TW201527846A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

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 alignment treatment agent and liquid crystal display element using 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 by the liquid crystal alignment treatment agent, and a liquid crystal display element obtained by using the liquid crystal alignment film.

The liquid crystal display element is currently widely used as a display device capable of realizing a thin type and a light weight. Usually, in this liquid crystal display element, a liquid crystal alignment film which can determine a liquid crystal alignment state is often used.

One of the characteristics sought for the liquid crystal alignment film is that the alignment tilt angle of the liquid crystal molecules on the substrate surface can be maintained at an arbitrary value, that is, the control of the pretilt angle of the liquid crystal. It is known that the magnitude of the pretilt angle can be changed by the structure of the selected polyimine which constitutes the liquid crystal alignment film. In the technique of controlling the pretilt angle using the structure of polyimine, and using a diamine having a side chain as a part of the polyimine raw material, the pretilt angle can be controlled by the ratio of the use of the diamine. In view of the fact that the pretilt angle of the desired purpose can be more easily obtained, it is highly suitable as a means for expanding the pretilt angle (for example, Patent Document 1). Moreover, there is also a purpose of improving the stability of the pretilt angle or the dependence of the process on the diamine component which can increase the pretilt angle of the liquid crystal. And study the structure. Further, a side chain structure used therein has been proposed to use a ring structure containing a phenyl group or a cyclohexyl group (for example, Patent Document 2).

Further, with the increase in the precision of the liquid crystal display element, it is possible to maintain a high voltage holding ratio in the liquid crystal alignment film to be used, or to suppress the deterioration of the liquid crystal display element or to reduce the image sticking phenomenon. It is becoming more important to reduce the accumulated charge, or how to quickly slow down the charge accumulated by the DC voltage.

In the polyimine-based liquid crystal alignment film, the time until the disappearance of the residual voltage due to the DC voltage can be shortened, and it is known to use, for example, polyacetamide or polyamido acid containing a ruthenium group. A liquid crystal alignment treatment agent containing a tertiary amine of a specific structure (for example, Patent Document 3), or a liquid crystal alignment treatment agent containing a soluble polyimine having a specific diamine such as a pyridine skeleton as a raw material (for example, a patent) Literature 4) and so on. Further, it has a high voltage holding ratio and can shorten the time until the image is broken due to the DC voltage. For example, it is known to use a polyelectron acid or a ruthenium imidized polymer. A small amount of a liquid crystal alignment treatment agent of a compound selected from a compound containing one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound having one tertiary amino group in the molecule (for example, patent document) 5).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2-282726

[Patent Document 2] JP-A-9-278724

[Patent Document 3] JP-A-9-316200

[Patent Document 4] Japanese Patent Publication No. Hei 10-104633

[Patent Document 5] Japanese Patent Publication No. 8-76128

The liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, even when used to control the pretilt angle of the liquid crystal. In particular, in the VA (Vertical Alignment) mode or the PSA (Polymer Sustained Alignment) mode, when the liquid crystal must be vertically aligned, in the liquid crystal alignment film, the ability to vertically align the liquid crystal (also referred to as vertical alignment or High pretilt angle). In addition, in the liquid crystal alignment film, not only the high vertical alignment property but also the stability of the liquid crystal alignment film is extremely important. In particular, in order to obtain high brightness, the heat generation amount is increased, and a liquid crystal display element of a backlight which uses a large amount of light irradiation, for example, a car navigation system or a large television, is exposed to a high temperature and a light irradiation environment for a long time. Use under, or place. Among the severe conditions, if the vertical alignment property is lowered, the initial display characteristics or the display streaks may not be obtained.

Further, the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is also sought to be highly stable under the above severe conditions. In other words, when the voltage holding ratio is lowered by the light generated by the backlight, the image defect of one of the display failures of the liquid crystal display element is likely to occur. (Also known as linear afterimage), it is impossible to produce a liquid crystal display element with high reliability. Therefore, the liquid crystal alignment film is required to have a good initial characteristic, for example, a characteristic that the voltage holding ratio is not easily lowered after exposure to light for a long period of time. Further, for the interface melting phenomenon of another afterimage defect, there is also a need for a liquid crystal alignment film which can quickly alleviate the residual charge accumulated by the DC voltage even if it is irradiated with light by a backlight.

Therefore, the present invention has an object of providing a liquid crystal alignment treatment agent having the above characteristics. That is, an object of the present invention is to provide a liquid crystal alignment film having a stable pretilt angle even after exposure to high temperature for a long period of time and light irradiation. Further, in order to provide a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after long-time exposure to light irradiation, and can quickly alleviate residual charges accumulated by a DC voltage.

Further, a liquid crystal display element which can provide the liquid crystal display element having the above liquid crystal alignment film and which can provide the above liquid crystal alignment film is provided.

Further, the present invention has an object of providing a liquid crystal display element having a liquid crystal alignment film corresponding to the above requirements.

The present inventors have conducted intensive studies and found that liquid crystal alignment treatment agents having two polymers having a specific structure are extremely effective in achieving the above object, and the present invention has been completed.

That is, the present invention is the one having the following main features.

(1) A liquid crystal alignment treatment containing the following (A) component and (B) component Agent.

(A) Component: a polymer containing at least any one selected from the group consisting of a polyimide intermediate having a structure containing a nitrogen atom and a polyimine.

(B) Component: a polymer containing at least one selected from the group consisting of a polyimine precursor having a structure represented by the following formula [2] and a polyimine.

Further, at least one of the components (A) and (B) has a structure represented by the following formula [3].

(In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a carbon number of 1~). 3 alkylene), -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 a carbon number of 1) At least one organic group selected from ~3 alkylene), -CH ₂ O-, -COO-, and -OCO-, and Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent 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 represents 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 from 1 to 15), B ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, B ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, or a divalent group having a carbon number of 17 to 51 having a cholesterol skeleton The organic group, any hydrogen atom on the above cyclic group, may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3; 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, and B ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be It is substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is represented by n. An integer of 0 to 4, and B ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. ).

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

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

(3) The liquid crystal alignment treatment agent according to the above (1), wherein the polymer of the component (A) is a raw material using a diamine compound represented by the following formula [1-1]. A part of the polymer produced.

(In the formula [1-1], X ^A represents an organic group having at least one structure selected from the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² each independently represent a hydrogen atom. Or an alkyl group having a carbon number of 1 to 5).

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

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

(5) The liquid crystal alignment treatment agent according to the above (4), wherein the diamine compound is at least one selected from the diamine compounds represented by the following formula [1-1a] to formula [1-4a]. Diamine compound.

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

The liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of the component (B) is a diamine compound represented by the following formula [2-1]. A polymer produced as part of a raw material.

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

(7) The liquid crystal alignment treatment agent according to the above (6), wherein the diamine compound is a polymer obtained by using a diamine compound represented by the following formula [2a] as a raw material.

(In the formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a carbon number of 1~). 3 alkylene), -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 a carbon number of 1) At least one organic group selected from ~3 alkylene), -CH ₂ O-, -COO-, and -OCO-, and Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent 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 ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms) .

The liquid crystal alignment treatment agent according to the above-mentioned (7), wherein the diamine compound is at least one selected from the diamine compounds represented by the following formula [2-1a] to formula [2-3a]. Diamine compound.

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

The liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of at least one of the components (A) and (B) is used. The diamine compound represented by the formula [3a] is used as a part of the raw material.

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

(10) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of the component (A) and the component (B) The polymer is at least one polymer selected from the group consisting of a polyimine precursor obtained by using a tetracarboxylic acid component represented by the following formula [4] and a polyimine.

(In the formula [4], Z represents a structure selected from at least one of the 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, respectively, in the formula [4g], Z ⁵ and Z ⁶ represent a hydrogen atom or a methyl group, which may be the same or different, respectively.

(11) The liquid crystal alignment treatment agent according to the above (10), wherein the tetracarboxylic acid component is such that Z in the above formula [4] is from the above formula [4a] and formula [4e] to formula [4g]. The tetracarboxylic acid component of at least one structure selected for the structure shown.

The liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of the component (A) has the formula [1a-1] to the formula [1c-1]. The diamine compound shown in the formula is from 5 mol% to 95 mol% in 100 mol% of the total diamine component.

The liquid crystal alignment treatment agent according to any one of the above (1), wherein the diamine compound represented by the above formula [2a] is used in the polymer of the component (B). The diamine component is 100 mol%, and is 5 mol% to 95 mol%.

(14) The polymer of the component (B) of the liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of the component (A) is 100 parts by mass of the polymer. 0.5 parts by mass to 950 parts by mass.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the solvent of the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone and N- At least one solvent selected from ethyl-2-pyrrolidone and γ-butyrolactone.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the solvent of the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2- At least one selected from ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether Solvent.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonic acid. a crosslinkable compound of an ester group, a crosslinkable compound having at least one substituent selected from a group consisting of a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group, and a polymerizable unsaturated bond At least one crosslinkable compound selected from the crosslinkable compound.

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

(19) A liquid crystal alignment film obtained by the inkjet method using the liquid crystal alignment treatment agent according to any one of the above (1) to (17).

(20) A liquid crystal display element comprising the liquid crystal alignment film according to (18) or (19) above.

(21) A liquid crystal alignment film according to the above (18) or (19), which is used in a liquid crystal display device, characterized in that the liquid crystal display element is between a substrate having one pair of electrodes A liquid crystal layer having a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the liquid crystal composition is continuously applied with a voltage between the electrodes The step of polymerizing the aforementioned polymerizable compound is obtained.

(22) A liquid crystal display device comprising the liquid crystal alignment film of (21) above.

(23) The liquid crystal alignment film according to the above (18) or (19), which is used in a liquid crystal display device, characterized in that the liquid crystal display element has a liquid crystal layer between substrates having one pair of electrodes A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and a heat is disposed between the pair of substrates, and the liquid crystal alignment film is continuously applied with a voltage between the electrodes to cause the polymerization. Produced by the steps of the radical polymerization.

(24) A liquid crystal display element comprising the liquid crystal alignment film of (23) above.

The liquid crystal alignment treatment agent containing two types of polymers selected from the group consisting of a polyimine precursor having a specific structure or a polyimine is a long-term exposure to high temperature and light irradiation. A liquid crystal alignment film having a stable pretilt angle can also be obtained. In addition, it is also a kind of residual charge liquid crystal alignment film which can suppress the decrease of the voltage holding ratio even after long-term exposure to light irradiation, and can quickly alleviate the accumulation of the DC voltage. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is highly suitable for a liquid crystal television having a large screen and high precision.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

The present invention is a composition comprising the following (A) component and (B) component A liquid crystal alignment treatment agent, 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.

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

(A) Component: a polymer (also referred to as a specific polymer (A)) containing at least any one selected from a polyimine precursor having a structure containing a nitrogen atom and a polyimine.

(B) Component: a polymer containing at least one selected from the group consisting of a polyimine precursor having a structure represented by the following formula [2] (also referred to as a specific structure (2)) and a polyimine ( Also known as a specific polymer (B)).

Further, at least one of the polymer 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).

(In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a carbon number of 1~). 3 alkylene), -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 a carbon number of 1) At least one organic group selected from ~3 alkylene), -CH ₂ O-, -COO-, and -OCO-, and Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent 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 represents 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 from 1 to 15), B ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, B ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, or a divalent group having a carbon number of 17 to 51 having a cholesterol skeleton The organic group, any hydrogen atom on the above cyclic group, may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3; 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, and B ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be It is substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is represented by n. An integer of 0 to 4, and B ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. ).

The liquid crystal alignment film prepared by the liquid crystal alignment treatment agent of the present invention, which can solve the problem of the present invention, is not fully understood, but should be The following instructions.

That is, the specific side chain structure represented by the above 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 a side chain portion. Or a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 of a cholesterol skeleton. The side chain structure of the ring and the organic group has a more rigid structure than a side chain structure of a long-chain alkyl group which is a vertical alignment of a liquid crystal. Thus, a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent having a specific side chain structure of the present invention can provide a higher and stable liquid crystal vertical alignment when compared with a conventional side chain structure having a long-chain alkyl group. .

Further, when the specific side chain structure of the present invention is compared with the side chain structure of the conventional long-chain alkyl group, it is known that it has stability to light such as ultraviolet rays. Therefore, the specific side chain structure of the present invention can suppress the decrease in the voltage holding ratio even when exposed to light for a long period of time, and can suppress the decomposition of the side chain component which accumulates the residual electric charge by the direct current voltage.

