polymer (A) and the specific polymer (B) described above.

The liquid crystal alignment treatment agent of the present invention includes, in addition to the above poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film, and a compound that promotes charge removal, As long as the effects of the present invention are not impaired, a dielectric or conductive material for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.

<Liquid crystal alignment film and liquid crystal display element>
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 then subjected to alignment treatment by rubbing treatment or light irradiation. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a highly transparent substrate. In addition to a 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 for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.

After applying the liquid crystal aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.

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

As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.

Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The liquid crystal composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray. The wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

The above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.

That is, in the liquid crystal display element of the present invention, a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is produced by at least one of irradiation with ultraviolet rays and heating. The orientation of the liquid crystal molecules can be controlled by polymerizing.

To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. Can be mentioned.

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. The seizure characteristics of the steel deteriorate.

After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferable to use it for a liquid crystal display element manufactured through a step of arranging a liquid crystal alignment film containing a group and applying a voltage between electrodes, that is, an SC-PVA mode. Here, ultraviolet rays are suitable as the active energy ray. The wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned.

To give an example of SC-PVA mode liquid crystal cell preparation, a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared. The other substrate is bonded so that the inner side is on the inside and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed The method of performing etc. is mentioned.

After the liquid crystal cell is produced, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.

As described above, the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, even after being exposed to light irradiation for a long time, a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained. Therefore, the liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.

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

"Abbreviations used in the synthesis examples, examples and comparative examples of the present invention"
Abbreviations used in the synthesis examples, examples and comparative examples are as follows.

<Monomer for producing the polyimide polymer of the present invention>
(Specific diamine compound (1) of the present invention)
A1: Diamine compound represented by the following formula [A1] A2: Diamine compound represented by the following formula [A2] A3: Diamine compound represented by the following formula [A3]

(Specific diamine compound (2) of the present invention)
B1: Diamine compound represented by the following formula [B1]

(Specific side chain diamine compound of the present invention)
C1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene C2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene C3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene C4: Diamine compound represented by C4]

(Other diamine compounds)
D1: p-phenylenediamine D2: 3,5-diaminobenzoic acid D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic acid component of the present invention)
E1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride E2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride E3: the following formula [E3 E4: tetracarboxylic dianhydride represented by the following formula [E4] E5: tetracarboxylic dianhydride represented by the following formula [E5]

"Crosslinkable compound used in the present invention"
K1: Crosslinkable compound represented by the following formula [K1]

<Solvent used in the present invention>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether
DME: Dipropylene glycol dimethyl ether

"Measurement of molecular weight of polyimide polymer of the present invention"
The molecular weights of the polyimide precursor and the polyimide in the synthesis example are determined using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as follows.

Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample 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 Laboratory).

"Measurement of imidization ratio of polyimide of the present invention"
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. Using the integrated value, the following formula was used.

Imidation rate (%) = (1−α · x / y) × 100

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

"Synthesis of polyimide polymer of the present invention"
<Synthesis Example 1>
E1 (4.50 g, 23.0 mmol), A1 (1.85 g, 9.30 mmol), C1 (0.88 g, 2.32 mmol) and D1 (1.26 g, 11.6 mmol) NMP (25.5 g) Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25 mass%. The number average molecular weight of this polyamic acid was 24,200, and the weight average molecular weight was 86,500.

<Synthesis Example 2>
E1 (4.10 g, 20.9 mmol), B1 (3.16 g, 10.6 mmol), D1 (0.46 g, 4.24 mmol) and D2 (0.97 g, 6.35 mmol) were converted to NMP (26.1 g). Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. The number average molecular weight of this polyamic acid was 25,200, and the weight average molecular weight was 89,100.

<Synthesis Example 3>
E2 (3.96 g, 15.8 mmol), A1 (1.91 g, 9.61 mmol), C1 (6.09 g, 16.0 mmol) and D2 (0.97 g, 6.41 mmol) with NEP (32.1 g) After mixing at 80 ° C. for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (16.0 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution (3) was obtained. The number average molecular weight of this polyamic acid was 20,100, and the weight average molecular weight was 64,100.

<Synthesis Example 4>
NEP was added to the polyamic acid solution (3) (30.0 g) obtained by the synthesis method of Synthesis Example 3 and diluted to 6% by mass, and then acetic anhydride (3.45 g) and pyridine (2. 50 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,500, and the weight average molecular weight was 49,300.

<Synthesis Example 5>
E2 (4.47 g, 17.9 mmol), B1 (3.24 g, 10.9 mmol), C1 (2.75 g, 7.23 mmol) and D2 (2.75 g, 18.1 mmol) with NEP (33.4 g) After mixing at 80 ° C. for 5 hours, E1 (3.50 g, 17.9 mmol) and NEP (16.7 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution (5) was obtained. The number average molecular weight of this polyamic acid was 22,100, and the weight average molecular weight was 68,500.

