TW201522422A - 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.

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.

In recent years, liquid crystal display devices have been widely used in conjunction with large-screen liquid crystal televisions or high-precision portable applications (digital cameras or display portions of mobile phones). Therefore, when used in comparison with conventional ones, substrates used are formed. The enlargement and the unevenness of the substrate step are also increased. Under such circumstances, part of the display characteristics, for a large substrate or step, seeks a liquid crystal alignment film which can form a uniform coating film. In the production step of the liquid crystal alignment film, a liquid crystal alignment treatment agent (also referred to as coating) of polylysine or solvent-soluble polyimine (also referred to as soluble polyimine) which is a polyimide precursor. In the case where the solution is applied to a substrate, a relief printing method, a spray coating method, or the like is generally used in the industry. In this case, in addition to the N-methyl-2-pyrrolidone or γ-butyrolactone of a solvent (also referred to as a good solvent) having excellent solubility to the resin, the solvent of the coating solution is used to improve the liquid crystal alignment. For the purpose of film uniformity of the film, there is also a solvent having a low solubility of the mixed resin. (also known as a poor solvent) butyl cellosolve or the like (for example, Patent Document 1).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2-37324

In the liquid crystal alignment film, the liquid crystal alignment state (also referred to as liquid crystal alignment property) is controlled, and the electrical characteristics such as reliability or image sticking characteristics in the liquid crystal display element are also sought to be improved. In this regard, a liquid crystal alignment treatment agent obtained by mixing a polymer of a polyamic acid or a soluble polyimine having a liquid crystal alignment property with a polymer having electrical properties is used to improve the aforementioned characteristics. The method.

However, in these polymers, there are many cases in which the solvent solubility of the polymer is different and the polarity of the polymer is different. In the liquid crystal alignment treatment agent containing these polymers, the polymer component is often easily precipitated during storage of the liquid crystal alignment treatment agent. When the polymer component is deposited on the substrate, the uniformity of the coating film of the liquid crystal alignment film tends to decrease when the liquid crystal alignment agent is applied to the substrate. That is, a depression or a sand hole or the like is generated by the influence of the precipitated polymer component, and when it is used as a liquid crystal display element, the portion is defective in display. Moreover, even if it has the advantage of improving the storage stability of the liquid crystal alignment treatment agent, it is processed in liquid crystal alignment. When the agent is applied to the substrate, agglomeration of the polymer component (also referred to as whitening and aggregation) occurs on the substrate. When the whitening and the aggregation are caused, as in the above description, the uniformity of the coating film of the liquid crystal alignment film is lowered, and uniform coating properties are not obtained, which is also a display defect in the liquid crystal display device.

In recent years, liquid crystal display elements using backlights having a large amount of light irradiation, for example, car navigation systems or large televisions, have been used for a long time in exposure to high temperature and light irradiation environments, or placed. Therefore, even under such severe conditions, the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is required to have a high degree of stability. In other words, when the voltage holding ratio is lowered by the light generated by the backlight, the image defect (also referred to as linear afterimage) which is one of the display defects of the liquid crystal display element is likely to occur, and the high reliability cannot be obtained. Liquid crystal display element. Therefore, the liquid crystal alignment film is sought to have a characteristic that it is good in addition to the initial characteristics, for example, the voltage holding ratio is not easily lowered after exposure to light for a long period of time.

Therefore, the present invention has an object of providing a liquid crystal alignment treatment agent having the above characteristics. In other words, the object of the present invention is to provide a liquid crystal alignment treatment agent containing two or more different types of polymers, which is a liquid crystal alignment treatment agent having excellent storage stability, and is applied to a substrate on a liquid crystal alignment treatment agent. In the above, it is possible to suppress the whitening and aggregation of the polymer component, and to provide a liquid crystal alignment film having excellent coating film uniformity. In addition, it provides a liquid which can suppress a decrease in voltage holding ratio even after long-term exposure to light irradiation, in addition to having good initial characteristics. The crystal is oriented to the film.

Moreover, the present invention has an object of providing a liquid crystal display element having the liquid crystal alignment film.

Further, the present invention has an object of providing a liquid crystal alignment treatment agent which can provide the aforementioned liquid crystal alignment film.

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 agent containing the following (A) component and (B) component.

(A) Component: a polymer containing at least any one selected from a polyimine precursor having a structure having 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.

(In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkyl 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 a C 1 to 3 alkyl group), -N(R ³ )CO- (R ³ represents a hydrogen atom or a carbon number At least one organic group selected from 1 to 3 alkyl groups, -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).

(2) The liquid crystal alignment treatment agent according to the above (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]. Structure.

(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], 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) or (2), wherein the polymer of the component (A) is a part of a raw material using a diamine compound represented by the following formula [1-1]. And the resulting polymer.