Further, the nitrogen atom in the structure of the nitrogen atom-containing structure contained in the specific polymer (A) of the present invention interacts with the carboxyl group (COOH group) in the specific polymer (B), and the specific polymer (B) The interaction of the nitrogen atom in the above formula [2] with the carboxyl group in the specific polymer (A) is thought to cause a charge shift between the atoms. Along with this reaction, the accumulated residual charge can be efficiently moved in or between molecules of the polymer. That is, it is assumed that the residual charge generated by the DC voltage can be released.

Further, the structure having a nitrogen atom in the specific polymer (A) of the present invention is presumed to be trapped to cause a decrease in the voltage retention rate. Impurity ingredients. In other words, the liquid crystal display element can trap ionic impurities generated by exposure to light for a long period of time, and therefore, it is also possible to suppress a decrease in the voltage holding ratio.

From the above, it is known that the liquid crystal alignment treatment agent containing at least one polymer selected from the group consisting of a polyimine precursor having a specific structure or a polyimine is a long time A liquid crystal alignment film having a stable pretilt angle can also be obtained after exposure to high temperature and light irradiation. In addition, it is also a kind of residual charge liquid crystal alignment film which can suppress the decrease of the voltage holding ratio even after long-term exposure to light irradiation, and can quickly alleviate the accumulation of the DC voltage.

<Structure with nitrogen atom>

The specific polymer (A) of the present invention is a polymer containing at least one selected from the group consisting of a polyimine precursor having a structure containing a nitrogen atom and a polyimine.

The specific structure of the structure containing a nitrogen atom is, for example, a structure represented by the following formula [1a] to formula [1c].

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

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

Further, 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 represent an aromatic group having 6 to 15 carbon atoms and having 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 or a biphenyl group having 2 to 5 carbon atoms.

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 the structures represented by the following formulas [1c-a] and [1c-b].

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

<Specific structure (2)>

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

In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N(R ¹ )- (R ¹ represents a hydrogen atom or carbon. a number 1 to 3 alkylene), -CON(R ² )- (R ² represents a hydrogen atom or a C 1 to 3 alkyl group), -N(R ³ )CO- (R ³ represents a hydrogen atom or At least one organic group selected from the group consisting of a C 1 to 3 alkyl group, -CH ₂ O-, -COO-, and -OCO-. Among them, a single bond, -O-, -S-, -OCO- or -COO- is preferred. More preferably, the liquid crystal alignment property and the film hardness of the liquid crystal alignment film may be, for example, a single bond, -O- or -S-.

In the formula [2], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferred, and the structure may be either linear or branched. Specifically, from the viewpoints of the liquid crystal alignment property and the film hardness of the liquid crystal alignment film, a methyl group (-CH ₂ -) or an extended ethyl group (-CH ₂ CH) having a structure having a freely rotating portion and having a small steric hindrance is preferable. ₂ -), propyl (-(CH ₂ ) ₃ -) or isopropyl (-C(CH ₂ ) ₂ -) is preferred.

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

In the formula [2], Y ⁴ represents an oxygen atom or a sulfur atom. Among them, in view of the film hardness of the liquid crystal alignment film, an oxygen atom is preferred.

<specific side chain structure>

The specific side chain structure represented by the above 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].

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 them, from the viewpoints 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 preferably, it 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 them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

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-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis and the like. More preferably, it 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 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be an alkane having 1 to 3 carbon atoms. The group may be substituted with an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Further, B ⁴ may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 of a cholesterol skeleton. Among them, in view of easiness of synthesis, etc., it is preferred to use a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a cholesterol skeleton.

In the formula [3], B ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be an alkane having 1 to 3 carbon atoms. The group may be substituted with an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [3], n represents an integer of 0 to 4. Among them, from the viewpoints of the availability of raw materials and the ease of synthesis, it is preferably 0 to 3. The better 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 alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. . Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Preferred combinations of B ¹ to B ⁶ and n in the formula [3] are as disclosed in Tables 6 to 47 of pages 13 to 34 of International Publication WO2011/132751 (2011.10.27). 2-1)~(2-629) are the same combination and the like. Further, in each table of the international publication, as in the present invention, B ¹ to B ⁶ are represented by Y1 to Y6, and Y1 to Y6 are replaced by B ¹ to B ⁶ . Further, in (2-605) to (2-629) disclosed in the respective tables of the International Publications, the organic group having a carbon number of 17 to 51 having a cholesterol skeleton in the present invention has a carbon number of 12 having a cholesterol skeleton. The organic basis of ~25 indicates that the organic group having a carbon number of 12 to 25 having a cholesterol skeleton is replaced by an organic group having a carbon number of 17 to 51 having a cholesterol skeleton.

<Specific polymer (A) ‧ Specific polymer (B) >

The specific polymer (A) and the specific polymer (B) of the present invention are at least one selected from the group consisting of a polyimide precursor and a polyimine (also collectively referred to as a polyimine polymer). Things. Among them, the polyimine-based polymer of the present invention is preferably a polyimide precursor or a polyimine which is obtained by reacting a diamine component with a tetracarboxylic acid component.

The polyimine 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 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and A ³ and A; ⁴ each independently represents a hydrogen atom, an alkylene group or an ethylidene group having a carbon number of 1 to 5, and n represents a positive integer).

The above diamine component is, for example, a diamine compound having two primary or secondary amine groups in the molecule.

Further, 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, or a tetracarboxylic acid dialkyl ester dihalide compound. .

When a polyphthalic acid in which A ¹ and A ² in the formula [A] are a hydrogen atom is produced, for example, a diamine compound having two primary or secondary amine groups in the molecule may be obtained, and a tetracarboxylic acid. A compound or a tetracarboxylic anhydride can be obtained by reacting.

A method for producing a polyalkyl amide of A ¹ and A ² in the formula [A] which is an alkylene group having 1 to 5 carbon atoms, for example, the diamine compound and the tetracarboxylic acid dihalide can be obtained. A compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound can be obtained by reacting. Further, an alkylene group having 1 to 5 carbon atoms of A ¹ and A ² represented by the formula [A] may be introduced into the polyamic acid obtained by the above method.

The specific polymer (A) of the present invention has a nitrogen-containing atom Structure of the polymer. Among them, the structure represented by the above formula [1a] to formula [1c] is preferred.

The method of introducing a structure containing a nitrogen atom into the specific polymer (A) is not particularly limited, and a diamine compound having a structure represented by the above formula [1a] to formula [1c] is used as a raw material. Some users are better.

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

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 above 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, it is preferred to use a diamine compound represented by the following formula [1a-1] to formula [1c-1].

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

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

Further, 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. , X ¹ represents a benzene ring.

In the formula [1b-1], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and having 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 or a biphenyl group having 2 to 5 carbon atoms.

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

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

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

Specific examples of the specific diamine compound of the specific diamine compound (1) of the present invention include a diamine compound represented by the following formula [1-1a] to formula [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 formula [1-1a] to the formula [1-4a], A ¹ to A ⁸ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

Among them, the diamine compound represented by the above formula [1-3a] or the formula [1-4a] is preferably used.

The specific diamine compound (1) in the specific polymer (A) of the present invention is 1 mol% to 95 mol% based on 100 mol% of the diamine component. % is better. Among them, it is preferably 5 mol% to 95 mol%. More preferably, it is 20% by mole to 80% by mole.

Specific diamine compound (1) of the present invention, solubility of a specific polymer (A) of the present invention to a solvent or coating property of a liquid crystal alignment treatment agent, liquid crystal alignment property as a liquid crystal alignment film, and voltage retention From the viewpoint of characteristics such as rate and charge accumulation, one type or two types or more may be used in combination.

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

The method of introducing the specific structure (2) of the present invention into the specific polymer (B) is not particularly limited, and it is preferred to use a diamine compound having a specific structure (2). It is particularly preferred to use a diamine compound having the structure represented by the above formula [2].

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

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

In the 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, the diamine represented by the following formula [2a] is used. The compound is preferred.

In the formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N(R ¹ )- (R ¹ represents a hydrogen atom or carbon. a number 1 to 3 alkylene), -CON(R ² )- (R ² represents a hydrogen atom or a C 1 to 3 alkyl group), -N(R ³ )CO- (R ³ represents a hydrogen atom or At least one organic group selected from the group consisting of a C 1 to 3 alkyl group, -CH ₂ O-, -COO-, and -OCO-. Among them, a single bond, -O-, -S-, -OCO- or -COO- is preferred. More preferably, from the viewpoints of liquid crystal alignment and film hardness, it is preferred to use a single bond of a structure which is as soft as possible and has a smaller steric hindrance, -O- or -S-.

In the formula [2a], Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferred, and the structure may be either linear or branched. Specifically, from the viewpoints of the liquid crystal alignment property and the film hardness of the liquid crystal alignment film, a methyl group (-CH ₂ -) or an extended ethyl group (-CH ₂ CH) having a structure having a freely rotating portion and having a small steric hindrance is preferable. ₂ -), propyl (-(CH ₂ ) ₃ -) or isopropyl (-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. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred. Particularly preferred is a hydrogen atom.

In the formula [2a], Y ⁴ represents an oxygen atom or a sulfur atom. Among them, in view of the film hardness of the liquid crystal alignment film, an oxygen atom is preferred.

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

Among them, the combination of 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] is preferred. .

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

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

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

The specific diamine compound (2) in the specific polymer (B) of the present invention is preferably from 1 mol% to 95 mol% based on 100 mol% of the total diamine component. Among them, it is preferably 5 mol% to 95 mol%. More preferably 20% by mole to 80% by mole.

Specific diamine compound (2) of the present invention, solubility of a specific polymer (B) of the present invention to a solvent or coating property of a liquid crystal alignment treatment agent, liquid crystal alignment property as a liquid crystal alignment film, and voltage retention From the viewpoint of characteristics such as rate and charge accumulation, one type or two types or more may be used in combination.

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 of introducing the specific side chain structure of the present invention into the specific polymer (A) or the specific polymer (B) is not particularly limited, and a diamine compound having a specific side chain structure is used as the diamine component. It is better.

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

In the formula [3a], B represents the above formula [3]. Further, a preferred combination of B ¹ to B ⁶ and n in the formula [3] is 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. Among them, a hydrogen atom or an alkylene group having 1 or 2 carbon atoms is preferred.

In the formula [3a], m represents an integer of 1 to 4. Among them, 1 is better.

Specifically, the specific side chain type diamine compound of the present invention is, for example, a diamine compound represented by the following formula [3a-1] to formula [3a-31], and further, such an amine group is a secondary amine group. Diamine compounds and the like.

(In the formula [3a-1] to the formula [3a-3], R ¹ , R ³ and R ⁵ each independently represent -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, in the formula [3a-1] to the formula [3a-3], R ² , R ⁴ and R ⁶ each independently represent a linear or branched alkyl group having 1 to 22 carbon atoms and a carbon number of 1~. a linear or branched alkoxy group of 22, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkoxy group).

(In the formula [3a-4] to the formula [3a-6], R ¹ , R ³ and R ⁵ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, in the formula [3a-4] to the formula [3a-6], R ² , R ⁴ and R ⁶ each independently represent a carbon number of 1~ a linear or branched alkyl group of 22, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms or Fluoroalkoxy).

(In the formula [3a-7] and the formula [3a-8], R ¹ and R ³ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO- , -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- or -NH-, R ² and R ⁴ each independently represent a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group , formazan, acetyl, ethoxy or hydroxy).

(In the formula [3a-9] and the formula [3a-10], R ¹ and R ² each independently represent a linear or branched alkyl group having a carbon number of 3 to 12, and a 1,4-cyclohexylene group. Cis-trans isomerism, which are each a trans isomer).

(In the formula [3a-11] and the formula [3a-12], R ¹ and R ² each independently represent a linear or branched alkyl group having a carbon number of 3 to 12, and a 1,4-cyclohexylene group. Cis-trans isomerism, which are each a 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 by a fluorine atom, and A ₃ is a 1,4-cyclohexyl group or 1,4- Phenyl is extended, A ₂ is an oxygen atom or -COO-* (wherein the bond with "*" is bonded to A ₃ ), and A ₁ is an oxygen atom or -COO-* (where " The bond key of *" is bonded to (CH ₂ )a ₂ )). Further, 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.