<Synthesis Example 6>
After adding NEP to the polyamic acid solution (5) (30.0 g) obtained by the synthesis method of Synthesis Example 5 and diluting to 6% by mass, acetic anhydride (3.40 g) and pyridine (2. 65 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 58%, the number average molecular weight was 19,800, and the weight average molecular weight was 52,900.

<Synthesis Example 7>
E2 (1.37 g, 5.46 mmol), A2 (1.18 g, 5.53 mmol), C2 (2.91 g, 7.38 mmol), D1 (0.20 g, 1.84 mmol) and D2 (0.56 g, 3.69 mmol) was mixed in NMP (17.4 g) and reacted at 80 ° C. for 5 hours, then E1 (2.50 g, 12.8 mmol) and NMP (8.72 g) were added, and the mixture was stirred at 40 ° C. for 6 hours. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.45 g) and pyridine (3.30 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,100, and the weight average molecular weight was 47,800.

<Synthesis Example 8>
E2 (1.37 g, 5.46 mmol), B1 (1.38 g, 4.61 mmol), C2 (1.09 g, 2.77 mmol) and D2 (1.68 g, 11.1 mmol) to NMP (16.0 g) After mixing at 80 ° C. for 5 hours, E1 (2.50 g, 12.8 mmol) and NMP (8.02 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,800, and the weight average molecular weight was 49,800.

<Synthesis Example 9>
E3 (7.20 g, 32.1 mmol), A2 (2.78 g, 13.0 mmol), C2 (5.14 g, 13.0 mmol) and D2 (0.99 g, 6.51 mmol) to NEP (48.3 g) Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (9) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 21,200, and the weight average molecular weight was 65,400.

<Synthesis Example 10>
NEP was added to the polyamic acid solution (9) (30.0 g) obtained by the synthesis method of Synthesis Example 9 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 63 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 57%, the number average molecular weight was 18,200, and the weight average molecular weight was 48,300.

<Synthesis Example 11>
E3 (3.85 g, 17.2 mmol), A3 (0.53 g, 2.61 mmol), C4 (2.14 g, 4.35 mmol) and D2 (1.59 g, 10.4 mmol) were added to NMP (24.3 g). Then, the mixture was reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.65 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 68%, the number average molecular weight was 17,500, and the weight average molecular weight was 47,900.

<Synthesis Example 12>
E4 (1.64 g, 5.46 mmol), B1 (1.65 g, 5.53 mmol), C1 (1.40 g, 3.69 mmol), D1 (0.20 g, 1.84 mmol) and D2 (1.12 g, 7.38 mmol) was mixed in NMP (17.0 g) and reacted at 80 ° C. for 6 hours, and then E1 (2.50 g, 12.8 mmol) and NMP (8.52 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.15 g) and pyridine (2.95 g) were added as an imidization catalyst, and the mixture was maintained at 70 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (12). The imidation ratio of this polyimide was 64%, the number average molecular weight was 18,100, and the weight average molecular weight was 49,600.

<Synthesis Example 13>
E4 (2.87 g, 9.56 mmol), A3 (0.98 g, 4.84 mmol), C3 (2.44 g, 5.65 mmol), D1 (0.26 g, 2.42 mmol) and D2 (0.49 g, 3.23 mmol) was mixed in NEP (16.6 g) and reacted at 80 ° C. for 6 hours, and then E1 (1.25 g, 6.37 mmol) and NEP (8.30 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, then acetic anhydride (4.55 g) and pyridine (3.35 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 81%, the number average molecular weight was 16,300, and the weight average molecular weight was 45,100.

<Synthesis Example 14>
E4 (3.57 g, 11.9 mmol), A1 (1.37 g, 6.89 mmol), C4 (1.70 g, 3.44 mmol) and D2 (1.05 g, 6.89 mmol) NMP (17.4 g) After mixing at 80 ° C. for 6 hours, E1 (1.00 g, 5.10 mmol) and NMP (8.69 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, then acetic anhydride (3.75 g) and pyridine (2.35 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (14). The imidation ratio of this polyimide was 53%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,900.

<Synthesis Example 15>
E2 (1.73 g, 6.91 mmol), A1 (0.70 g, 3.50 mmol), A2 (0.75 g, 3.50 mmol), C2 (2.76 g, 7.00 mmol) and D2 (0.53 g, 3.50 mmol) was mixed in NMP (17.3 g) and reacted at 80 ° C. for 6 hours, and then E5 (2.20 g, 10.4 mmol) and NMP (8.67 g) were added. The reaction was carried out for a time to obtain a polyamic acid solution (15) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 20,100, and the weight average molecular weight was 62,600.