(In the formula [1-1], X ^A represents an organic group having 5 to 50 carbon atoms having a structure selected from the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

(4) The liquid crystal alignment treatment agent according to the above (3), wherein the diamine compound is prepared by using a diamine compound represented by the following formula [1a-1] to formula [1c-1] as a raw material. The resulting 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 of 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-1 In the above, A ¹ to A ⁶ each independently represent a hydrogen atom or an alkylene 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 group consisting of the diamine compounds represented by the following formulas [1-1a] to [1-4a]. 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 alkyl group having 1 to 5 carbon atoms.

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

(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 alkyl 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 a C 1 to 3 alkyl group), -N(R ³ )CO- (R ³ represents a hydrogen atom or a carbon number At least one organic group selected from the group consisting of 1 to 3 alkyl groups, -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. ).

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

(9) The liquid crystal alignment treatment agent according to any one of the above (1) to (8), wherein the polymer of the component (A) and the polymer of the component (B) are obtained by using the following formula [3] A polyimine precursor prepared by the tetracarboxylic acid component and at least one polymer selected from the polyimine.

(In the formula [3], Z represents a structure selected from at least one of the structures represented by the following formulas [3a] to [3k]).

(In the formula [3a], Z ¹ to Z ⁴ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [3g], Z ⁵ and Z ⁶ represent a hydrogen atom or a methyl group, which may be the same or different, respectively.

(10) The liquid crystal alignment treatment agent according to the above (9), wherein the tetracarboxylic acid component is such that Z in the formula [3] is a structure represented by the formula [3a] and the formula [3e] to the formula [3g]. A tetracarboxylic acid component of at least one selected structure.

(11) Any of the above (4) to (10) In the liquid crystal alignment treatment agent, the diamine compound represented by the above formula [1a-1] to the formula [1c-1] in the polymer of the component (A) is contained in 100% by mole of the total diamine component. 5 mole %~95 mole%.

(12) The liquid crystal alignment treatment agent according to any one of the above (11), wherein the diamine compound represented by the formula [2a] is a diamine compound in the polymer of the component (B). In the component 100% by mole, it is 5 mol% to 95 mol%.

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

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

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

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

(17) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of (1) to (16) above.

(18) A liquid crystal alignment film obtained by the inkjet method using the liquid crystal alignment treatment agent described in any one of the above (1) to (16).

(19) A liquid crystal display element comprising the liquid crystal alignment film according to (17) or (18) above.

A liquid crystal alignment treatment agent containing two types of polymers selected from a polyimine precursor having a specific structure or a polyimine, which is a liquid crystal alignment treatment agent having excellent storage stability. Further, when the liquid crystal alignment agent is applied onto the substrate, the whitening and aggregation of the polymer component can be suppressed, and a liquid crystal alignment film having excellent uniformity of the coating film can be obtained. Further, it is a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after exposure to light for a long period of time in addition to good initial characteristics. 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.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

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

(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 having 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 It is called a specific polymer (B)).

(In the formula [2], Y ¹ and Y ⁷ each independently represent a single bond, an alkyl 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 a C 1 to 3 alkyl group), -N(R ³ )CO- (R ³ represents a hydrogen atom or a carbon number At least one organic group selected from 1 to 3 alkyl groups, -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).

Liquid crystal alignment prepared by liquid crystal alignment treatment agent of the present invention The reason why the film can solve the problem of the present invention is not fully understood, but should be described below.

That is, the nitrogen atom in the structure having a nitrogen atom contained in the specific polymer (A) interacts with the carboxyl group (COOH group) in the specific polymer (B), and the above formula [2] in the specific polymer (B) As a result of the interaction of the nitrogen atom in the specific polymer (A) with the carboxyl group in the specific polymer (A), the specific polymer (A) is compatible with the specific polymer (B), and the polymerization can be inhibited during the storage of the liquid crystal alignment treatment agent. The precipitation of the components and the whitening and condensing phenomenon that occurs when applied to the substrate.

Further, in the specific polymer (A), a structure having a nitrogen atom is presumed to trap an ionic impurity component which causes a decrease in the voltage holding ratio. 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 two types of polymers selected from the group consisting of a polyimine precursor having a specific structure or a polyimine is excellent in preservation. When the liquid crystal alignment treatment agent is applied to the substrate, the liquid crystal alignment treatment agent can suppress whitening and aggregation of the polymer component, and a liquid crystal alignment film having excellent uniformity of the coating film can be obtained. Further, it is also a liquid crystal alignment film which can suppress a decrease in voltage holding ratio even after long-term exposure to light irradiation, in addition to having good initial characteristics.

<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 having a nitrogen atom and a polyimine.