In the above formulas [3a-1] to [3a-31], the diamine compound having a particularly preferred structure may, for example, be a formula [3a-1] to a formula [3a-6] or a formula [3a-9]. [3a-13] or formula [3a-22]~[3a-31].

The specific side chain type diamine compound of the present invention may be at least one of a specific polymer (A) and a specific polymer (B), or a specific polymer using the same. Among them, it is preferred to use 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. It is particularly preferably 10 mol% or more and 70 mol% or less.

The specific side chain type diamine compound of the present invention, the solubility of the specific polymer (A) and the specific polymer (B) of the present invention with respect to a solvent, or the coating property of a liquid crystal alignment treatment agent, as a liquid crystal alignment film From the viewpoints of characteristics such as alignment property, voltage holding ratio, and accumulated charge of the liquid crystal, one type or two types or more may be used in combination.

The specific diamine component (1), the specific diamine compound (2), and the specific diamine component (2) of the specific polymer (A) of the present invention and the specific polymer (B) can be used within a range not impairing the effects of the present invention. Other diamine compounds other than the specific side chain type diamine compound (also referred to as other diamine compounds).

Specifically, for example, 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'-diaminobiphenyl, 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, 3,4'- 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'-sulfonate Mercaptodiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl) ) decane, dimethyl-bis(3-aminophenyl)decane, 4,4'- Diphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenyl Amine, 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'-diaminodiyl) Phenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Methyl ketone, 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, 1,3-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-aminobenzene) Oxy)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(methyl)diphenylamine, 4,4'-[1,3-stretch Phenyl bis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3-phenylene bis( Methyl)]diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylene bis(methyl) Diphenylamine, 1,4-phenylene bis[(4-amino) Methyl ketone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1, 3-phenylphenylbis[(3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), 1,4-phenylene bis(3-amine) Benzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-amine Phenylphenyl) terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminobenzene) Isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene) double (4-Aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene) Bis(3-aminobenzamide), N,N'-bis(4-aminophenyl) pair Indoleamine, N,N'-bis(3-aminophenyl)-p-amine, N,N'-bis(4-aminophenyl) meta-amine, N,N'-double (3 -aminophenyl)m-decylamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2' - bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-double (4-Aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxyl) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminobenzene Oxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-amino group Phenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-amino Phenoxy)octane, 1,9-bis(4-amino group Oxy) decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxyl) Base) decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxyl 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-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane Further, as the above, the amine group is a secondary amine group-containing diamine compound or the like.

In addition, a diamine compound may also be used, which has a carboxyl group. A diamine compound (COOH group) or a hydroxyl group (OH group).

Specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamine Resorcinol, 2,4-diaminobenzoic acid, 2,5-diamino benzoic acid or 3,5-diamino benzoic acid. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferred. Further, a diamine compound represented by the following formula [3b-1] to formula [3b-4] and a diamine compound in which the amine group is a secondary amine group can also be used.

(In the formula [3b-1], A ¹ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-, m ¹ and m ² each independently represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, in the formula [3b-2], m ³ and m ⁴ each independently represent an integer of 1 to 5, and in the formula [3b-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m ⁵ represents an integer of 1 to 5, In [3b-4], A ³ and A ⁴ each independently represent 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-, m ⁶ represents an integer from 1 to 4).

Further, as the diamine compound, a diamine compound having a nitrogen-containing hetero ring represented by the following formula [3c] and a diamine compound in which the amine group is a secondary amine group can also be used.

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- are easy to synthesize. A diamine compound or the like is preferred. More preferably, it 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.

An aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be linear Yes, branchers can also. Also, it may have an unsaturated bond. Among them, an alkylene group having a carbon number of 1 to 10 is preferred.

Specific examples of the non-aromatic hydrocarbon group, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, and a ring Undecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, ring nineteen An alkane ring, a cyclohexadecane ring, a tricyclohexadecane ring, a tricyclotetracosane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring is preferred.

Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring or an anthracene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring or an anthracene ring is preferred.

Preferred D ² in the formula [3c], for example, 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, an anthracene ring or an anthracene ring. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferred.

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 from 1 to 5). Among them, a single bond, -O-, -COO-, -OCO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5) is preferred. More preferably, it 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, and examples thereof include aromatic impurities having a structure selected from at least one of the following formulas [a], (b) and (c). ring.

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

More specifically, for example, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an indazole ring, an anthracene ring Thiadiazole ring, hydrazine Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridyl Benzimidazole ring, Benzoimidazole ring, thioquinoline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine (phenothiazine) ring, oxadiazole ring or acridine ring. Among them, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, hydrazine Ring, three Ring, triazole ring, pyridyl A ring, a Benzimidazole ring or a Benzoimidazole ring is preferred. More preferably, it is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

Further, D ³ in the formula [3c] is preferably a bond which is not adjacent to the substituent of the formula [a], the formula [b] and the formula [c] contained in D ⁴ .

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

The combination of D ¹ to D ⁴ and n in the formula [3c] is such that D ¹ represents -CONH-, D ² represents an alkyl group having 1 to 5 carbon atoms, D ³ represents a single bond, and D ⁴ represents an imidazole ring or a pyridine. Ring, n represents a diamine compound of 1.

In the formula [3c], the bonding position of the two amine groups (-NH ₂ ) is not particularly limited. Specifically, for example, the bonding group (B ¹ ) with respect to the side chain is a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, 3, 4 position or 3, 5 position, etc. Among them, from the viewpoint of the reactivity at the time of synthesizing polyglycine, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferable. Further, when the ease of synthesizing the diamine compound is considered, the position of 2, 4 or the position of 2, 5 is more preferable.

Further, as the other diamine compound, a diamine compound represented by the following formula [3d-1] to formula [3d-13] and a diamine compound in which the amine group is a secondary amine group can also be used.

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

(In the formula [3d-5], A ¹ and A ³ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, and in the formula [3d-6], A ⁴ and A ⁶ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ⁵ represents a carbon number of 1 to 22 A chain or branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [3d-7], A ¹ and A ³ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, in the formula [3d-8], A ⁴ and A ⁶ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ⁵ represents a carbon number of 1 to 22 A chain or branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [3d-9], A ¹ and A ³ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, in the formula [3d-10], A ⁴ and A ⁶ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ⁵ represents a carbon number of 1 to 22 A chain or branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

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

In the other diamine compound of the present invention, the solubility of the specific polymer (A) and the specific polymer (B) of the present invention with respect to the solvent or the coating property of the liquid crystal alignment treatment agent, and the liquid crystal in the case of the liquid crystal alignment film are considered. From the viewpoints of characteristics such as an orientation, a voltage holding ratio, and an accumulated charge, one type or two types or more may be used in combination.

The specific polymer (A) and the specific polymer (B) of the present invention, that is, the tetracarboxylic acid component used in the production of the polyimine-based polymer, are represented by the following formula [4]. Tetracarboxylic dianhydride is preferred. In this case, not only the tetracarboxylic dianhydride represented by the formula [4] but also a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound or a tetracarboxylic acid as a tetracarboxylic acid derivative thereof may be used. The acid dialkyl ester dihalide compound (the tetracarboxylic dianhydride represented by the formula [4] and its derivative are also collectively referred to as a specific tetracarboxylic acid component).

(In the formula [4], Z represents a structure selected from at least one of the 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, and they may be the same or different.

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

In the Z in the formula [4], the ease of synthesis or the production of poly From the viewpoint of easiness of polymerization reactivity in the case of a compound, a tetracarboxylic dianhydride having a structure represented by the formula [4a], the formula [4c] to the formula [4g] or the formula [4k], and a tetracarboxylic acid derivative thereof It is better. More preferably, it is a structure represented by the formula [4a] or the formula [4e] to the formula [4g]. Particularly preferred are tetracarboxylic dianhydrides of the formula [4a], formula [4e] or formula [4f] and tetracarboxylic acid derivatives thereof.

The specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) of the present invention is preferably from 1 mol% to 100 mol% in 100 mol% of the total tetracarboxylic acid component. Among them, it is preferably 5 mol% to 95 mol%. More preferably, it is 20% by mole to 80% by mole.

The specific tetracarboxylic acid component of the present invention is used in consideration of the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent, or the coatability of a liquid crystal alignment treatment agent, as a liquid crystal alignment film. From the viewpoints of characteristics such as the alignment property of the liquid crystal, the voltage holding ratio, and the charge accumulation, one type or two types or more may be used in combination.

In the polyamidene-based polymer of the specific polymer (A) and the specific polymer (B) of the present invention, other tetracarboxylic acids other than the specific tetracarboxylic acid component may be used within a range not impairing the effects of the present invention. Acidic ingredients.

Examples of the other tetracarboxylic acid component include dicarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds or dicarboxylic acid dialkyl esters which are shown below. Compounds and the like.

That is, other tetracarboxylic acid components may, for example, be 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid. 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-dicarboxyl) Phenyl, 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)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3, 4,9,10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid or the like.

The other tetracarboxylic acid component of the present invention is considered as a liquid crystal alignment film in consideration of solubility of a specific polymer (A) and a specific polymer (B) of the present invention in a solvent or a coating property of a liquid crystal alignment agent. From the viewpoints of characteristics such as liquid crystal alignment, voltage holding ratio, and accumulated charge, one type or two types or more may be used in combination.

<Specific Polymer (A) ‧ Specific Polymer (B) Production Method>

In the present invention, the specific polymer (A) and the specific polymer (B), that is, the method for producing the polyimine-based polymer are not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and a derivative of a tetracarboxylic acid thereof is the same as that of one or more kinds of diamine compounds. A method in which an amine component is reacted to obtain a polyamic acid. Specifically, for example, a method in which a tetracarboxylic dianhydride is subjected to a polycondensation reaction with a primary or secondary diamine compound to obtain a polyamic acid, a tetracarboxylic acid and a primary or secondary diamine compound can be used. A method of producing a poly-proline by performing a dehydration polycondensation reaction to obtain a poly-proline acid, or a polycondensation reaction of a tetracarboxylic acid dihalide with a primary or secondary diamine compound.

In the method for producing a polyalkyl amide, for example, a method in which a tetracarboxylic acid obtained by dialkylating a carboxylic acid group is subjected to polycondensation with a primary or secondary diamine compound, and a carboxylic acid group can be used. A method of polycondensation of a dialkyl esterified tetracarboxylic acid dihalide with a primary or secondary diamine compound or a method of converting a carboxyl group of a polylysine to an ester.

As a method of producing a polyimine, for example, a method of subjecting the aforementioned polyamic acid or polyalkyl amide to a ring closure reaction to form a polyimine can be used.

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent in which the diamine component and the tetracarboxylic acid component are carried out. The solvent to be used at this time is not particularly limited as long as it can dissolve the produced polyimide precursor. Specific examples of the solvent used in the reaction are listed below, but are not limited to the examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamidine An amine, dimethyl hydrazine or 1,3-dimethyl-tetrahydroimidazolidone or the like. Further, in the case where the solvent solubility of the polyimide precursor is high, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following may be used. A solvent represented by the formula [D-1] to the formula [D-3].

(In the formula [D-1], D ¹ represents an alkylene group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkylene group having 1 to 3 carbon atoms, and the formula [D-3] , D ³ represents an alkylene group having a carbon number of 1 to 4).

These solvents may be used singly or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it may be used in combination with the solvent as long as it does not precipitate the range of the produced polyimide precursor. Further, the moisture in the solvent is a cause of hindering the polymerization reaction, and may even cause hydrolysis of the produced polyimide precursor. Therefore, it is preferred that the solvent be dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, a solution in which a diamine component is dispersed or dissolved in a solvent may be used, and the tetracarboxylic acid component may be left untreated or dispersed or dissolved. a method of adding in a solvent, or conversely, a method in which a tetracarboxylic acid component is dispersed in a solvent or dissolved, a method of adding a diamine component, a method of mutually adding a diamine component and a tetracarboxylic acid component, and the like, Any of the above methods can be used. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a state of being mixed in advance, or the respective reactions may be carried out in sequence, and the low molecular weight bodies obtained by the respective reactions may be mixed. The reaction can also be carried out to obtain a polymer. The polymerization temperature at this time may be selected from any temperature of from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, the reaction may be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is too high to facilitate uniform stirring. Therefore, it is preferably 1 to 50% by mass, More preferably 5 to 30% by mass. It may be carried out at a high concentration in the initial stage of the reaction, and then a solvent may be added.

In the polymerization reaction of the polyimine 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. It is the same as the usual polycondensation reaction, and the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimine precursor.