<Synthesis Example 16>
E2 (0.88 g, 3.54 mmol), B1 (1.60 g, 5.37 mmol), C1 (1.36 g, 3.58 mmol) and D2 (1.36 g, 8.95 mmol) to NMP (16.4 g) After mixing at 80 ° C. for 6 hours, E5 (3.00 g, 14.1 mmol) and NMP (8.21 g) were added, and the mixture was reacted at 80 ° C. for 6 hours. % Polyamic acid solution (16) was obtained. The number average molecular weight of this polyamic acid was 21,600, and the weight average molecular weight was 65,100.

<Synthesis Example 17>
NMP was added to the polyamic acid solution (16) (30.0 g) obtained by the synthesis method of Synthesis Example 16 and diluted to 6% by mass, and then acetic anhydride (4.50 g) and pyridine (3. 30 g) was added and reacted at 80 ° C. for 3 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (17). The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,800, and the weight average molecular weight was 52,200.

<Synthesis Example 18>
E2 (1.73 g, 6.91 mmol), A3 (0.89 g, 4.38 mmol), C3 (2.65 g, 6.13 mmol) and D2 (1.07 g, 7.00 mmol) were replaced with NEP (17.1 g). After mixing at 80 ° C. for 6 hours, E5 (2.20 g, 10.4 mmol) and NEP (8.54 g) were added, and the mixture was reacted at 80 ° C. for 6 hours. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (4.10 g) and pyridine (3.05 g) were added as an imidization catalyst, and 2. at 70 ° C. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (18). The imidation ratio of this polyimide was 74%, the number average molecular weight was 17,900, and the weight average molecular weight was 48,300.

<Synthesis Example 19>
E2 (0.80 g, 3.18 mmol), A1 (0.96 g, 4.83 mmol), C1 (3.37 g, 8.86 mmol) and D2 (0.37 g, 2.42 mmol) were combined with NMP (16.4 g). After mixing at 80 ° C. for 6 hours, E5 (2.70 g, 12.7 mmol) and NMP (8.20 g) were added and reacted at 80 ° C. for 6 hours. % Polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.75 g) and pyridine (2.55 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (19). The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,800, and the weight average molecular weight was 46,200.

<Synthesis Example 20>
E1 (5.00 g, 25.5 mmol), C1 (0.98 g, 2.58 mmol) and D1 (2.51 g, 23.2 mmol) were mixed in NMP (25.5 g) and reacted at 40 ° C. for 8 hours. Thus, a polyamic acid solution (20) having a resin solid content concentration of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 25,800, and the weight average molecular weight was 88,900.

<Synthesis Example 21>
E1 (5.00 g, 25.5 mmol), D1 (1.96 g, 18.1 mmol) and D2 (1.18 g, 7.75 mmol) were mixed in NMP (24.4 g) and reacted at 40 ° C. for 8 hours. Thus, a polyamic acid solution (21) having a resin solid content concentration of 25% by mass was obtained. The number average molecular weight of this polyamic acid was 27,100, and the weight average molecular weight was 90,100.

<Synthesis Example 22>
E2 (4.08 g, 16.3 mmol), C1 (6.29 g, 16.5 mmol), D1 (1.07 g, 9.92 mmol) and D2 (1.01 g, 6.61 mmol) with NEP (31.3 g) After mixing at 80 ° C. for 5 hours, E1 (3.20 g, 16.3 mmol) and NEP (15.7 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution (22) was obtained. The number average molecular weight of this polyamic acid was 22,500, and the weight average molecular weight was 66,900.

<Synthesis Example 23>
NEP was added to the polyamic acid solution (22) (30.0 g) obtained by the synthesis method of Synthesis Example 22 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 50 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (23). The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,200, and the weight average molecular weight was 50,600.

<Synthesis Example 24>
E2 (4.72 g, 18.9 mmol), C1 (2.91 g, 7.64 mmol), D1 (1.24 g, 11.5 mmol) and D2 (2.91 g, 19.1 mmol) to NEP (31.0 g) After mixing at 80 ° C. for 5 hours, E1 (3.70 g, 18.9 mmol) and NEP (15.5 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution (24) was obtained. The number average molecular weight of this polyamic acid was 23,000, and the weight average molecular weight was 68,800.

<Synthesis Example 25>
NEP was added to the polyamic acid solution (24) (30.0 g) obtained by the synthesis method of Synthesis Example 24 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 65 g) was added and reacted at 60 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (25). The imidation ratio of this polyimide was 57%, the number average molecular weight was 20,100, and the weight average molecular weight was 54,100.

<Synthesis Example 26>
E2 (2.04 g, 8.16 mmol), A1 (0.99 g, 4.96 mmol), D2 (0.50 g, 3.31 mmol) and D3 (3.11 g, 8.26 mmol) were replaced with NEP (16.5 g). After mixing at 80 ° C. for 5 hours, E1 (1.60 g, 8.16 mmol) and NEP (8.25 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, then acetic anhydride (3.45 g) and pyridine (2.65 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (26). The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,600, and the weight average molecular weight was 49,200.