The specific structure of the structure having 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 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 (2) 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 alkyl group having 1 to 10 carbon atoms, -O-, -S-, -N(R ¹ )- (R ¹ represents a hydrogen atom or a C 1 to 3 alkyl group, -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 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. .

In order to obtain a polyamic acid in which A ¹ and A ² in the formula [A] are a hydrogen atom, a diamine compound having two primary or secondary amine groups in the molecule, and a tetracarboxylic acid compound or a tetracarboxylic acid are used. An acid anhydride can be obtained by carrying out a reaction.

In order to obtain an alkyl amide of the formula (A) wherein A ¹ and A ² are an alkylene group having 1 to 5 carbon atoms, the diamine compound and the tetracarboxylic acid dihalide compound may be used. A dicarboxylic acid carboxylic acid compound or a dicarboxylic 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 is a polymer having a structure having a nitrogen atom. Among them, the above formula [1a]~[1c] The structure is preferred.

The method of introducing the nitrogen atom-containing structure of the present invention 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. Part of it is preferred to the user.

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 a structure selected from at least one 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 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 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, it is 20% by mole to 80% by mole.

The specific diamine compound (1) of the present invention may have solubility in a solvent or a coating property of a liquid crystal alignment agent according to the specific polymer (A) of the present invention, liquid crystal alignment property and voltage in the case of a liquid crystal alignment film. Mixing one type or two types or more, the characteristics of retention rate, accumulated charge, etc. use.

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) as a diamine component. It is particularly preferred to use a diamine compound having the structure represented by the above formula [2].

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

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

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 a C 1 to 3 alkyl group, -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 viewpoint of liquid crystal alignment and film hardness, for example, a single bond having a structure which is softer and has a small 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.

In the formula [2a], a combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ^{7 is} preferred, for example, as 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% in 100 mol% of the total diamine component. Among them, it is preferably 5 mol% to 95 mol%. More preferably, it is 20% by mole to 80% by mole.

The specific diamine compound (2) of the present invention may have solubility in a solvent or a coating property of a liquid crystal alignment agent according to the specific polymer (B) of the present invention, liquid crystal alignment property and voltage in the case of a liquid crystal alignment film. The characteristics of the retention ratio, the accumulated charge, and the like are used in combination of one type or two types or more.

The specific polymer (A) of the present invention and the diamine component of the specific polymer (B) may be used in a range which does not impair the effects of the present invention, and a specific diamine compound (1) and a specific diamine compound (2) may also be used. Other diamine compounds (also known as other diamine compounds).

Specifically, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'- Diamine linkage Benzene, 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'-diamine linkage Benzene, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 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'-sulfonyldiphenylamine, 3 , 3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl - bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'- Diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2 -diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3' -diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N- Methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diamine Benzophenone, 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-di Amino naphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-double (4-Aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-amino) Phenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-amine Phenoxy group) benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl) Benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(... Methyl)]diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylene bis(methyl) Diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3 , 3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylene Bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminobenzene) Methyl ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-benzene Bis(4-aminobenzoic acid ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, double 3-aminophenyl) pair Dicarboxylate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene) Bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-stretch Phenyl) bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4- Aminophenyl) p-guanamine, N, N'-bis(3-aminophenyl) p-decylamine, N, N'-bis(4-aminophenyl) m-decylamine, N, N'-bis(3-aminophenyl) meta-amine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl碸, 2,2'-bis[4-(4-amino group) Phenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoro Propane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis ( 4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3- Bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-double (3-Aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6- Bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7 -(3-Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9 - bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10 -(3-Aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12 -(4-Aminophenoxy)dodecane, 1,12-(3 -aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4 -diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane, in addition, for example, the amine groups are secondary An amine diamine compound or the like.

Further, a diamine compound of a long-chain alkyl group having a highly hydrophobic side chain of a diamine compound can also be used.

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

The specific polymer (A) of the present invention and the specific polymer (B), that is, the tetracarboxylic acid component used in the production of the polyamidene-based polymer, are represented by the following formula [3]. Carboxylic dianhydride is preferred. In this case, not only the tetracarboxylic dianhydride represented by the formula [3] but also a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a dicarboxylic acid dialkylate compound or a tetracarboxylic acid II of the tetracarboxylic acid derivative thereof may be used. The alkyl ester dihalide compound (the tetracarboxylic dianhydride represented by the formula [3] and derivatives thereof are also collectively referred to as a specific tetracarboxylic acid component).

(In the formula [3], Z represents a structure selected from at least one of the structures represented by the following formulas [3a] to [3k]).

In the formula [3a], 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 [3g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group, and they may be the same or different.