The polyimine of the present invention is a polyimine obtained by subjecting the polyimine precursor to ring closure, and the ring closure ratio of the proline group in the polyimine (also referred to as a ruthenium imidization ratio) It does not have to be 100%, but can be adjusted to suit the purpose or purpose.

The method for imidating the polyimine precursor oxime may, for example, be a method in which the solution of the polyimide precursor is heated to be imidized without treatment, or in the case of a polyimide precursor. A method in which a catalyst is added to a solution to carry out a catalyst oxime imidization.

The temperature at which the polyimine precursor is subjected to hot imine in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the ruthenium reaction is excluded from the reaction. It is better to do it outside the system.

The catalyst of the polyimine precursor is imidized by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° It is carried out by stirring in °C. The amount of the basic catalyst is 0.5 moles to 30 moles, preferably 2 moles to 20 moles, of the prolyl group, and the amount of the anhydride is 1 mole of the prolyl group to 50. Mohr times, preferably 3 moles to 30 moles. Alkaline catalyst, can be listed For example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine is preferred, and it is preferred to maintain proper basicity when pyridine is used for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction. The imidization rate of the imidization of the catalyst oxime can be controlled according to the amount of the catalyst, the reaction temperature, and the reaction time.

The method of recovering the produced polyimine precursor or polyimine from the reaction solution of the polyimine precursor or the polyimine may be carried out by adding the reaction solution to a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. After the solvent is added and the precipitated polymer is recovered by filtration, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, after repeating the process of re-dissolving the precipitated polymer in the solvent and reprecipitating and recovering twice to 10 times, the impurities in the polymer can be lowered. In the case of the solvent, for example, an alcohol, a ketone or a hydrocarbon, etc., when three or more types of solvents are used, it is preferable to further improve the efficiency of purification.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution used to form a liquid crystal alignment film (also referred to as a resin film), which is a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B), and a solvent. The coating solution used.

For the specific polymer (A) of the present invention, polylysine can be used, Any of polyalkylenimine polymers and polyamidiene polymers may be used. Among them, polyalkyl amide or polyimide is preferred. More preferably, it is a polyimine.

As the specific polymer (B) of the present invention, any of polyacrylamide, polyalkylenimine and polyamidiene may be used. Among them, polylysine or polyalkyl phthalate is preferred. More preferably, it is polyamic acid.

In the liquid crystal alignment treatment agent of the present invention, the ratio of the specific polymer (A) to the specific polymer (B) is 0.5 parts by mass to 950 per 100 parts by mass of the specific polymer (A). The quality is preferred. Among them, it is preferably 10 parts by mass to 900 parts by mass, more preferably 10 parts by mass to 400 parts by mass.

In the liquid crystal alignment treatment agent of the present invention, all of the polymer components may be all of the specific polymer (A) and the specific polymer (B) of the present invention, or may be mixed with other polymers other than the above. . Examples of the polymer other than the above include a polyimide-based polymer having no structure of the tertiary nitrogen atom of the present invention and a polyimide-based polymer having no specific structure (2). Further, for example, a cellulose-based polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine or polyoxyalkylene or the like. In this case, the content of the polymer other than the above is 0.5 parts by mass to 30 parts by mass based on 100 parts by mass of the specific polymer of the specific polymer (A) and the specific polymer (B) of the present invention. Among them, it is preferably 1 part by mass to 20 parts by mass.

Further, the solvent in the liquid crystal alignment treatment agent of the present invention contains The amount is preferably 70% by mass to 99.9% by mass. This content can be appropriately changed in accordance with the coating method of the liquid crystal alignment agent or the film thickness of the intended liquid crystal alignment film.

The solvent used for the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) capable of dissolving the specific polymer (A) and the specific polymer (B). Specific examples of the good solvent will be listed below, but are not limited to the examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Anthracene, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.

Further, in the case where the specific polymer (A) and the specific polymer (B) are highly soluble in the solvent, it is preferred to use the solvent represented by the above formula [D-1] to the formula [D-3].

The good solvent in the liquid crystal alignment agent of the present invention is preferably 20% by mass to 99% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably 20% by mass to 90% by mass. More preferably, it is 30% by mass to 80% by mass.

The liquid crystal alignment treatment agent of the present invention can use a solvent (also referred to as a poor solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, without impairing the effects of the present invention. . Specific examples of the poor solvent will be listed below, but are not limited to the examples. Show.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 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-ethanediol, 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 ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2- Hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acid ester, ethylene glycol single B Acid ester, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol single Hexyl ether, 2-(hexyloxy)ethanol, decyl 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 Ester, ethylene glycol monoacetate, 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 lactate, lactate B Ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid Methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or a solvent represented by the above formula [D-1] to formula [D-3].

Among them, 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.

The amount of the poor solvent is preferably from 1% by mass to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably 10% by mass to 80% by mass. More preferably, it is 20% by mass to 70% by mass.

In the liquid crystal alignment treatment agent of the present invention, it is selected by introducing a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. A crosslinkable compound having at least one substituent or a crosslinkable compound having a polymerizable unsaturated bond is preferred. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

a crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four Glycidylamine diphenylene, tetraglycidyl-m-xylenediamine, tetrahydration Glycerol-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3- Bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxylate) Base) nonafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethylxylenediamine, 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-glycidoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl) Phenyl)-2-propanol and the like.

A crosslinkable compound having an oxypropylene group, for example, a crosslinkable compound having at least two oxypropylene groups represented by the following formula [4A].

Specifically, for example, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of the publication of WO2011/132751 (2011.10.27).

The crosslinkable compound having a cyclic carbonate group is, for example, a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

Specifically, for example, a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in pages 76 to 82 of International Publication WO2012/014898 (published in 2012.2.2).

A crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a hydrazine Resin, acetylene urea-formaldehyde resin, amber decyl amide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative or a benzindene in which an amino group hydrogen atom is substituted with a methylol group or an alkoxymethyl group or both thereof can be used. Derivative, or acetylene urea. The melamine derivative or benzopyrene The derivative may also be present as a 2-mer or a 3-mer. Each of these three It is preferred that the ring has an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups.

These melamine derivatives or benzopyrene Examples of derivatives, for example, each of the three commercially available products The ring has an average of 3.7 substituted methoxymethyl MX-750, each three MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or CYMEL-300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., having an average of 5.8 substituted methoxymethyl groups. Oxyoxymethylated melamine, CYMEL-235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, CYMEL-506, 508, etc. butoxymethylated melamine Carboxy-containing methoxymethylated isobutoxymethylated melamine such as CYMEL-1141, methoxymethylated ethoxymethylated benzopyrene such as CYMEL-1123 , CYMEL-1123-10 and other methoxymethylated butoxymethylated benzopyrene , CYMEL-1128 and other butoxymethylated benzopyrene a carboxy-containing methoxymethylated ethoxymethylated benzopyrene such as CYMEL-1125-80 (above, manufactured by Mitsui Cyanide Co., Ltd.). Further, examples of the acetylene urea include a butoxymethylated acetylene urea such as CYMEL-1170, a methylolated acetylene urea such as CYMEL-1172, and the like, and a methoxymethylolated acetylene urea represented by POWER-LINK 1174.

a benzene or a phenolic compound having a hydroxyl group or an alkoxy group, for example, 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, for example, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO01/132751 (2011.10.27).

A crosslinkable compound having a polymerizable unsaturated bond, for example, has three trimethylolpropane tri(meth)acrylates, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid in the molecule. a crosslinkable compound of a polymerizable unsaturated group such as an ester, tris(meth)acryloxyethoxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate, in addition, For example, 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, butanediol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, oxyethylene bisphenol A type di(meth) acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol II (Meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, decanoic acid a crosslinkable compound having two polymerizable unsaturated groups in the molecule such as glycidyl di(meth)acrylate or hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, and, in addition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (methyl) Acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth) acrylate 2-(methyl) propylene A crosslinkable compound having one polymerizable unsaturated group in the molecule such as methoxyethyl phosphate or N-methylol (meth) acrylamide.

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

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

The above compound is exemplified as one of the crosslinkable compounds, but is not limited to these contents. In addition, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or a combination of two or more types.

In the liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably from 0.1 part by mass to 150 parts by mass based on 100 parts by mass of the total polymer component. In addition, from the viewpoint of the effect of achieving the purpose of the crosslinking reaction, it is preferably 0.1 parts by mass to 100 parts by mass based on 100 parts by mass of all the polymer components. More preferably, it is 1 part by mass to 50 parts by mass.

In the liquid crystal alignment treatment agent of the present invention, when the liquid crystal alignment treatment agent is applied, a compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film can be used without departing from the effects of the present invention.

A compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film, for example, a fluorine-based surfactant, a polyoxyn-based surfactant, a nonionic surfactant, or the like.

More specifically, for example, F-Top EF301, EF303, EF352 (above, manufactured by Dow Corning Chemical Manufacturing Co., Ltd.), MEGAFACE F171, F173, R-30 (above, manufactured by Dainippon Coatings Co., Ltd.), FLUORAD FC430, FC431 (above, Sumitomo 3M), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above) , Asahi Glass Co., Ltd.).

The use ratio of the surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment treatment agent of the present invention, as a compound which accelerates the charge transfer in the liquid crystal alignment film, the charge releasing compound can be added, for example, from 69 pages to 73 of International Publication WO2011/132751 (2011.10.27 publication). The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156] disclosed in the above. The amine compound may be added directly to the liquid crystal alignment treatment agent, and it may be preferably added in a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, using a suitable solvent. The solvent is not particularly limited as long as it can dissolve the solvent of the specific polymer (A) and the specific polymer (B).

In the liquid crystal alignment treatment agent of the present invention, the poor solvent, the crosslinkable compound, the compound for improving the film thickness uniformity or the surface smoothness of the resin film or the liquid crystal alignment film, and the compound for promoting the charge release are not damaged. A dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the electrical conductivity of the liquid crystal alignment film can be added to the range of the effects of the invention.

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be applied as a liquid crystal alignment film by applying an alignment treatment such as rubbing treatment or light irradiation after being applied and sintered on a substrate. Further, in the case of use in a vertical alignment or the like, it may be used as a liquid crystal alignment film without applying an alignment treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO electrode or the like is formed from the viewpoint of liquid crystal driving. Further, in the case of a reflective liquid crystal display device, when it is only a single-sided substrate, an opaque substrate such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it can be generally carried out by screen printing, lithography, letterpress printing, or inkjet method. Other coating methods, for example, a dipping method, a roll coating method, a slit coating method, a spinning method, or a spray method, may be used in combination with the purpose.

After the liquid crystal alignment agent is applied onto the substrate, a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven may be used, and a solvent used for the liquid crystal alignment agent may be used at 30 to 300 ° C, preferably The temperature of 30 to 250 ° C causes the solvent to evaporate to form a liquid crystal alignment film. The thickness of the liquid crystal alignment film after sintering is unfavorable from the viewpoint of the power consumption of the liquid crystal display element when it is too thick, and the liquid crystal display element is caused when it is too thin. Since the reliability is lowered, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. In order to make the liquid crystal horizontally or obliquely aligned, the liquid crystal alignment film after sintering may be treated by rubbing or irradiating with polarized ultraviolet rays.

In the liquid crystal display device of the present invention, a liquid crystal alignment cell can be produced by a liquid crystal alignment film of the present invention, and a liquid crystal cell can be produced as a liquid crystal display device by a known method.

For the method of fabricating a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed may be prepared, and a spacer may be spread on a liquid crystal alignment film of one substrate to make the liquid crystal alignment film surface inner side, and the other side The substrate is bonded together, and the liquid crystal is sealed under reduced pressure, or the liquid crystal is dropped into the liquid crystal alignment film surface on which the spacer is dispersed, and then the substrate is bonded and sealed.

Further, the liquid crystal alignment treatment agent of the present invention is also suitably used for a liquid crystal layer between substrates having one pair of electrodes, and the polymerization between the pair of substrates is carried out by polymerization of at least one of an active energy ray and heat. A liquid crystal display device produced by the step of polymerizing a polymerizable compound by applying a voltage to the liquid crystal composition of the compound and continuing to apply a voltage between the electrodes and irradiating the active energy ray. Among them, the active energy ray is preferably UV-based. The wavelength of the ultraviolet light is 300 to 400 nm, preferably 310 to 360 nm. In the case where the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, it is also possible to carry out the simultaneous irradiation of the ultraviolet rays and the heating.