<Synthesis Example 27>
E2 (2.23 g, 8.92 mmol), B1 (1.62 g, 5.42 mmol), D2 (1.38 g, 9.04 mmol) and D3 (1.36 g, 3.62 mmol) to NEP (16.7 g) After mixing at 80 ° C. for 5 hours, E1 (1.75 g, 8.92 mmol) and NEP (8.34 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, then acetic anhydride (3.45 g) and pyridine (2.65 g) were added as an imidization catalyst, and the mixture was heated at 60 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (27). The imidation ratio of this polyimide was 57%, the number average molecular weight was 18,600, and the weight average molecular weight was 51,500.

Tables 2 to 4 show the polyimide polymers of the present invention.

* 1: Polyamic acid.

* 1: Polyamic acid.

* 1: Polyamic acid.

“Production of Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 19 and Comparative Examples 1 to 8 described below, production examples of liquid crystal aligning agents are described. Moreover, this liquid crystal aligning agent is used also for evaluation.

Tables 5 to 7 show the liquid crystal aligning agents of the present invention.

Using the liquid crystal aligning agents obtained in the examples and comparative examples of the present invention, "Evaluation of ink-jet coating properties of liquid crystal aligning agents", "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "Voltage Evaluation of retention rate (normal cell), evaluation of relaxation of residual charge (normal cell), and production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) were performed.

"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
The liquid crystal aligning agent (4) obtained in Example 4 of the present invention, the liquid crystal aligning agent (9) obtained in Example 9 and the liquid crystal aligning agent (15) obtained in Example 15 were finely divided. Pressure filtration was performed with a membrane filter having a pore diameter of 1 μm, and the inkjet coating property was evaluated. As the ink jet coater, HIS-200 (manufactured by Hitachi Plant Technology) was used. Application is on ITO (Indium Tin Oxide) vapor-deposited substrate cleaned with pure water and IPA, nozzle pitch is 0.423 mm, scan pitch is 0.5 mm, application speed is 40 mm / second, from application to temporary drying For 60 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.

The coating properties of the obtained substrate with a liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in any of the liquid crystal alignment films obtained in any of the examples, no pinhole was found on the coating film, and a liquid crystal alignment film having excellent coating properties was obtained.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"
The liquid crystal aligning agent obtained in Examples and Comparative Examples of the present invention was pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal cell (normal cell). This solution was spin-coated on the ITO surface of a 40 × 30 mm ITO electrode substrate (40 mm long × 30 mm wide, 0.7 mm thick) washed with pure water and IPA, and heated on a hot plate at 100 ° C. for 5 minutes. Then, heat treatment was performed at 230 ° C. for 30 minutes in a heat circulation clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal aligning agent (4) obtained in Example 4 of the present invention, the liquid crystal aligning agent (9) obtained in Example 9 and the liquid crystal aligning agent (15) obtained in Example 15 are: Then, under the same conditions as in the above-mentioned “Evaluation of Inkjet Applicability of Liquid Crystal Alignment Treatment Agent”, a substrate with a liquid crystal alignment film is prepared, and then heat-treated at 230 ° C. for 30 minutes in a thermal circulation clean oven, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.

The coated surface of this ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film thus obtained were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

In the liquid crystal cell using the liquid crystal aligning agent (1) obtained in Example 1 and the liquid crystal aligning agent (21) obtained in Comparative Example (1), MLC-2003 (Merck Japan) was used as the liquid crystal. Used). Further, MLC-6608 (manufactured by Merck Japan Co., Ltd.) was used for the liquid crystal in the cell using the liquid crystal aligning agent obtained in the other examples and comparative examples.

Next, the pretilt angle of this liquid crystal cell (normal cell) was measured. The pretilt angle was measured after the liquid crystal cell was subjected to isotropic treatment (heat treatment at 95 ° C. for 5 minutes) and then heat treatment (heat treatment at 120 ° C. for 5 hours).

Furthermore, after the isotropic treatment was performed on the liquid crystal cell produced under the same conditions as described above, the liquid crystal cell after being irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm was also measured. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).

The evaluation is based on the pretilt angle after the liquid crystal isotropic treatment (also referred to after the Iso treatment) and after the heat treatment (also referred to as the high temperature treatment) and after the ultraviolet irradiation (also referred to as the ultraviolet irradiation). The smaller the change in angle, the better. (Tables 8 to 10 show pretilt angle values after Iso treatment, after high temperature treatment and after ultraviolet irradiation).

Tables 8 to 10 show the results obtained in the examples and comparative examples.

"Evaluation of voltage holding ratio (normal cell)"
The voltage holding ratio was evaluated using a liquid crystal cell (ordinary cell) produced under the same conditions as those described above for “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a voltage of 1 V is applied to the liquid crystal cell (ordinary cell) obtained by the above method at a temperature of 80 ° C. for 60 μs, the voltage after 50 ms is measured, and how much the voltage is maintained. It was calculated as a voltage holding ratio (also referred to as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Frame Period: 50 ms.