In the formula Z, the viewpoint of the ease of synthesis or the ease of polymerization reactivity in the production of a polymer is expressed by the formula [3a], the formula [3c] to the formula [3g] or the formula [3k]. The tetracarboxylic dianhydride of the structure and its tetracarboxylic acid derivative are preferred. More preferably, it is a structure represented by the formula [3a] or the formula [3e] to the formula [3g]. Particularly preferred are tetracarboxylic dianhydrides of the formula [3a], formula [3e] or formula [3f] 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 can be combined with the present invention The solubility of the specific polymer (A) and the specific polymer (B) in a solvent, or the coating property of a liquid crystal alignment agent, the alignment property of a liquid crystal in the case of a liquid crystal alignment film, a voltage retention ratio, and an accumulated charge However, one type or two types or more can 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.

The other tetracarboxylic acid component may, for example, be 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 shown below. Compounds, etc.

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-dicarboxyphenyl)anthracene, 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-dicarboxybenzene) 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-nonanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4- Cyclobutane tetracarboxylic acid and the like.

The other tetracarboxylic acid component of the present invention may be combined with the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent or The coating property of the liquid crystal alignment agent, the liquid crystal alignment property, the voltage holding ratio, and the charge accumulation in the case of the liquid crystal alignment film are used in combination of one type or two types or more.

<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, for example, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and a derivative of tetracarboxylic acid thereof, and one or more kinds of diamine compounds may be mentioned. A method in which a diamine 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, and 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 polycondensation reaction of a polyamic acid or a tetracarboxylic acid dihalide with a primary or secondary diamine compound.

A method for producing an alkyl amide, for example, a method of polycondensing a tetracarboxylic acid obtained by dialkylating a carboxylic acid group with a primary or secondary diamine compound, and a carboxylic acid group by dioxane A method of polycondensation of a tetracarboxylic acid dihalide obtained by esterification 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, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following may be used. The solvent of 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 a solvent which does not dissolve the polyimide precursor is used in combination with the solvent as long as it does not precipitate a range of the produced polyimide precursor. Moreover, the moisture in the solvent is a hindrance to the polymerization reaction, and may even cause hydrolysis of the formed polyimine precursor, so the solvent is dehydrated and dried. It is better.

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 from 1 to 50% by mass, more preferably from 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) , not necessarily 100%, but can be matched Use or purpose for any adjustment.

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 thermally imidized 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. It is preferred to carry out the reaction outside the reaction system.

The method for imidizing the ruthenium imide of the polyimide precursor is to add a basic catalyst and an acid anhydride to the solution of the polyimide precursor at -20 ° C to 250 ° C, preferably 0 ° C. Stirring was carried out at ~180 °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. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is used to maintain proper alkalinity in the reaction. good. 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, only The reaction solution is poured into a solvent to precipitate it. 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.

As the specific polymer (A) of the present invention, any of polyacrylamide, polyalkylenimine and polyamidiene may be used. Among them, polyalkyl amide or polyimide is preferred. More preferably, it is a polyimine. Specifically, a polyimide having a ruthenium iodide ratio of 50% or more is preferable, and a polyimine having a ruthenium iodide ratio of 70% or more is more preferable.

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 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 content of the solvent in the liquid crystal alignment agent of the present invention 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.

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-methylcyclohexane Alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butylene glycol, 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 B Acid ester, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate Ester, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl 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, three Glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate , diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethyl Glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, 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, a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group is introduced, and has a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. A crosslinkable compound having at least one substituent selected from the group 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-xylylenediamine, tetraglycidyl-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-epoxypropoxy)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-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl Ethyl)phenoxy)-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, for example, a melamine derivative in which a hydrogen atom of an amine group is substituted by a methylol group or an alkoxymethyl group or both, a benzofluorene 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 butoxymethylated acetylene urea such as CYMEL-1170, methylolated acetylene urea such as CYMEL-1172, and methoxymethylolated acetylene urea such as 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, there are two ethylene glycol di(meth)acrylates, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(methyl) in the molecule. Acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A Type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol II (meth) acrylate, ethylene glycol diglycidyl ether di(meth) propylene Acid ester, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl diglycidyl di(meth)acrylate or hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate a crosslinkable compound of a polymerizable unsaturated group, and further, as a molecule, has one 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl group (Meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-(methyl) propylene methoxyethyl phosphate or N- hydroxymethyl (meth) acrylamide A crosslinkable compound of a polymerizable unsaturated group or the like.

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

(In the formula [7A], E ¹ is a group represented by a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring. The selected group, 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 Not limited to this content. 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 Paint Co., Ltd.), FLUORAD FC430, FC431 (above, Sumitomo 3M Company, AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).