The above liquid crystal display element is PSA (Polymer) Sustained Alignment) to control the pretilt angle of liquid crystal molecules. In the PSA method, a small amount of a photopolymerizable compound is mixed with a liquid crystal material, for example, a photopolymerizable monomer is mixed, and after a liquid crystal cell is combined, a photopolymerizable property is irradiated with ultraviolet rays or the like while a specific voltage is applied to the liquid crystal layer. A compound that controls the pretilt angle of the liquid crystal molecules with the polymer formed. The alignment state of the liquid crystal molecules at the time of polymer formation is still memorized after the voltage is removed, and the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. Further, in the PSA method, since it is not necessary to perform the rubbing treatment, it is suitable for a method of forming a vertical alignment type liquid crystal layer which is extremely difficult to use a rubbing treatment to control the pretilt angle.

In other words, the liquid crystal display device of the present invention is obtained by preparing a liquid crystal cell by using a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention, and using at least one of irradiation and heating using ultraviolet rays. The polymerizable compound is polymerized to control the alignment of the liquid crystal molecules.

Hereinafter, an example in which a liquid crystal cell is produced by a PSA method, that is, a pair of substrates on which a liquid crystal alignment film is formed, is prepared, and a spacer is spread on a liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inside. In the method, the substrate on the other side is bonded, and the liquid crystal is injected under reduced pressure to seal it, or the liquid crystal is dropped into the liquid crystal alignment film surface on which the spacer is dispersed, and then the substrate is bonded and sealed.

In the liquid crystal, a polymerizable compound polymerizable by heat or ultraviolet irradiation is mixed. The polymerizable compound has, for example, one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. Compounds, etc. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound cannot be polymerized, and the alignment of the liquid crystal cannot be controlled. When the amount is more than 10 parts by mass, the residual property of the liquid crystal display element is lowered due to excessive unreacted polymerizable compound. .

After the liquid crystal cell is produced, the alternating polymer or DC voltage is continuously applied to the liquid crystal cell, and the polymerizable compound is polymerized by using heat or ultraviolet light. In this way, the alignment of the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between substrates provided with one pair of electrodes, and the substrate between the pair of substrates is disposed to be polymerized via at least one of an active energy ray and heat. The liquid crystal alignment element which is a polymerizable group liquid crystal alignment film and which is obtained by applying a voltage or the like between the electrodes, that is, it is preferably used in the SC-PVA mode. Among them, the active energy ray is suitable for ultraviolet rays. The wavelength of the ultraviolet light is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization using heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, it is also possible to use ultraviolet rays simultaneously with heating.

In the method of producing a liquid crystal alignment film containing a polymerizable group by polymerization using at least one of an active energy ray and heat, for example, a method of adding a polymerizable group-containing compound to a liquid crystal alignment treatment agent, or using A method of polymerizing a polymer component containing a polymerizable group.

An example of fabrication of a liquid crystal cell of the SC-PVA mode is exemplified, for example, preparing a pair of substrates of the present invention in which a liquid crystal alignment film is formed. a plate in which a spacer is disposed on a liquid crystal alignment film of a substrate on one side, and a liquid crystal alignment film surface is disposed inside, a substrate on the other side is bonded, and a liquid crystal is decompressed and sealed, or a liquid crystal is sealed. After dropping the liquid crystal alignment film surface on which the spacer is dispersed, the substrate is bonded to the method of sealing.

After the liquid crystal cell is produced, the alignment of the liquid crystal molecules can be controlled by continuously applying an alternating current or a direct current voltage to the liquid crystal cell, and irradiating heat or ultraviolet rays.

As described above, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment film having a stable pretilt angle even after exposure to high temperature for a long period of time and light irradiation. In addition, it is also a kind of residual charge liquid crystal alignment film which can suppress the decrease of the voltage holding ratio even after long-term exposure to light irradiation, and can quickly alleviate the accumulation of the DC voltage. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is suitable for use in a large-screen and high-precision liquid crystal television, or a small-sized car navigation system or an intelligent type. Mobile phones, etc.

[Examples]

The present invention will be described in more detail below by way of examples, but is not limited thereto.

"Abbreviations used in the synthesis examples, examples and comparative examples of the present invention"

The abbreviations used in the synthesis examples, examples, and comparative examples are as follows. Show.

<Monomer used in the production of the polyimine-based polymer of the present invention> (Specific diamine compound (1) of the present invention)

A1: a diamine compound represented by the following formula [A1]

A2: a diamine compound represented by the following formula [A2]

A3: a diamine compound represented by the following formula [A3]

(Specific diamine compound (2) of the present invention)

B1: a diamine compound represented by the following formula [B1]

(Specific side chain type 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-heptylcyclohexyl)phenoxymethyl]benzene

C3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

C4: a diamine compound represented by the following formula [C4]

(other diamine compounds)

D1: p-phenylenediamine

D2: 3,5-diamino benzoic acid

D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic acid component of the present invention)

E1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

E2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

E3: tetracarboxylic dianhydride represented by the following formula [E3]

E4: tetracarboxylic dianhydride represented by the following formula [E4]

E5: tetracarboxylic dianhydride represented by the following formula [E5]

"Crosslinking compound used in the present invention"

K1: a 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

"Determination of molecular weight of polyimine-based polymer of the present invention"

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803). , KD-805) (manufactured by Shodex Co., Ltd.), measured as follows.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (additive, lithium bromide-water (LiBr‧H ₂ O) is 30 mmol/L (liter), phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol/ L, tetrahydrofuran (THF) is 10ml / L)

Flow rate: 1.0ml/min

Standard samples for the production of calibration lines: TSK standard polyoxyethylene (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (made by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (Polymer Laboratories) Company system).

"Determination of the oxime imidization ratio of the polyimine of the present invention"

The oxime imidization ratio of the polyimine in the synthesis example is determined by the following formula. That is, 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sampling tube (NMR standard sampling tube, 5 (manufactured by Kusano Scientific Co., Ltd.), deuterated dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed product) (0.53 ml) was added, and ultrasonic waves were applied thereto to completely dissolve. The 500 MHz proton NMR of this solution was measured using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM Co., Ltd.). The sulfhydrylation rate is determined by the protons produced by the unaltered structure before and after the imidization as the reference proton. The peak value of the proton is used, and the NH group of the proline is present near 9.5 ppm to 10.0 ppm. The resulting proton peak product is calculated and evaluated according to the following formula.

醯 imidization rate (%) = (1-α‧x/y) × 100

In the above formula, x is a proton peak product value generated by the NH group of valine acid, y is a peak product integrated value of the reference proton, and α is a polyproline (the imidization ratio is 0%). The ratio of the number of reference protons to one NH proton of proline.

"Synthesis of Polyimine 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) were mixed in NMP (25.5 g) and reacted at 40 ° C After 8 hours, a polyamic acid solution (1) having a resin solid content concentration of 25% by mass was obtained. The polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 86,500.

<Synthesis Example 2>

E1 (4.10g, 20.9mmol), B1 (3.16g, 10.6mmol), D1 (0.46g, 4.24mmol) and D2 (0.97g, 6.35mmol) were mixed in NMP (26.1g) and reacted at 40 ° C After 8 hours, a polyamic acid solution (2) having a resin solid concentration of 25% by mass was obtained. The polyamic acid had a number average molecular weight of 25,200 and a weight average molecular weight of 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) were mixed in NEP (32.1 g) and reacted at 80 ° C After 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (16.0 g) were further added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (3) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 20,100 and a weight average molecular weight of 64,100.

<Synthesis Example 4>

In the polyamic acid solution (3) (30.0 g) obtained by the synthetic method of Synthesis Example 3, after adding NEP to 6% by mass, acetic anhydride (3.45 g) and pyridine (as the ruthenium amide) were added. 2.50 g), and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyamidimide had a quinone imidization ratio of 55%, a number average molecular weight of 18,500, and a weight average molecular weight of 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) were mixed in NEP (33.4 g) and reacted at 80 ° C After 5 hours, E1 (3.50 g, 17.9 mmol) and NEP (16.7 g) were further added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (5) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 22,100 and a weight average molecular weight of 68,500.

<Synthesis Example 6>

In the polyamic acid solution (5) (30.0 g) obtained by the synthetic method of Synthesis Example 5, after adding NEP to 6% by mass, acetic anhydride (3.40 g) and pyridine as a ruthenium amide catalyst were added. 2.65 g), and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. A polyimide pigment (6) was obtained. This polyimine had a quinone imidization ratio of 58%, a number average molecular weight of 19,800, and a weight average molecular weight of 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) in NMP (17.4 g) After mixing for 5 hours at 80 ° C, E1 (2.50 g, 12.8 mmol) and NMP (8.72 g) were further added and reacted at 40 ° C for 6 hours to obtain a polymer having a solid concentration of 25% by mass. Proline solution.

After the NMP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.45 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 17,100, and a weight average molecular weight of 47,800.

<Synthesis Example 8>

E2 (1.37g, 5.46mmol), B1 (1.38g, 4.61mmol), C2 (1.09g, 2.77mmol) and D2 (1.68g, 11.1mmol) were mixed in NMP (16.0g) and reacted at 80 ° C After 5 hours, E1 (2.50 g, 12.8 mmol) and NMP (8.02 g) were further added and reacted at 40 ° C for 6 hours to obtain a resin. A polyamic acid solution having a solid concentration of 25% by mass.

After the NMP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.50 g) and pyridine (3.35 g) as a ruthenium amide catalyst were added, and the mixture was reacted at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had an oxime imidization ratio of 81%, a number average molecular weight of 18,800, and a weight average molecular weight of 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) were mixed in NEP (48.3 g) and reacted at 40 ° C After 8 hours, a polyamic acid solution (9) having a resin solid concentration of 25% by mass was obtained. The polyamic acid had a number average molecular weight of 21,200 and a weight average molecular weight of 65,400.

<Synthesis Example 10>

In the polyamic acid solution (9) (30.0 g) obtained by the synthetic method of Synthesis Example 9, after adding NEP to 6% by mass, acetic anhydride (3.40 g) and pyridine as a ruthenium-imiding catalyst were added. 2.63 g), and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide has a ruthenium iodide ratio of 57%, a number average molecular weight of 18,200, and a weight average molecular weight of 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 mixed in NMP (24.3 g) and reacted at 40 ° C After 8 hours, a polyamic acid solution having a resin solid concentration of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (30.0 g), and after diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.65 g) as a ruthenium catalyst were added, and the reaction was carried out at 60 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazine imidation ratio of 68%, a number average molecular weight of 17,500, and a weight average molecular weight of 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) in NMP (17.0 g) After mixing and reacting at 80 ° C for 6 hours, E1 (2.50 g, 12.8 mmol) and NMP (8.52 g) were further added and reacted at 40 ° C for 6 hours to obtain a polymer having a solid concentration of 25% by mass. Proline solution.

After the NMP was diluted to 6% by mass in the obtained polyaminic acid solution (30.0 g), acetic anhydride was added as a ruthenium catalyst. (4.15 g) and pyridine (2.95 g) were reacted at 70 ° C for 3 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimine had a hydrazide conversion ratio of 64%, a number average molecular weight of 18,100, and a weight average molecular weight of 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) in NEP (16.6 g) The mixture was mixed and reacted at 80 ° C for 6 hours, and then E1 (1.25 g, 6.37 mmol) and NEP (8.30 g) were added, and reacted at 40 ° C for 6 hours to obtain a polycondensate having a resin solid content concentration of 25% by mass. Amino acid solution.

After the NEPP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), acetic anhydride (4.55 g) and pyridine (3.35 g) as a ruthenium catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (13). The polyamidimide had a ruthenium iodide ratio of 81%, a number average molecular weight of 16,300, and a weight average molecular weight of 45,100.

<Synthesis Example 14>

E4 (3.57g, 11.9mmol), A1 (1.37g, 6.89mmol), C4 (1.70g, 3.44mmol) and D2 (1.05g, 6.89mmol) in NMP (17.4g) After mixing and reacting at 80 ° C for 6 hours, E1 (1.00 g, 5.10 mmol) and NMP (8.69 g) were further added and reacted at 40 ° C for 6 hours to obtain a polythene having a resin solid concentration of 25% by mass. Amino acid solution.