Furthermore, a UV light of 50 J / cm ^{2 in} terms of 365 nm was converted into a liquid crystal cell for which the measurement of the voltage holding ratio immediately after the liquid crystal cell was finished, using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Irradiation was performed, and the voltage holding ratio was measured under the same conditions as described above.

The value of the voltage holding ratio immediately after the production of the liquid crystal cell is higher, and the evaluation is better as the value after the ultraviolet irradiation is smaller than the value of the voltage holding ratio immediately after the production of the liquid crystal cell (Table 11). Table 13 shows the values of VHR immediately after the liquid crystal cell was produced and after ultraviolet irradiation.

Tables 11 to 13 show the results obtained in the examples and comparative examples.

"Evaluation of residual charge relaxation (normal cell)"
Evaluation of relaxation of residual charge was performed using a liquid crystal cell (normal cell) manufactured under the same conditions as the above-mentioned “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a DC voltage of 10 V was applied to the liquid crystal cell for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. In addition, the measurement used the 6254 type liquid crystal physical-property evaluation apparatus (Toyo Technica company make).

Furthermore, the residual charge immediately after the above liquid crystal cell was measured was irradiated with 30 J / cm ² of UV converted to 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Then, the residual charge was measured under the same conditions as described above.

In the evaluation, the smaller the value of the residual charge immediately after the production of the liquid crystal cell and after the ultraviolet irradiation, the better the value (Tables 11 to 13 show the values of the residual charge immediately after the production of the liquid crystal cell and after the ultraviolet irradiation).

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Liquid crystal aligning agent (3) obtained in Example 3, liquid crystal aligning agent (5) obtained in Example 5, liquid crystal aligning agent (6) obtained in Example 6, obtained in Example 8 The liquid crystal alignment treatment agent (8) obtained and the liquid crystal alignment treatment agent (16) obtained in Example 16 were pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal cell and evaluate liquid crystal alignment (PSA Cell). This solution was washed with pure water and IPA at the center with a 10 × 10 mm ITO electrode substrate with a pattern spacing of 20 μm (vertical 40 mm × width 30 mm, thickness 0.7 mm) and at the center with a 10 × 40 mm ITO electrode substrate Spin coated on ITO surface (length 40mm x width 30mm, thickness 0.7mm), heat-treated on a hot plate at 100 ° C for 5 minutes, and heat-circulating clean oven at 230 ° C for 30 minutes to form a film A polyimide coating film having a thickness of 100 nm was obtained.

This substrate with a liquid crystal alignment film was combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and an empty cell was prepared by adhering the periphery with a sealant. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

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

The response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured.

The PSA cell obtained in any of the examples confirmed that the orientation direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

<Example 1>
Polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2 NMP (18.2 g) and BCS (8.16 g) were added to the solution (2) (3.33 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (1), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 2>
Polyamic acid solution (3) (4.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.4 g) and PB (14.1 g) were added to the solution (5) (4.50 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (2), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of residual charge relaxation ( Normal cell) ”.

<Example 3>
NEP (21.6 g) was added to polyimide powder (4) (1.15 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (1.15 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (14.4 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (3), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of residual charge relaxation ( “Normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)”.

<Example 4>
NEP (14.9 g) is added to polyimide powder (4) (0.65 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (0.43 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.97 g), PB (8.96 g) and K1 (0.032 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (4), “evaluation of ink-jet coating property of liquid crystal aligning agent”, “production of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio ( Normal cell) ”and“ Evaluation of residual charge relaxation (normal cell) ”.

<Example 5>
NMP (20.3 g) is added to polyimide powder (7) (1.65 g) obtained by the synthesis method of Synthesis Example 7 and polyimide powder (8) (0.71 g) obtained by the synthesis method of Synthesis Example 8. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. BCS (12.9 g) and DME (3.69 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (5), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of residual charge relaxation ( “Normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)”.

<Example 6>
Polyamic acid solution (9) (3.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 9 and a polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 To the solution (5) (5.25 g), NEP (14.0 g), PB (10.3 g) and EC (3.43 g) were added and stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (6). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (6), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of residual charge relaxation ( “Normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)”.

<Example 7>
NEP (15.0 g) was added to the polyimide powder (10) (1.75 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (11.0 g) and DME (1.37 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

On the other hand, NEP (3.80 g) was added to polyimide powder (6) (0.44 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (2.70 g) and DME (0.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

The two solutions obtained above were mixed, K1 (0.153 g) was further added, and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (7), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 8>
To the polyimide powder (11) (0.75 g) obtained by the synthesis method of Synthesis Example 11 and the polyimide powder (8) (1.39 g) obtained by the synthesis method of Synthesis Example 8, NMP (6.71 g) and NEP (13.4 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.4 g) and K1 (0.107 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (8), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of residual charge relaxation ( “Normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)”.