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

In addition, in the liquid crystal alignment treatment agent of the present invention, as a compound which promotes the charge release of the element used for the movement of the charge in the liquid crystal alignment film, a page 69 to 73 of International Publication WO2011/132751 (2011.10.27 publication) can be added. A nitrogen-containing heterocyclic amine compound represented by the formula [M1] to formula [M156]. The amine compound may be added directly to the liquid crystal alignment treatment agent, and may be appropriately added to a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. 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 used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used. 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 when the thickness is too thin, the reliability of the liquid crystal display element is lowered, etc., so it is preferably 5 to 300 nm. More preferably, it is 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 polarized ultraviolet irradiation.

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, and the liquid crystal is injected under reduced pressure to be sealed, 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.

As described above, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having excellent storage stability, and when the liquid crystal alignment treatment agent is applied onto a substrate, whitening and aggregation of the polymer component can be suppressed. Phenomenon, a liquid crystal alignment film having excellent uniformity of coating film can be obtained. Further, in addition to having good initial characteristics, the liquid crystal alignment film having a reduced voltage holding ratio can be suppressed even after exposure to light for a long period of time. 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]

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

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

(other diamine compounds)

C1: p-phenylenediamine

C2: a diamine compound represented by the following formula [C2]

C3: a diamine compound represented by the following formula [C3]

(Specific tetracarboxylic acid component of the present invention)

D1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

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

(other tetracarboxylic acid components)

E1: pyromellitic dianhydride

"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

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

DPM: dipropylene glycol monomethyl 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>

D3 (13.5 g, 45.0 mmol), B1 (2.69 g, 9.02 mmol), C1 (3.40 g, 31.4 mmol) and C3 (1.56 g, 4.48 mmol) were mixed in NMP (84.7 g) and reacted at 40 ° C After 20 hours, a polyamic acid solution having a resin solid concentration of 20% by mass was obtained. The polyglycolic acid has a viscosity of 900 mPa ‧ at a temperature of 25 ° C.

NMP (200.0 g) was added to the obtained polyamic acid solution (80.0 g), and then acetic anhydride (36.5 g) and pyridine (17.0 g) as a ruthenium-imidation catalyst were added, and the mixture was reacted at 40 ° C for 3 hours. This reaction solution was poured into methanol (1170 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (1). The polyamidimide had a quinone imidization ratio of 85%, a number average molecular weight of 11,900, and a weight average molecular weight of 28,500.

<Synthesis Example 2>

D2 (2.25 g, 8.99 mmol), D3 (10.8 g, 36.0 mmol), B1 (2.68 g, 8.98 mmol), C1 (3.40 g, 31.4 mmol) and C3 (1.57 g, 4.50 mmol) in NMP (82.9 g) The mixture was mixed and reacted at 40 ° C for 24 hours to obtain a polyaminic acid solution having a resin solid concentration of 20% by mass. The polyglycolic acid had a viscosity of 980 mPa ‧ at a temperature of 25 ° C.

After NMP (200.0 g) was added to the obtained polyamic acid solution (80.0 g), the acetic anhydride was added as a ruthenium amide catalyst. (37.2 g) and pyridine (17.3 g) were reacted at 40 ° C for 3 hours. This reaction solution was poured into methanol (1170 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (2). The polyamidimide had a ruthenium iodide ratio of 65%, a number average molecular weight of 10,200, and a weight average molecular weight of 21,500.

<Synthesis Example 3>

D1 (3.92 g, 20.0 mmol), E1 (3.66 g, 16.8 mmol), A2 (2.55 g, 12.0 mmol) and C2 (5.55 g, 28.0 mmol) in NMP (44.2 g) and γ-BL (44.2 g) The mixture was mixed and reacted at 25 ° C for 2 hours to obtain a polyamic acid solution (3) having a resin solid concentration of 15% by mass. The polyglycolic acid had a viscosity of 340 mPa ‧ at a temperature of 25 ° C. Further, the polyamic acid had a number average molecular weight of 14,200 and a weight average molecular weight of 29,900.

<Synthesis Example 4>

D1 (3.92 g, 20.0 mmol), E1 (3.66 g, 16.8 mmol), A1 (2.39 g, 12.0 mmol) and C2 (5.55 g, 28.0 mmol) in NMP (44.2 g) and γ-BL (44.2 g) The mixture was mixed and reacted at 25 ° C for 2 hours to obtain a polyamic acid solution (4) having a resin solid concentration of 15% by mass. The polyglycolic acid had a viscosity of 330 mPa ‧ at a temperature of 25 ° C. Further, the polyamic acid had a number average molecular weight of 13,300 and a weight average molecular weight of 27,900.