After the NEPP was diluted to 6% by mass in the obtained polyaminic acid solution (30.0 g), acetic anhydride (3.75 g) and pyridine (2.35 g) as a ruthenium catalyst were added, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (14). The polyimine had a ruthenium iodide ratio of 53%, a number average molecular weight of 17,800, and a weight average molecular weight of 48,900.

<Synthesis Example 15>

E2 (1.73g, 6.91mmol), A1 (0.70g, 3.50mmol), A2 (0.75g, 3.50mmol), C2 (2.76g, 7.00mmol) and D2 (0.53g, 3.50mmol) in NMP (17.3g) After mixing for 6 hours at 80 ° C, E5 (2.20 g, 10.4 mmol) and NMP (8.67 g) were further added and reacted at 80 ° C for 6 hours to obtain a polymer having a solid concentration of 25% by mass. Proline solution (15). The polyamic acid had a number average molecular weight of 20,100 and a weight average molecular weight of 62,600.

<Synthesis Example 16>

E2 (0.88g, 3.54mmol), B1 (1.60g, 5.37mmol), C1 (1.36g, 3.58mmol) and D2 (1.36g, 8.95mmol) were mixed in NMP (16.4g) and reacted at 80 ° C After 6 hours, add E5 (3.00g, 14.1 mmol) and NMP (8.21 g) were reacted at 80 ° C for 6 hours to obtain a polyamic acid solution (16) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 21,600 and a weight average molecular weight of 65,100.

<Synthesis Example 17>

In the polyamic acid solution (16) (30.0 g) obtained by the synthetic method of Synthesis Example 16, after adding NMP to 6 mass%, acetic anhydride (4.50 g) and pyridine as a ruthenium catalyst were added. (3.30 g), reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (17). The polyimine had an oxime imidation ratio of 81%, a number average molecular weight of 18,800, and a weight average molecular weight of 52,200.

<Synthesis Example 18>

E2 (1.73g, 6.91mmol), A3 (0.89g, 4.38mmol), C3 (2.65g, 6.13mmol) and D2 (1.07g, 7.00mmol) were mixed in NEP (17.1g) and reacted at 80 °C After 6 hours, E5 (2.20 g, 10.4 mmol) and NEP (8.54 g) were further added, and the mixture was reacted at 80 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6% by mass in the obtained polyamidic acid solution (30.0 g), acetic anhydride (4.10 g) and pyridine (3.05 g) as a ruthenium catalyst were added, and the reaction was carried out at 70 ° C. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate is The mixture was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (18). The polyamidimide had a ruthenium iodide ratio of 74%, a number average molecular weight of 17,900, and a weight average molecular weight of 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 mixed in NMP (16.4 g) and reacted at 80 ° C After 6 hours, E5 (2.70 g, 12.7 mmol) and NMP (8.20 g) were further added and reacted at 80 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride (3.75 g) and pyridine (2.55 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 60 ° C. 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (19). The polyimine had a quinone imidization ratio of 55%, a number average molecular weight of 16,800, and a weight average molecular weight of 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 to obtain a solid concentration of the resin. 25 mass% polylysine solution (20). The polyamic acid had a number average molecular weight of 25,800 and a weight average molecular weight of 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 to obtain a solid concentration of the resin. 25 mass% polylysine solution (21). The polyamic acid had a number average molecular weight of 27,100 and a weight average molecular weight of 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) were mixed in NEP (31.3 g) and reacted at 80 ° C After 5 hours, E1 (3.20 g, 16.3 mmol) and NEP (15.7 g) were further added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (22) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 22,500 and a weight average molecular weight of 66,900.

<Synthesis Example 23>

In the polyamic acid solution (22) (30.0 g) obtained by the synthetic method of Synthesis Example 22, after adding NEP to 6 mass%, acetic anhydride (3.40 g) and pyridine as a ruthenium catalyst were added. (2.50 g), and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (23). The polyamidimide has a quinone imidization ratio of 55%, a number average molecular weight of 19,200, and a weight average molecular weight of 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) were mixed in NEP (31.0 g) and reacted at 80 ° C After 5 hours, E1 (3.70 g, 18.9 mmol) and NEP (15.5 g) were further added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (24) having a resin solid concentration of 25% by mass. This polyamic acid had a number average molecular weight of 23,000 and a weight average molecular weight of 68,800.

<Synthesis Example 25>

In the polyamic acid solution (24) (30.0 g) obtained by the synthetic method of Synthesis Example 24, after adding NEP to 6% by mass, acetic anhydride (3.40 g) and pyridine as a ruthenium catalyst were added. (2.65 g), and reacted at 60 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (25). The polyamidimide had a ruthenium iodide ratio of 57%, a number average molecular weight of 20,100, and a weight average molecular weight of 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 mixed in NEP (16.5 g) and reacted at 80 ° C After 5 hours, add E1 (1.60g, 8.16 mmol) and NEP (8.25 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25% by mass.

After the NEPP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride (3.45 g) and pyridine (2.65 g) as a ruthenium catalyst were added, and the reaction was carried out at 60 ° C. 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (26). The polyimine had a ruthenium iodide ratio of 54%, a number average molecular weight of 17,600, and a weight average molecular weight of 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) were mixed in NEP (16.7 g) and reacted at 80 ° C After 5 hours, E1 (1.75 g, 8.92 mmol) and NEP (8.34 g) were further added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NEPP was diluted to 6% by mass in the obtained polyamic acid solution (30.0 g), acetic anhydride (3.45 g) and pyridine (2.65 g) as a ruthenium catalyst were added, and the reaction was carried out at 60 ° C. 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (27). This polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 18,600, and a weight average molecular weight of 51,500.

The polyimide-based polymer of the present invention is as shown in Tables 2 to 4 Show.

"Manufacture of Liquid Crystal Alignment Treatment Agent of the Present Invention"

In the following Examples 1 to 19 and Comparative Examples 1 to 8, the production examples of the liquid crystal alignment treatment agent are described. Further, the liquid crystal alignment treatment agent is also used in the evaluation contents.

The liquid crystal alignment treatment agent of the present invention is shown in Tables 5 to 7.

Using the liquid crystal alignment treatment agent obtained in the examples and the comparative examples of the present invention, "evaluation of spray coating property of liquid crystal alignment treatment agent", "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", and " Evaluation of voltage holding ratio (general unit cell), "evaluation of residual charge (general unit cell)" and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell)".

"Evaluation of spray coating properties of liquid crystal alignment agents"

The liquid crystal alignment treatment agent (4) obtained in Example 4 of the present invention, the liquid crystal alignment treatment agent (9) obtained in Example 9, and the liquid crystal alignment treatment agent (15) obtained in Example 15 were formed into a membrane having a pore diameter of 1 μm. The filter was subjected to pressure filtration to evaluate the spray coating property. The spray coater was a HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.). The coating was applied to an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA at a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed of 40 mm/sec. The time until pre-drying was 60 seconds, and pre-drying was performed on the hot plate at 70 ° C for 5 minutes.

The coating property of the obtained substrate with the liquid crystal alignment film was confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of sand holes. As a result, it was found that the liquid crystal alignment film obtained in any of the examples had no sand holes on the coating film, and a liquid crystal alignment film having excellent film properties was obtained.

"Production of Liquid Crystal Cell and Evaluation of Pretilt Angle (General Cell)"

The liquid crystal alignment treatment agent obtained in the examples and the comparative examples of the present invention was subjected to pressure filtration using a membrane filter having a pore size of 1 μm to prepare a liquid crystal cell (general unit cell). This solution was spin-coated on an ITO surface of a 40×30 mm substrate (length 40 mm × width 30 mm, thickness 0.7 mm) washed with pure water and IPA, and dried at 100 ° C, 5 on a hot plate. The ITO substrate with a polyimine liquid crystal alignment film having a film thickness of 100 nm was heat-treated at 230 ° C for 30 minutes in a minute, heat cycle type dust-free oven. Further, the liquid crystal alignment treatment agent (4) obtained in Example 4 of the present invention, the liquid crystal alignment treatment agent (9) obtained in Example 9, and the liquid crystal alignment treatment agent (15) obtained in Example 15 are in accordance with the above "liquid crystal". The evaluation of the spray coating property of the alignment treatment agent was carried out under the same conditions to prepare a substrate with a liquid crystal alignment film, followed by heat treatment at 230 ° C for 30 minutes in a heat cycle type dust-free oven to obtain a film. An ITO substrate having a thickness of 100 nm and having a polyimide film alignment film.

The coating film surface of the ITO substrate was placed in a friction device having a drum diameter of 120 mm, and rayon cloth was used, and rubbing treatment was performed under the conditions of a drum rotation number of 1000 rpm, a drum traveling speed of 50 mm/sec, and a pressing amount of 0.1 mm. .

Two sheets of the obtained ITO substrate with the liquid crystal alignment film were prepared, and a spacer of 6 μm was sandwiched so that the liquid crystal alignment film faces inward, and an empty cell was formed by using a sealant and then surrounding. This empty unit cell was injected into the nematic liquid crystal by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (general unit cell).

Further, in the liquid crystal cell obtained by using the liquid crystal alignment treatment agent (1) obtained in Example 1 and the liquid crystal alignment treatment agent (21) obtained in Comparative Example (1), the liquid crystal was MLC-2003 (Merck ‧ Japanese company system). In the liquid crystal cells used in the liquid crystal alignment treatment agents obtained in the examples and the comparative examples, the liquid crystal was MLC-6608 (manufactured by Merck & Co., Ltd.).

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

Further, after the isotropic treatment of the liquid crystal cell prepared under the same conditions as described above, the liquid crystal cell after irradiation with ultraviolet rays of 10 J/cm ² in terms of 365 nm was also measured. Further, the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Further, the irradiation of ultraviolet rays was carried out by using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT).

It is evaluated as the pretilt angle after liquid crystal isotropic treatment (also known as Iso treatment) after heat treatment (also known as high temperature treatment) and after ultraviolet irradiation (also known as ultraviolet irradiation). Pretilt angle change The smaller the amount, the better (in Table 8 to Table 10, the value of the pretilt angle after Iso treatment, high temperature treatment, and ultraviolet irradiation).

In Tables 8 to 10, the results obtained by labeling the examples and the comparative examples are shown.

"Evaluation of Voltage Retention Rate (General Cell)"

The liquid crystal cell (general cell) prepared under the same conditions as the above-mentioned "production of liquid crystal cell and evaluation of pretilt angle (general cell)" was used to evaluate the voltage holding ratio. Specifically, on the liquid crystal cell (general unit cell) obtained by the above method, a voltage of 1 V is applied at a temperature of 80 ° C for 60 μs, and the voltage after 50 ms is measured, and the degree to which the voltage can be maintained is calculated. As a result, it is used as a voltage holding ratio (also referred to as VHR). Further, the measurement was carried out using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Kagyo Co., Ltd.) under the settings of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

In addition, the liquid crystal cell after the completion of the instantaneous voltage holding ratio after the production of the liquid crystal cell was measured, and a table type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT Co., Ltd.) was used, and the irradiation was performed at 365 nm in an amount of 50 J/cm ² . Ultraviolet rays were measured under the same conditions as above.

It is evaluated that the value of the voltage holding ratio immediately after the liquid crystal cell is produced is higher, and the value of the voltage holding ratio immediately after the liquid crystal cell is produced is smaller as the value after the ultraviolet irradiation is smaller. Marked as good (in Tables 11 to 13), immediately after the marking liquid crystal cell is fabricated, and The value of VHR after ultraviolet irradiation).

In Tables 11 to 13, the results obtained by labeling the examples and the comparative examples are shown.

"Evaluation of Residual Charge Reduction (General Cell)"

The liquid crystal cell (general unit cell) produced under the same conditions as the above-mentioned "production of liquid crystal cell and evaluation of pretilt angle (general cell)" was used to evaluate the residual charge. Specifically, a direct current voltage of 10 V for 30 minutes was applied to the liquid crystal cell, and after short-circuiting for 1 second, the potential generated in the liquid crystal cell was measured at 1800 seconds. Here, the value of the residual charge after 50 seconds was used as an evaluation for slowing down the residual charge. Further, it was measured to use a 6254 liquid crystal physical property evaluation device (manufactured by Toyo Corporation).

In addition, the liquid crystal cell after the completion of the residual charge immediately after the production of the liquid crystal cell was measured and irradiated with ultraviolet rays of 30 J/cm ² at 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT Co., Ltd.). The residual charge was measured under the same conditions as above.