<Example 9>
NEP (15.2 g) and polyimide powder (11) (0.55 g) obtained by the synthesis method of Synthesis Example 11 and polyimide powder (8) (0.83 g) obtained by the synthesis method of Synthesis Example 8 γ-BL (3.79 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (15.2 g) and DME (3.79 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (9), “Evaluation of ink-jet coating property of liquid crystal aligning agent”, “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio ( Normal cell) ”and“ Evaluation of residual charge relaxation (normal cell) ”.

<Example 10>
NMP (1.73 g) and NEP (6.90 g) were added to the polyimide powder (4) (1.10 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

On the other hand, NMP (1.73 g) and NEP (6.90 g) were added to the polyimide powder (12) (1.10 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (10), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 11>
To the polyimide powder (13) (1.25 g) obtained by the synthesis method of Synthesis Example 13 and the polyimide powder (8) (0.83 g) obtained by the synthesis method of Synthesis Example 8, NEP (13.1 g) and γ-BL (3.26 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (13.1g) and EC (3.26g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (11), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 12>
To the polyimide powder (10) (0.65 g) obtained by the synthesis method of Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained by the synthesis method of Synthesis Example 8, NMP (17.0 g) and γ-BL (1.70 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (6.79 g) and PB (8.49 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (12). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (12), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Residual charge relaxation evaluation ( Normal cell) ”.

<Example 13>
Polyamic acid solution (15) (4.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 15 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 16 To solution (16) (4.50 g), NMP (14.4 g), BCS (3.53 g), PB (10.6 g) and K1 (0.225 g) were added and stirred at 40 ° C. for 6 hours. A liquid crystal aligning agent (13) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (13), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 14>
NEP (15.9 g) is added to polyimide powder (7) (0.90 g) obtained by the synthesis method of Synthesis Example 7 and polyimide powder (17) (1.35 g) obtained by the synthesis method of Synthesis Example 17. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.29 g) and PB (14.1 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (14), “production of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 15>
To the polyimide powder (7) (0.55 g) obtained by the synthesis method of Synthesis Example 7 and the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17, NMP (3.79 g) and NEP (15.2 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (19.0 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (15), “evaluation of inkjet coating property of liquid crystal aligning agent”, “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio ( Normal cell) ”and“ Evaluation of residual charge relaxation (normal cell) ”.

<Example 16>
NMP (8.82 g) was added to the polyimide powder (18) (1.25 g) obtained by the synthesis method of Synthesis Example 18, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (2.94 g) and PB (7.86 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

On the other hand, NMP (5.88 g) was added to the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.96 g) and PB (5.24 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (16). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (16), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)”, “Evaluation of residual charge relaxation ( “Normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)”.

<Example 17>
K1 (0.06 g) was added to the liquid crystal aligning agent (16) (20.0 g) obtained by the adjustment method of Example 16, and the mixture was stirred at 40 ° C. for 6 hours to give the liquid crystal aligning agent (17). Obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (17), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 18>
NEP (21.2 g) was added to polyimide powder (19) (0.45 g) obtained by the synthesis method of Synthesis Example 19 and polyimide powder (6) (1.80 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (3.53 g) and PB (10.6 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (18). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (18), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Example 19>
Polyimide powder (19) (1.63 g) obtained by the synthesis method of Synthesis Example 19 and a polyamic acid solution (5) (6.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (19.4 g) was added thereto and stirred at 70 ° C. for 24 hours for dissolution. To this solution, BCS (6.47 g) and PB (6.47 g) were added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (19). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (19), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative Example 1>
The polyamic acid solution (20) (4.95 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 20 and the polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 21 NMP (18.0 g) and BCS (8.08 g) were added to the solution (21) (3.30 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (20). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (20), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative example 2>
Polyamic acid solution (3) (4.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and a polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 24 NEP (14.4 g) and PB (14.1 g) were added to the solution (24) (4.50 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (21). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (21), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative Example 3>
Polyamic acid solution (22) (4.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 22 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.4 g) and PB (14.1 g) were added to the solution (5) (4.50 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (22). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (22), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative example 4>
Polyamic acid solution (22) (4.50 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 22 and polyamic acid having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 24 NEP (14.4 g) and PB (14.1 g) were added to the solution (24) (4.50 g), and the mixture was stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (23). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (23), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative Example 5>
NEP (20.7 g) was added to polyimide powder (4) (1.10 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (24). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (24), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative Example 6>
NEP (20.7 g) was added to polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and polyimide powder (6) (1.10 g) obtained by the synthesis method of Synthesis Example 6. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (25). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (25), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of residual charge relaxation ( Normal cell) ”.

<Comparative Example 7>
NEP (20.7 g) was added to polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (26). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (26), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

<Comparative Example 8>
NEP (20.7 g) was added to polyimide powder (26) (1.10 g) obtained by the synthesis method of Synthesis Example 26 and polyimide powder (27) (1.10 g) obtained by the synthesis method of Synthesis Example 27. In addition, it was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (27). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

Using the obtained liquid crystal aligning agent (27), “preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) ”.