<Synthesis Example 5>

D1 (5.65 g, 28.8 mmol), D3 (2.40 g, 7.99 mmol), A1 (6.38 g, 32.0 mmol) and C2 (1.58 g, 7.97 mmol) in NMP (44.2 g) and γ-BL (44.2 g) The mixture was mixed and reacted at 25 ° C for 2 hours to obtain a polyamic acid solution (5) having a resin solid concentration of 10% by mass. The polyglycolic acid had a viscosity of 170 mPa ‧ at a temperature of 25 ° C. Further, the polyamic acid had a number average molecular weight of 16,700 and a weight average molecular weight of 35,700.

<Synthesis Example 6>

D3 (14.4 g, 48.0 mmol), C1 (4.67 g, 43.2 mmol) and C3 (1.67 g, 4.79 mmol) were mixed in NMP (83.0 g), and reacted at 40 ° C for 20 hours to obtain a resin solid concentration. It is a 20% by mass polyamine solution. The polyglycolic acid had a viscosity of 890 mPa ‧ at a temperature of 25 ° C.

NMP (200.0 g) was added to the obtained polyamic acid solution (80.0 g), and then acetic anhydride (41.7 g) and pyridine (19.1 g) as a ruthenium catalyst were added, and the mixture was reacted at 40 ° C for 3 hours. This reaction solution was poured into methanol (1190 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had an oxime imidization ratio of 85%, a number average molecular weight of 10,300, and a weight average molecular weight of 22,800.

<Synthesis Example 7>

D1 (3.92 g, 20.0 mmol), E1 (3.66 g, 16.8 mmol) and C2 (7.93 g, 40.0 mmol) were mixed in NMP (44.2 g) and γ-BL (44.2 g), and reacted at 25 ° C 2 In an hour, a polyamic acid solution (7) having a resin solid concentration of 15% by mass was obtained. The polyglycolic acid had a viscosity of 330 mPa ‧ at a temperature of 25 ° C. Further, the polyamic acid had a number average molecular weight of 13,600 and a weight average molecular weight of 34,200.

The polyimide-based polymer of the present invention is shown in Table 2.

* 1: Polyglycine.

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

In the following Examples 1 to 6 and Comparative Examples 1 to 3, 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 3 and 4.

Using the liquid crystal alignment treatment agent obtained in the examples and the comparative examples of the present invention, the "evaluation of the storage stability of the liquid crystal alignment treatment agent", the "evaluation of the liquid crystal alignment treatment agent, the evaluation of the aggregation" and the "evaluation of the voltage retention rate" were carried out. .

"Evaluation of Preservation Stability of Liquid Crystal Alignment Treatment Agents"

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, and stored at -15 ° C for 48 hours. Subsequently, it was confirmed by visual observation whether or not turbidity or precipitates were generated in the liquid crystal alignment treatment agent.

In Tables 5 and 6, the results obtained by labeling the examples and the comparative examples are shown. Further, in the table, those in which no turbidity or precipitates were found to be a homogeneous solution were marked as ○, and those in which turbidity or precipitates were found were marked as ×.

Moreover, the liquid crystal alignment treatment agent which was stored at -15 ° C for 48 hours was spin-coated on a substrate (30 mm long × 30 mm horizontal, thickness 0.7 mm) with a 30×40 mm ITO electrode which was washed with pure water and IPA. On the ITO surface, heat treatment was performed on a hot plate at 100 ° C for 5 minutes to obtain an ITO substrate with a liquid crystal alignment film. Subsequently, the sand holes on the substrate to which the liquid crystal alignment film was attached were evaluated.

The evaluation was performed by visually observing the substrate under a sodium lamp. Specifically, the number of sand holes observed on the substrate with the liquid crystal alignment film was counted, and the smaller the number of sand holes, the smaller the number of precipitates in the liquid crystal alignment treatment agent, which was evaluated as excellent in the evaluation (Table) 5 and Table 6 are the number of marked sand holes).

In Tables 5 and 6, the results obtained by labeling the examples and the comparative examples are shown.

"Evaluation of Whitening and Condensation of Liquid Crystal Alignment Treatment Agents"

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, and 1 ml of a Cr substrate of 100 × 100 mm was dropped. Subsequently, it was placed in an environment of a temperature of 27 ° C and a humidity of 65%, and the time until the liquid crystal alignment treatment agent was dropped until turbidity (whitening and aggregation) was measured.

As a result of the evaluation, the longer the time until turbidity occurred, the better the whitening and condensing characteristics of the liquid crystal alignment treatment agent were obtained (Tables 5 and 6 indicate the labeling time).

In Tables 5 and 6, the results obtained by labeling the examples and the comparative examples are shown.