It is evaluated that the liquid crystal cell is immediately after the production, and the value of the residual charge after the ultraviolet irradiation is small, which is expressed as good (in Tables 11 to 13), immediately after the production of the labeled liquid crystal cell, and the residual charge after the ultraviolet irradiation. value).

In Tables 11 to 13, the results obtained by labeling the examples and the comparative examples are shown.

"Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)"

The liquid crystal alignment treatment agent (3) obtained in Example 3, the liquid crystal alignment treatment agent (5) obtained in Example 5, the liquid crystal alignment treatment agent (6) obtained in Example 6, and the liquid crystal alignment treatment agent obtained in Example 8 ( 8) The liquid crystal alignment treatment agent (16) obtained in Example 16 was subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and liquid crystal cell production and liquid crystal alignment (PSA unit cell) were evaluated. This solution was spin-coated on a substrate with an ITO electrode (length 40 mm × width 30 mm, thickness 0.7 mm) of a 10 μm 10 × 10 mm pattern having a space of 100 °m in the center of pure water and IPA washing, and attached to the center. The ITO surface of a substrate having a 10×40 mm ITO electrode (40 mm in length × 30 mm in width, 0.7 mm in thickness) was placed on a hot plate at 300 ° C for 5 minutes in a heat-recycling type dust-free oven at 230 ° C for 30 minutes. The film was heat-treated to obtain a polyimide film having a film thickness of 100 nm.

The substrate to which the liquid crystal alignment film was attached was combined so that the liquid crystal alignment film surface was inside, and a spacer of 6 μm was sandwiched, and an empty cell was obtained by encapsulating the periphery. This empty cell is injected into a nematic liquid crystal (MLC-6608) (manufactured by Merck & Co., Inc.) as a polymerizable compound (1) represented by the following formula, and mixed with a nematic liquid crystal (for the liquid crystal cell). After the liquid crystal obtained by the polymerizable compound (1) of 100% by mass of 100% by mass of MLC-6608), the injection port was sealed to obtain a liquid crystal cell.

In the obtained liquid crystal cell, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was cut by using a metal halide lamp having an illuminance of 60 mW, and irradiation was performed using ultraviolet rays of 20 J/cm ² in terms of 365 nm to obtain a liquid crystal alignment direction. Controlled liquid crystal cell (PSA unit cell). When the liquid crystal cell was irradiated with ultraviolet rays, the temperature in the irradiation device was 50 °C.

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

When the PSA unit cell obtained in any of the examples was compared with the liquid crystal cell before the ultraviolet irradiation, it was found that the response speed of the liquid crystal cell after the ultraviolet irradiation was faster, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, in any of the liquid crystal cells, it was confirmed that the liquid crystal exhibited uniform alignment when observed using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation).

<Example 1>

A polyamic acid solution (1) (5.00 g) having a solid content of 25% by mass of a resin obtained by the synthetic method of Synthesis Example 1 and a synthetic method of Synthesis Example 2. NMP (18.2 g) and BCS (8.16 g) were added to a polyamic acid solution (2) (3.33 g) having a solid concentration of 25% by mass of a resin, and stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent. (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (1), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 2>

The resin having a solid concentration of 25% by mass of the polyaminic acid solution (3) (4.50 g) obtained by the synthetic method of Synthesis Example 3 and the synthetic method of Synthesis Example 5 have a solid concentration of 25% by mass of polyamine. NEP (14.4 g) and PB (14.1 g) were added to the acid solution (5) (4.50 g), and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (2). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (2), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage retention rate (general cell)" and "evaluation of residual charge" General unit cell)".

<Example 3>

Polyimine powder (4) (1.15 g) obtained by the synthetic method of Synthesis Example 4 and polyimine powder obtained by the synthetic method of Synthesis Example 6 (6) In (1.15 g), NEP (21.6 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (14.4 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (3). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (3), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)", and "evaluation of residual charge" "General cell") and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 4>

NEP (14.9 g) was added to the polyimine powder (6) (0.43 g) obtained by the synthetic method of Synthesis Example 4 and the polyimine powder (6) (0.43 g) obtained by the synthetic method of Synthesis Example 6. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (5.97 g), PB (8.96 g) and K1 (0.032 g) were added, and the mixture was stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (4). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment agent (4), "evaluation of spray coating property of liquid crystal alignment treatment agent", "production of liquid crystal cell and evaluation of pretilt angle (general cell)", and evaluation of voltage holding ratio ( "General unit cell" and "Evaluation of residual charge reduction (general unit cell)".

<Example 5>

NMP (20.3 g) was added to the polyimine powder (8) (0.71 g) obtained by the synthetic method of Synthesis Example 7 and the polyimine powder (8) (0.71 g) obtained by the synthetic method of Synthesis Example 8. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (12.9 g) and DME (3.69 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (5). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment agent (5), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)", "evaluation of residual charge" (general "Unit cell" and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 6>

The resin obtained by the synthetic method of Synthesis Example 9 has a solid concentration of 25% by mass of a polyaminic acid solution (9) (3.50 g) and a synthetic method of Synthesis Example 5, and a resin having a solid concentration of 25% by mass of polyamine. NEP (14.0 g), PB (10.3 g) and EC (3.43 g) were added to the acid solution (5) (5.25 g), and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (6). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment agent (6), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)", "evaluation of residual charge" (general "Unit cell" and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 7>

NEP (15.0 g) was added to the polyimine powder (10) (1.75 g) obtained by the synthetic method of Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To this solution, PB (11.0 g) and DME (1.37 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a solution.

On the other hand, NEP (3.80 g) was added to the polyimine powder (6) (0.44 g) obtained by the synthetic method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, PB (2.70 g) and DME (0.34 g) were added, and the mixture was 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). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (7), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 8>

NMP (6.71 g) was added to the polyimine powder (8) (1.39 g) obtained by the synthetic method of Synthesis Example 11 and the polyimine powder (8) (1.39 g) obtained by the synthetic method of Synthesis Example 8. And NEP (13.4 g) was stirred at 70 ° C for 24 hours to dissolve. In this solution, PB (13.4g) and K1 (0.107 g) was stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (8). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (8), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)", and "evaluation of residual charge" (general "Unit cell" and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 9>

In the polyimine powder (8) (0.83 g) obtained by the synthetic method of Synthesis Example 11 and the polyimine powder (8) (0.83 g) obtained by the synthetic method of Synthesis Example 8, NEP (15.2 g) was added. And γ-BL (3.79 g) were stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (15.2 g) and DME (3.79 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (9), "evaluation of spray coating property of liquid crystal alignment treatment agent", "production of liquid crystal cell and evaluation of pretilt angle (general cell)", and evaluation of voltage holding ratio ( "General unit cell" and "Evaluation of residual charge reduction (general unit cell)".

<Example 10>

In the polyimine powder (4) (1.10 g) obtained by the synthetic method of Synthesis Example 4, NMP (1.73 g) and NEP (6.90 g) were added at 70 ° C. Stir for 24 hours to dissolve. To this solution, BCS (1.73 g) and PB (6.90 g) were added, and the mixture was 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 polyimine powder (12) (1.10 g) obtained by the synthetic method of Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours. It dissolves. To this solution, BCS (1.73 g) and PB (6.90 g) were added, and the mixture was 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 alignment treatment agent (10). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (10), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 11>

In the polyimine powder (13) (1.25 g) obtained by the synthetic method of Synthesis Example 13 and the polyimine powder (8) (0.83 g) obtained by the synthetic method of Synthesis Example 8, NEP (13.1 g) was added. And γ-BL (3.26 g) were stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (13.1 g) and EC (3.26 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (11). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (11), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage retention rate (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 12>

NMP (17.0 g) was added to the polyimine powder (8) (1.52 g) obtained by the synthetic method of Synthesis Example 10 and the polyimine powder (8) (1.52 g) obtained by the synthetic method of Synthesis Example 8. And γ-BL (1.70 g), and stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (6.79 g) and PB (8.49 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (12). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (12), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 13>

The polyacetamide solution (15) (4.50 g) having a solid concentration of 25% by mass of the resin obtained by the synthetic method of Synthesis Example 15 and the resin having a solid concentration of 25% by mass of the synthetic method of Synthesis Example 16 To the acid 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 the mixture was stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent. (13). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (13), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 14>

In the polyimine powder (17) (1.35 g) obtained by the synthetic method of Synthesis Example 7 and the polyimine powder (17) (1.35 g) obtained by the synthetic method of Synthesis Example 17, NEP (15.9 g) was added. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (5.29 g) and PB (14.1 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (14). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (14), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 15>

NMP (3.79 g) was added to the polyimine powder (17) (0.83 g) obtained by the synthetic method of Synthesis Example 7 and the polyimine powder (17) (0.83 g) obtained by the synthetic method of Synthesis Example 17. ) and NEP (15.2g), stirred at 70 ° C Mix for 24 hours to dissolve. To the solution, PB (19.0 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (15), "evaluation of spray coating property of liquid crystal alignment treatment agent", "production of liquid crystal cell and evaluation of pretilt angle (general cell)", and evaluation of voltage retention rate ( "General unit cell" and "Evaluation of residual charge reduction (general unit cell)".

<Example 16>

NMP (8.82 g) was added to the polyimine powder (18) (1.25 g) obtained by the synthetic method of Synthesis Example 18, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (2.94 g) and PB (7.86 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a solution.

On the other hand, NMP (5.88 g) was added to the polyimine powder (17) (0.83 g) obtained by the synthetic method of Synthesis Example 17, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To this solution, BCS (1.96 g) and PB (5.24 g) were added, and the mixture was 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 alignment treatment agent (16). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment agent (16), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)", "evaluation of residual charge" (general Unit cell) And "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)".

<Example 17>

To the liquid crystal alignment treatment agent (16) (20.0 g) obtained by the method of Example 16, K1 (0.06 g) was added, and the mixture was stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (17). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (17), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 18>

In the polyimine powder (19) (0.45 g) obtained by the synthetic method of Synthesis Example 19 and the polyimine powder (6) (1.80 g) obtained by the synthetic method of Synthesis Example 6, NEP (21.2 g) was added. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (3.53 g) and PB (10.6 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (18). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (18), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general Unit cell)".

<Example 19>

Polyurethane powder (19) (1.63 g) obtained by the synthetic method of Synthesis Example 19 and a synthetic method of Synthesis Example 5, a solid concentration of a resin having a solid concentration of 25% by mass of a polyaminic acid solution (5) (6.50 g) Among them, NEP (19.4 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, BCS (6.47 g) and PB (6.47 g) were added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (19). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (19), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Comparative Example 1>

The polyacetamide solution (20) (4.95 g) having a solid concentration of 25% by mass of the resin obtained by the synthetic method of Synthesis Example 20 and the resin having a solid concentration of 25% by mass of the synthetic method of Synthesis Example 21 NMP (18.0 g) and BCS (8.08 g) were added to the acid solution (21) (3.30 g), and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (20). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (20), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "voltage retention rate" Evaluation (general unit cell) and "evaluation of residual charge (general unit cell)".

<Comparative Example 2>

The resin having a solid concentration of 25% by mass of the polyaminic acid solution (3) (4.50 g) obtained by the synthetic method of Synthesis Example 3 and the synthetic method of Synthesis Example 24 have a solid concentration of 25% by mass of polyamine. To the acid solution (24) (4.50 g), NEP (14.4 g) and PB (14.1 g) were added, and the mixture was stirred at 25 ° C for 6 hours, and the liquid crystal alignment treatment agent (21). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (21), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Comparative Example 3>

The polyamic acid solution (22) (4.50 g) of the resin having a solid concentration of 25% by mass in the synthetic method of Synthesis Example 22 and the resin having a solid concentration of 25% by mass of the synthetic method of Synthesis Example 5 NEP (14.4 g) and PB (14.1 g) were added to the acid solution (5) (4.50 g), and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (22). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (22), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "voltage retention rate" Evaluation (general unit cell) and "evaluation of residual charge (general unit cell)".

<Comparative Example 4>

The resin obtained by the synthetic method of Synthesis Example 22 has a solid concentration of 25% by mass of a polyaminic acid solution (22) (4.50 g) and a synthetic method of Synthesis Example 24, and has a resin solid concentration of 25% by mass of polydecylamine. To the acid solution (24) (4.50 g), NEP (14.4 g) and PB (14.1 g) were added, and the mixture was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (23). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (23), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Comparative Example 5>

NEP (20.7 g) was added to the polyimine powder (25) (1.10 g) obtained by the synthetic method of Synthesis Example 4, and the polyimine powder (25) (1.10 g) obtained by the synthetic method of Synthesis Example 25. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (13.8 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (24). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (24), "liquid crystal crystal" Evaluation of cell fabrication and pretilt angle (general cell), "evaluation of voltage retention (general cell)" and "evaluation of residual charge (general cell)".