* 1: An introduction amount (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of all polymers.
* 2: Indicates the introduction amount (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of all polymers.
* 3: An introduction amount (parts by mass) of other polymer with respect to 100 parts by mass of all polymers.
* 4: An introduction amount (parts by mass) of a crosslinkable compound with respect to 100 parts by mass of all polymers.
* 5: An introduction amount (parts by mass) of each solvent with respect to 100 parts by mass of all the solvents.
* 6: Indicates the ratio of all the polymers in the liquid crystal aligning agent.

As can be seen from the above results, the liquid crystal aligning agent of the example of the present invention has a stable pretilt angle even when the liquid crystal cell is subjected to high temperature treatment and ultraviolet irradiation, as compared with the liquid crystal aligning agent of the comparative example. Indicated. Furthermore, even when UV irradiation was performed, the decrease in the voltage holding ratio was suppressed, and the residual charge accumulated by the DC voltage was quickly relaxed. That is, the liquid crystal composition treating agent of the present invention becomes a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, and in addition, has been exposed to light irradiation for a long time. Even after this, a liquid crystal alignment film is obtained in which the decrease in the voltage holding ratio is suppressed and the residual charge accumulated by the DC voltage is quickly relaxed.

Specifically, Examples of the liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) of the present invention, and Examples of the liquid crystal alignment treatment agent using only one of them. That is, the comparison between Example 2 and Comparative Example 2 or Comparative Example 3, and the comparison between Example 3 and Comparative Example 5 or Comparative Example 6. The comparative examples using only these specific polymers (A) or the comparative examples using only the specific polymers (B) are greatly reduced in voltage holding ratio, particularly with respect to ultraviolet irradiation, as compared with the corresponding examples. In addition, the residual charge value also increased.

Moreover, the Example of the liquid-crystal aligning agent using the specific polymer (A) and specific polymer (B) of this invention, the polymer which does not have the structure containing the tertiary nitrogen atom of this invention, and specific structure ( 2) A comparative example of a liquid crystal aligning agent using a polymer having no polymer, that is, a comparison between Example 1 and Comparative Example 1, a comparison between Example 2 and Comparative Example 4, and Example 3 and Comparative Example 7 is a comparison. In these comparative examples, compared with the corresponding examples, the voltage holding ratio was greatly reduced, and the value of the residual charge was also increased particularly with respect to ultraviolet irradiation.

In addition, an example of a liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) of the present invention, and a liquid crystal alignment treatment agent using a polymer having a conventional side chain structure This is a comparison with the comparative example, that is, a comparison between Example 3 and Comparative Example 8. Compared with the corresponding example, this comparative example has a large change width of the pretilt angle after the high temperature treatment and the ultraviolet irradiation, and the voltage holding ratio is greatly reduced with respect to the ultraviolet irradiation. The charge value also increased. In particular, the decrease in the voltage holding ratio was particularly large.

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to provide a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio even after being exposed to light irradiation for a long time and quickly relaxes residual charges accumulated by a DC voltage. In addition, the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. It is useful for a device, a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device.

Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, A liquid crystal produced by placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

Claims

Liquid crystal aligning agent containing the following (A) component and (B) component.
(A) Component: A polymer containing at least one selected from a polyimide precursor having a structure having a nitrogen atom and a polyimide.
(B) Component: A polymer containing at least one selected from a polyimide precursor having a structure represented by the following formula [2] and a polyimide.
In addition, at least one of the polymer of the component (A) and the component (B) contains a structure represented by the following formula [3].

(In Formula [2], Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) — (R 1 is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R 2 ) — (R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH 2 O—, —COO— and —OCO—, wherein Y 2 and Y 6 are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom).

(In the formula [3], B 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. B 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15), B 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—, wherein B 4 is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton A divalent organic group having 17 to 51, wherein any hydrogen atom on the cyclic group contains an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or fluorine having 1 to 3 carbon atoms May be substituted with an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom , B 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, having 1 to 3 carbon atoms May be substituted with an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom, n represents an integer of 0 to 4, and B 6 represents the number of carbon atoms An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms).
The liquid crystal aligning agent according to claim 1, wherein the structure having a nitrogen atom in the component (A) is at least one structure selected from structures represented by the following formulas [1a] to [1c].

(In the formula [1a], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms, 1b], X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X 4 and X 6 are each independently Represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X 5 represents an alkylene group or biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and in formula [1c], X 8 And X 10 each independently represents at least one structure selected from the structures represented by the following formulas [1c-a] and [1c-b], and X 9 represents an alkylene group having 1 to 5 carbon atoms. Or a benzene ring).
3. The liquid crystal alignment treatment according to claim 1, wherein the polymer of the component (A) is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material. Agent.