"Evaluation of Voltage Retention Rate"

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, and then spin-coated on a 40×30 mm ITO with purified water and IPA. The ITO surface of the substrate of the electrode (40 mm in length × 30 mm in width and 0.7 mm in thickness) was heat-treated on a hot plate at 80 ° C for 90 seconds in an IR (infrared) type dust-free oven at 230 ° C for 15 minutes 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 is placed at a roller diameter of 120 mm. The friction device was subjected to a rubbing treatment using a cotton cloth under the conditions of a drum rotation number of 1000 rpm, a drum speed of 35 mm/sec, and a pressurization amount of 0.7 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and a spacer having a thickness of 4 μm was formed by using a liquid crystal alignment film surface as an inner side, and an empty cell obtained by adhering the surrounding agent was adhered with a sealant. MLC-3018U (manufactured by Merck & Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell.

The obtained liquid crystal cell was used to evaluate the voltage holding ratio. Specifically, a voltage of 4 V of 60 μs was applied at a temperature of 90 ° C, and a voltage after 166.7 ms was measured, and the degree to which the voltage can be maintained was calculated 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: 166.7 ms.

In addition, a liquid crystal cell after measuring the instantaneous voltage holding ratio after the production of the liquid crystal cell was measured by using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT Co., Ltd.) in an ultraviolet ray of 5 J/cm ² in terms of 365 nm. And the measurement of the voltage holding ratio was carried out under the same conditions as above.

As a result of the evaluation, the value of the voltage holding ratio immediately after the liquid crystal cell is produced is high, and the value of the voltage holding ratio measured immediately after the liquid crystal cell is produced is smaller as the value of the value after the ultraviolet irradiation is smaller. Expressed as good (in Tables 5 and 6, to indicate immediately after liquid crystal cell fabrication) And the value of VHR after ultraviolet irradiation).

In Tables 5 and 6, the results obtained by labeling the examples and the comparative examples are shown.

<Example 1>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (1) (3.00 g) obtained by the synthetic method of Synthesis Example 1, and the mixture was stirred at 50 ° C for 20 hours to be dissolved. NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

In addition, NMP was added, and the solid content of the resin in the polyamic acid solution (3) obtained by the synthesis method of Synthesis Example 3 was 6% by mass to prepare a polymer solution.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Example 2>

In the polyimine powder (1) (3.00 g) obtained by the synthetic method of Synthesis Example 1, NMP (11.0 g) and γ-BL (11.0 g) were added thereto. The mixture was stirred at 50 ° C for 20 hours to dissolve. NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added, and the solid content concentration of the resin in the polyamic acid solution (4) obtained by the synthetic method of Synthesis Example 4 was 6% by mass to prepare a polymer solution.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Example 3>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (1) (3.00 g) obtained by the synthetic method of Synthesis Example 1, and stirred at 50 ° C for 20 hours to dissolve. . NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution having a solid concentration of the resin in the polyamic acid solution (5) obtained by the synthetic method of Synthesis Example 5 to 6 mass%.

Subsequently, the two polymer solutions are mixed and dissolved in the solution. Into the liquid, K1 (0.15 g) was added, and the mixture was stirred at 25 ° C for 20 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), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Example 4>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (2) (3.00 g) obtained by the synthetic method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve. . NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution in which the solid content of the resin in the polyamic acid solution (3) obtained by the synthetic method of Synthesis Example 3 was 6 mass%.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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 treatment agent (4), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Example 5>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (2) (3.00 g) obtained by the synthetic method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve. . NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution in which the solid content concentration of the resin in the polyamic acid solution (4) obtained by the synthesis method of Synthesis Example 4 was 6 mass%.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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 treatment agent (5), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Example 6>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (2) (3.00 g) obtained by the synthetic method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve. . NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

In addition, NMP is added to make the synthesis method according to Synthesis Example 5. The solid concentration of the resin in the obtained polyaminic acid solution (5) was 6% by mass to prepare a polymer solution.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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 treatment agent (6), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Comparative Example 1>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (6) (3.00 g) obtained by the synthetic method of Synthesis Example 6, and stirred at 50 ° C for 20 hours to dissolve. . NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution in which the solid content concentration of the resin in the polyamic acid solution (7) obtained by the synthesis method of Synthesis Example 7 was 6 mass%.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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), perform "liquid "Evaluation of the preservation stability of the crystal formulation to the treatment agent", "Evaluation of the whitening of the liquid crystal alignment treatment agent, evaluation of the aggregation" and "Evaluation of the voltage retention rate".

<Comparative Example 2>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (1) (3.00 g) obtained by the synthetic method of Synthesis Example 1, and the mixture was stirred at 50 ° C for 20 hours to be dissolved. NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution in which the solid content concentration of the resin in the polyamic acid solution (7) obtained by the synthesis method of Synthesis Example 7 was 6 mass%.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

<Comparative Example 3>

NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimine powder (6) (3.00 g) obtained by the synthetic method of Synthesis Example 6, and stirred at 50 ° C for 20 hours to dissolve. . In this solution, add NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g) and DPM (5.00 g) were stirred at 50 ° C for 20 hours to obtain a polymer solution.