<Comparative Example 6>

In the polyimine powder (6) (1.10 g) obtained by the synthetic method of Synthesis Example 23 and the polyimine powder (6) (1.10 g) obtained by the synthetic method of Synthesis Example 6, NEP (20.7 g) was added. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (13.8 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (25). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (25), "production of liquid crystal cell and evaluation of pretilt angle (general cell)", "evaluation of voltage holding ratio (general cell)" and "evaluation of residual charge" (general Unit cell)".

<Comparative Example 7>

NEP (20.7 g) was added to the polyimine powder (25) (1.10 g) obtained by the synthetic method of Synthesis Example 23, and the polyimine powder (25) (1.10 g) obtained by the synthetic method of Synthesis Example 25. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (13.8 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (26). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (26), "liquid crystal crystal" Evaluation of cell fabrication and pretilt angle (general cell), "evaluation of voltage retention (general cell)" and "evaluation of residual charge (general cell)".

<Comparative Example 8>

NEP (20.7 g) was added to the polyimine powder (27) (1.10 g) obtained by the synthetic method of Synthetic Example 26, and the polyimine powder (27) (1.10 g) obtained by the synthetic method of Synthesis Example 27. The mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, PB (13.8 g) was added, and the mixture was stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (27). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed to be a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (27), "production of liquid crystal cell and evaluation of pretilt angle (general unit cell)", "evaluation of voltage holding ratio (general unit cell)" and "evaluation of residual charge" (general use) Unit cell)".

From the above results, it is understood that the liquid crystal alignment treatment agent of the embodiment of the present invention is compared with the liquid crystal alignment treatment agent of the comparative example, In the liquid crystal cell, even if high temperature treatment and ultraviolet irradiation are performed, a stable pretilt angle is exhibited. Further, even when ultraviolet irradiation is performed, the decrease in the voltage holding ratio can be suppressed, and the effect of the residual charge accumulated by the DC voltage can be quickly alleviated. That is, the liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film which can produce a stable pretilt angle even after prolonged exposure to high temperature and light irradiation, and is also a kind of liquid crystal alignment film which is exposed to light even after prolonged exposure. The voltage holding ratio can be suppressed from being lowered, and the residual charge liquid crystal alignment film accumulated by the DC voltage can be quickly alleviated.

Specifically, the embodiment using the liquid crystal alignment treatment agent of the specific polymer (A) of the present invention and the specific polymer (B) is compared with the embodiment of the liquid crystal alignment treatment agent obtained without using any of them, that is, Comparison of Example 2 with Comparative Example 2 or Comparative Example 3, and Example 3 with Comparative Example 5 or Comparative Example 6. Comparing with the comparative examples using only the specific polymers (A) or the comparative examples using only the specific polymer (B), when compared with the corresponding examples, it was found that the voltage holding ratio was large for ultraviolet irradiation. Lower, and the value of residual charge is also larger.

Further, the embodiment using the liquid crystal alignment treatment agent of the specific polymer (A) of the present invention and the specific polymer (B), and the polymer having no structure of the tertiary nitrogen atom of the present invention have no specific structure. A comparative example of the liquid crystal alignment treatment agent of the polymer (2), that is, a comparison between Example 1 and Comparative Example 1, a comparison between Example 2 and Comparative Example 4, and a comparison between Example 3 and Comparative Example 7. When these comparative examples were compared with the corresponding examples, it was found that the voltage holding ratio was largely lowered for ultraviolet irradiation, and the value of the residual electric charge was also larger.

Further, a comparison of an example of a liquid crystal alignment treatment agent using a specific polymer (A) of the present invention and a specific polymer (B), and a comparative example of a liquid crystal alignment treatment agent using a polymer having a side chain structure of a conventional type That is, the comparison between Example 3 and Comparative Example 8. In this comparative example, when compared with the corresponding examples, it was found that the change in the pretilt angle after the high-temperature treatment and the ultraviolet irradiation was larger, and the voltage holding ratio was largely lowered for the ultraviolet irradiation, and further, the residual The value of the charge is also larger. Among them, in particular, the reduction in voltage holding ratio is larger.

[Industrial use]

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film which can produce a stable pretilt angle even after prolonged exposure to high temperature and light irradiation. In addition, it is also possible to suppress a decrease in the voltage holding ratio even after long-time exposure to light irradiation, and to quickly alleviate the residual charge liquid crystal alignment film accumulated by the DC voltage. Further, a liquid crystal display element having the above liquid crystal alignment film, a liquid crystal alignment treatment agent which can provide the above liquid crystal alignment film, and the like can be provided.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is highly suitable for a large-screen and high-precision liquid crystal television, etc., for TN elements and STN elements. A TFT liquid crystal element, in particular, a vertical alignment type liquid crystal display element is useful.

Further, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is required to be irradiated with ultraviolet rays when the liquid crystal display element is produced. The liquid crystal display element of the line is useful. In other words, a liquid crystal layer is provided between the substrates including the pair of electrodes, and a liquid crystal composition containing at least one polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates. The liquid crystal composition has a liquid crystal layer between the liquid crystal display element produced by the step of polymerizing the polymerizable compound and a substrate having one pair of electrodes, and the pair of the liquid crystal layer is continuously applied with a voltage between the electrodes. A liquid crystal alignment film containing a polymerizable group polymerizable via at least one of an active energy ray and heat is disposed between the substrates, and the liquid crystal alignment film is continuously applied with a voltage between the electrodes to form the polymerizable group. Liquid crystal display elements produced by the polymerization step are also useful.

Claims (25)

A liquid crystal alignment treatment agent containing the following (A) component and (B) component, (A) component: at least one selected from the group consisting of a polyimide precursor having a structure having a nitrogen atom and a polyimine. Polymer (B): a polymer containing at least one selected from the group consisting of a polyimine precursor having a structure represented by the following formula [2] and a polyimine, and (A) component And at least any one of the polymers of the component (B) is a structure represented by the following formula [3]. (In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a carbon number of 1~). 3 alkylene), -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 a carbon number of 1) At least one organic group selected from ~3 alkylene), -CH ₂ O-, -COO-, and -OCO-, and Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y ⁴ represents an oxygen atom or a sulfur atom) (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-, B ² Represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), B ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, B ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, or a divalent group having a carbon number of 17 to 51 having a cholesterol skeleton The organic group, any hydrogen atom on the above cyclic group, may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3; 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, and B ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be It is substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is represented by n. An integer of 0 to 4, and B ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. ). The liquid crystal alignment agent of claim 1, wherein the structure having a nitrogen atom in the component (A) is at least one selected from the structures represented by the following formulas [1a] to [1c]. , (In the formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic hetero ring, and X ² represents a disubstituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 12 carbon atoms, in the formula [1b], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and X ⁴ and X ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. X ⁵ represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms, and m represents an integer of 0 or 1. In the formula [1c], X ⁸ and X ¹⁰ each independently represent a formula [1c-a] and a formula At least one structure selected from the structures shown in [1c-b], X ⁹ represents an alkylene group or a benzene ring having a carbon number of 1 to 5) The liquid crystal alignment treatment agent 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 a raw material, (In the formula [1-1], X ^A represents an organic group having a structure selected from at least one of the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² each independently represent a hydrogen atom. Or an alkyl group having a carbon number of 1 to 5). The liquid crystal alignment treatment agent according to claim 3, wherein the diamine compound is obtained by using a diamine compound represented by the following formula [1a-1] to formula [1c-1] as a raw material. Object, (In the formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic hetero ring, and X ² represents a disubstituted amino group substituted by a hydrogen atom or an aliphatic group having 1 to 12 carbon atoms, and the formula [1b- In 1], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and X ⁴ and X ⁶ each independently represent a hydrogen atom or a carbon number of 1 to 5. An alkyl group, X ⁵ represents an alkylene group or a biphenyl group having a carbon number of 2 to 5, and m represents an integer of 0 or 1. In the formula [1c-1], X ⁸ and X ¹⁰ each independently represent the formula [1c] -a) and at least one structure selected from the structures represented by the formula [1c-b], and X ⁹ represents an alkylene group or a benzene ring having a carbon number of 1 to 5, and a formula [1a-1] to a formula [1c- In 1], A ¹ to A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The liquid crystal alignment treatment agent according to claim 4, wherein the diamine compound is at least one diamine compound selected from the diamine compounds represented by the following formula [1-1a] to formula [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] to the formula [ In 1-4a], A ¹ to A ⁸ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. The liquid crystal alignment treatment agent 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 raw material. (In the formula [2-1], Y ^A represents an organic group having a structure represented by the above formula [2], and each of A ¹ and A ² independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms). The liquid crystal alignment treatment 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 raw material. (In the formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a carbon number of 1~). 3 alkylene), -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 a carbon number of 1) At least one organic group selected from ~3 alkylene), -CH ₂ O-, -COO-, and -OCO-, and Y ² and Y ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, Y ³ and Y ⁵ each independently represent 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 ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms) . The liquid crystal alignment treatment agent according to claim 7, wherein the diamine compound is at least one diamine compound selected from the diamine compounds represented by the following formula [2-1a] to formula [2-3a]. (In the formula [2-1a] to the formula [2-3a], A ¹ to A ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms). The liquid crystal alignment agent of claim 1, wherein the polymer of at least one of the components (A) and (B) is a part of a diamine compound represented by the following formula [3a]. The recipient, (In the formula [3a], B represents the above formula [3], and A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and m represents an integer of 1 to 4). The liquid crystal alignment agent of claim 1, wherein the polymer of the component (A) and the polymer of the component (B) are polyfluorene obtained by using a tetracarboxylic acid component represented by the following formula [4]. a precursor and at least one polymer selected from the group consisting of polyimine, (In the formula [4], Z represents at least one structure selected from the 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, respectively, in the formula [4g], Z ⁵ and Z ⁶ represent a hydrogen atom or a methyl group, which may be the same or different, respectively. The liquid crystal alignment treatment agent according to claim 10, wherein the tetracarboxylic acid component is selected from the structure represented by the above formula [4a] and the formula [4e] to the formula [4g]. A tetracarboxylic acid component having at least one structure. The liquid crystal alignment treatment agent according to claim 4, wherein the polymer of the component (A), the diamine compound represented by the above formula [1a-1] to the formula [1c-1], is contained in all the diamine components. In the ear %, it is 5 mol% to 95 mol%. The liquid crystal alignment agent of claim 7, wherein the diamine compound represented by the above formula [2a] in the polymer of the component (B) is 5 mol% based on 100 mol% of the total diamine component. ~95 moles %. The liquid crystal alignment agent of claim 1, wherein the polymer of the component (B) is 0.5 parts by mass to 950 parts by mass based on 100 parts by mass of the polymer of the component (A). The liquid crystal alignment treatment agent according to claim 1, wherein the solvent of the liquid crystal alignment treatment agent comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. Select at least one solvent. The liquid crystal alignment treatment agent of claim 1, wherein the solvent of the liquid crystal alignment treatment agent comprises 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, At least one solvent selected from ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether. The liquid crystal alignment treatment agent of claim 1, wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, and has a hydroxyl group or a hydroxyalkyl group. a crosslinkable compound of at least one substituent selected from the group consisting of lower alkoxyalkyl groups, and at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond . A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 17. A liquid crystal alignment film obtained by an inkjet method using a liquid crystal alignment treatment agent according to any one of claims 1 to 17. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 18. A liquid crystal display element comprising the liquid crystal alignment film of claim 19. The liquid crystal alignment film according to claim 18, wherein the liquid crystal layer is provided between the substrates having one pair of electrodes, and the substrate between the pair of substrates is disposed to be polymerized via at least one of an active energy ray and heat. A liquid crystal composition of a polymerizable compound which is obtained by a step of polymerizing the polymerizable compound by continuously applying a voltage between the electrodes. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 22. The liquid crystal alignment film of claim 18, which is used for a liquid crystal layer between a substrate having one pair of electrodes, the pair of substrates A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and a heat, wherein the step of polymerizing the polymerizable group is continued by applying a voltage between the electrodes A liquid crystal display element produced. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 24.