(In Formula [1-1], X A represents an organic group having at least one structure selected from the structures represented by Formula [1a] to Formula [1c], and A 1 and A 2 are each independently selected. A hydrogen atom or an alkylene group having 1 to 5 carbon atoms).
4. The liquid crystal aligning agent according to claim 3, wherein the diamine compound is a polymer obtained by using a diamine compound represented by the following formulas [1a-1] to [1c-1] as a part of a raw material.
(In the formula [1a-1], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms, In the formula [1b-1], X 3 and X 7 each independently represents an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X 4 and X 6 are Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X 5 represents an alkylene group or biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and the formula [1c- 1], X 8 and X 10 each independently represent at least one structure selected from the structures represented by the formulas [1c-a] and [1c-b], and X 9 has 1 carbon atom Represents an alkylene group or a benzene ring represented by formulas [1a-1] to In [1c-1], A 1 to A 6 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
The liquid crystal aligning agent according to claim 4, wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [1-1a] to [1-4a].

(In the formula [1-3a], R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. In the formula [1-4a], n represents an integer of 1 to 10, and the formula [1-1a] In Formula [1-4a], A 1 to A 8 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
6. The polymer according to claim 1, wherein the polymer of the component (B) is a polymer obtained by using a diamine compound represented by the following formula [2-1] as a part of a raw material. The liquid crystal aligning agent of description.

(In Formula [2-1], Y A represents an organic group having the structure represented by Formula [2], and A 1 and A 2 are each independently a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Showing).
The liquid crystal aligning agent according to claim 6, wherein the diamine compound is a polymer obtained by using a diamine compound represented by the following formula [2a] as a part of a raw material.

(In Formula [2a], Y 1 and Y 7 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —N (R 1 ) — (R 1 is a hydrogen atom or carbon number) 1 to 3 alkylene group), —CON (R 2 ) — (R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), —N (R 3 ) CO— (R 3 represents a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), at least one organic group selected from —CH 2 O—, —COO— and —OCO—, wherein Y 2 and Y 6 are each independently carbon An alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, Y 4 represents an oxygen atom or a sulfur atom, and A 1 and A 5 2 each independently represent a hydrogen atom or a C 1-5 It represents an alkylene group).
8. The liquid crystal aligning agent according to claim 7, wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [2-1a] to [2-3a].

(In the formulas [2-1a] to [2-3a], A 1 to A 6 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).
The diamine compound represented by the following formula [3a] is used as a part of a raw material for at least one of the polymer of the component (A) and the component (B). The liquid crystal aligning agent according to item.

(In the formula [3a], B represents the above formula [3], A 1 and A 2 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and m represents an integer of 1 to 4. Show).
The polymer of the component (A) and the polymer of the component (B) are at least one polymer selected from a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [4] The liquid crystal aligning agent according to any one of claims 1 to 9, wherein

(In the formula [4], Z represents at least one structure selected from structures represented by the following formulas [4a] to [4k]).

(In the formula [4a], Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [4g] Z 5 and Z 6 each represent a hydrogen atom or a methyl group, and may be the same or different.
The tetracarboxylic acid component is a tetracarboxylic acid component having at least one structure selected from the structures represented by the formula [4a] and the formulas [4e] to [4g] in the formula [4]. The liquid-crystal aligning agent of Claim 10.
In the polymer of the component (A), the diamine compounds represented by the formulas [1a-1] to [1c-1] are 5 mol% to 95 mol% in 100 mol% of all diamine components. Item 12. The liquid crystal aligning agent according to any one of Items 4 to 11.
The polymer of component (B), wherein the diamine compound represented by the formula [2a] is 5 mol% to 95 mol% in 100 mol% of all diamine components. The liquid crystal aligning agent according to one item.
The polymer of the (B) component is 0.5 to 950 parts by mass with respect to 100 parts by mass of the polymer of the (A) component. Liquid crystal alignment treatment agent.
15. The solvent according to claim 1, which contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone as a solvent for the liquid crystal aligning agent. Liquid crystal aligning agent as described in.
As a solvent for the liquid crystal aligning agent, at least one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether The liquid crystal aligning agent according to any one of claims 1 to 15, which contains a solvent.
The liquid crystal aligning agent has at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group. The liquid crystal aligning agent according to any one of claims 1 to 16, comprising at least one crosslinkable compound selected from a crosslinkable compound and a crosslinkable compound having a polymerizable unsaturated bond.
A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 17.
A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to any one of claims 1 to 17.
A liquid crystal display element having the liquid crystal alignment film according to claim 18 or 19.
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes 20. The liquid crystal alignment film according to claim 18, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 21.
A liquid crystal layer comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; 20. The liquid crystal alignment film according to claim 18, wherein the liquid crystal alignment film is used in a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage therebetween.
24. A liquid crystal display element comprising the liquid crystal alignment film according to claim 23.