Further, NMP was added to obtain a polymer solution in which the solid content of the resin in the polyamic acid solution (3) obtained by the synthetic method of Synthesis Example 3 was 6 mass%.

Subsequently, the above two polymer solutions were mixed, and K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C for 20 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 storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and liquidification of liquid crystal alignment treatment agent", and "evaluation of voltage retention rate" were performed.

*1 indicates the amount of introduction (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of the total polymer.

* 2: indicates a specific polymerization with respect to 100 parts by mass of the total polymer The amount of introduction (parts by mass) of the substance (B).

*3: The amount of introduction of other polymers (parts by mass) with respect to 100 parts by mass of all the solvents.

*1 indicates the amount of introduction (parts by mass) of the specific polymer (A) with respect to 100 parts by mass of the total polymer.

*2: The amount of introduction (parts by mass) of the specific polymer (B) with respect to 100 parts by mass of the total polymer.

*3: The amount of introduction of other polymers (parts by mass) with respect to 100 parts by mass of all the solvents.

As a result of the above, it is understood that the liquid crystal alignment treatment agent of the embodiment of the present invention is a liquid crystal alignment treatment agent having excellent storage stability as compared with the liquid crystal alignment treatment agent of the comparative example, and is subjected to liquid crystal alignment treatment. When the agent is applied to the substrate, whitening and aggregation of the polymer component can be suppressed. Further, in addition to having good initial characteristics, it is possible to suppress a decrease in the voltage holding ratio even after exposure to light for a long period of time.

Specifically, an example of using a liquid crystal alignment treatment agent of a specific polymer (A) of the present invention and a specific polymer (B), and a polymer containing no specific diamine compound (1) and a specific diamine-free The comparison of the liquid crystal alignment treatment agent obtained from the polymer of the compound (2), that is, the comparison between Example 1 and Comparative Example 1. In this comparative example, when the liquid crystal alignment treatment agent is stored, turbidity or precipitates are likely to occur during storage, and when the liquid crystal alignment treatment agent is applied onto the substrate, the polymer component is likely to be generated. Whitening, condensation, etc. Further, regarding the voltage holding ratio, in addition to the value measured immediately after the production of the liquid crystal cell, the exposure to the long-time light irradiation was also greatly reduced.

Further, 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, the implementation Comparison of Example 1 with Comparative Example 2 or Comparative Example 3. In the comparative examples, as compared with the above-described examples, it is known that the liquid crystal alignment treatment agent is likely to be turbid or precipitated during storage, and the liquid crystal alignment treatment agent is applied to the substrate. On the other hand, the polymer component is prone to whitening and condensing. Further, regarding the voltage holding ratio, in addition to the value measured immediately after the production of the liquid crystal cell, the exposure to the long-time light irradiation was also greatly reduced.

[Industrial Applicability]

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having excellent storage stability, and when the liquid crystal alignment treatment agent is applied onto a substrate, it can suppress the whitening and aggregation of the polymer component, and can provide A liquid crystal alignment film excellent in film uniformity. Further, in addition to having good initial characteristics, the liquid crystal alignment film having a reduced voltage holding ratio can be suppressed even after exposure to light for a long period of time.

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.

Claims (20)

A liquid crystal alignment treatment agent comprising the following (A) component and (B) component, (A) component: containing a polyimine precursor having a structure having a nitrogen atom and a polyimine a polymer of at least one of: (B) a polymer comprising at least one selected from the group consisting of a polyimine precursor having a 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-, -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). The liquid crystal alignment treatment agent according to 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 by the structure 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 5 to 50 carbon atoms having a structure selected from the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. 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 of 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-1 In the above, 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 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, and Y ⁴ represents an oxygen atom or a sulfur atom ^' 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 the component (A) and the polymer of the component (B) are polyfluorene obtained by using a tetracarboxylic acid component represented by the following formula [3]. At least one polymer selected from the imine precursor and the polyimine, (In the formula [3], Z represents a structure selected from at least one of the structures represented by the following formulas [3a] to [3k]) (In the formula [3a], Z ¹ to Z ⁴ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [3g], 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 9, wherein the tetracarboxylic acid component is at least one selected from the group consisting of the formula [3a] and the formula [3e] to the formula [3g] in the above formula [3]. Structure of the tetracarboxylic acid component. 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, a hydroxyalkyl group or A crosslinkable compound having 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 16. A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent of any one of claims 1 to 16. A liquid crystal display element comprising the liquid crystal alignment film of claim 17. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 18.