TWI638008B - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided to improve the adhesion between the sealant and the liquid crystal alignment film, and to suppress the occurrence of display unevenness in the vicinity of the front edge of the liquid crystal display element under high temperature and high humidity conditions, and to suppress the liquid crystal alignment film and the liquid crystal display element with reduced voltage maintenance ratio. And liquid crystal alignment treatment agent.

At least one selected from the group consisting of an additive containing an isocyanate group, an additive containing an amine group and a hydroxyl group, and a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component A liquid crystal alignment treatment agent for a polymer.

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element

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

A film made of an organic material such as a polymer material is attracting attention for its difficulty in forming or insulating properties, and is widely used as an interlayer insulating film or a protective film in the field of electronic devices. Among them, in the liquid crystal display element which is well known as a display device, an organic film composed of polyimine is used as a liquid crystal alignment film.

The liquid crystal alignment film is intended for the purpose of controlling the alignment state of the liquid crystal. In particular, with the high definition of the liquid crystal display element, the comparison of the liquid crystal display element is lowered or the display failure accompanying long-term use is suppressed.

In the case where the polyimide is used as the liquid crystal alignment film, it is proposed to use a liquid crystal alignment in which an alkoxydecane compound is added as a method for improving the liquid crystal alignment property and causing a display defect in the peripheral portion of the liquid crystal display screen. A liquid crystal alignment film formed by a treatment agent (for example, Patent Document 1 or 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-171762

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-119226

In recent years, liquid crystal display elements have been used for mobile use such as smart phones or mobile phones. For such applications, in order to ensure a large number of display surfaces as much as possible, it is necessary to use a sealant having a width closer to the substrate between the substrates of the liquid crystal display element than in the related art. Further, for the above reasons, it is also desired to position the sealant at a position where the end portion of the liquid crystal alignment film having a weak adhesion to the sealant or the upper portion of the liquid crystal alignment film. In such a case, when it is used under high temperature and high humidity conditions, water is easily mixed between the sealant and the liquid crystal alignment film, and display unevenness occurs near the front edge of the liquid crystal display element.

In addition, when water is mixed in the liquid crystal display element, the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is largely lowered, and the image defect (also referred to as line residual image) of the display failure of the liquid crystal display element is liable to occur. A highly reliable liquid crystal display element is obtained.

Therefore, an object of the present invention is to provide a combination of the above characteristics, to improve the adhesion between a sealant and a liquid crystal alignment film, and to suppress display unevenness in the vicinity of the front edge of a liquid crystal display element under high temperature and high humidity conditions, and to suppress Liquid crystal alignment treatment of liquid crystal alignment film with reduced voltage maintenance rate A liquid crystal display element having the liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent containing at least one polymer selected from a compound having a specific structure and a polyimine precursor or a polyimine is extremely effective in achieving the above object. The present invention has been completed.

That is, the present invention is mainly as follows.

A liquid crystal alignment treatment agent comprising the following components (A), (B) and (C), (A) a compound represented by the following formula [1], and (B) a component: a compound represented by the following formula [2], and a component (C): at least one selected from the group consisting of a polyimine precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimine. polymer, (X ¹ is a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms; or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is represented by the following formula [ 1-1]~Structure selected by [1-6] (A ¹ is a hydrogen atom or a benzene ring, A ² is a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and A ³ is an alkane having 1 to 18 carbon atoms. Base, fluorine-containing alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or fluorine-containing alkoxy group having 1 to 18 carbon atoms) (W ¹ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and W ² is a single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, - N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, W ³ is a single bond, a benzene ring or a cyclohexane ring, W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO -, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, W ⁵ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and n is 1 to 5 Integer).

2. The liquid crystal alignment treatment agent according to claim 1, wherein X ¹ of the above formula [1] is an alkylene group having 1 to 10 carbon atoms.

3. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ² of the above formula [1] is a structure selected by the formula [1-1], the formula [1-2], and the formula [1-4] .

4. The liquid crystal alignment treatment agent according to any one of the above-mentioned, wherein the W ¹ of the above formula [2] is a linear or branched alkyl group having a carbon number of 1 to 10, and a cyclohexane ring. Or a bicyclohexyl ring.

The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein W ² of the above formula [2] is a single bond, -O- or -OCO-.

The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein W ³ of the above formula [2] is a single bond or a benzene ring.

The liquid crystal alignment treatment agent according to any one of claims 1 to 6, wherein W ⁴ of the above formula [2] is a single bond, -O-, -NH- or -CONH-.

The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the W ⁵ of the above formula [2] is a single bond, a linear or branched alkyl group having a carbon number of 1 to 10 or Cyclohexane ring.

The liquid crystal alignment treatment agent according to any one of the above-mentioned items (1), wherein the diamine component of the polymer of the component (C) contains at least one of the structures represented by the following formula [3]. Diamine compound,

(Y is a substituent selected by the following formula [3-1] to formula [3-6], and m is an integer of 1 to 4) (a is an integer from 0 to 4, b is an integer from 0 to 4, Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c - (c is 1 to 15) An integer), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a bivalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton a divalent organic group having 12 to 25 carbon atoms, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 to 3 a fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and these ring groups are Any of the hydrogen atoms may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Atom substitution, n is an integer from 0 to 4, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 Fluorinated alkoxy group, Y ⁷ is -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, Y ⁸ is an alkyl group having 8 to 22 carbon atoms, Y ⁹ And Y ^{10 is} independently a hydrocarbon group having 1 to 12 carbon atoms, and Y ¹¹ is an alkyl group having 1 to 5 carbon atoms).

The liquid crystal alignment treatment agent according to any one of the above-mentioned, wherein the tetracarboxylic acid component of the polymer of the component (C) contains a compound represented by the following formula [4]. (Z ¹ is a base of the structure selected by the following formula [4a] to formula [4j]) (Z ² to Z ⁵ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and Z ⁶ and Z ⁷ may each be a hydrogen atom or a methyl group, and each may be the same or different).

11. The liquid crystal alignment according to any one of claims 1 to 10. The treatment agent, wherein the polymer of the component (C) is a polyimine obtained by dehydrating a polyamic acid ring.

The liquid crystal alignment treatment agent according to any one of claims 1 to 11, wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C).

The liquid crystal alignment treatment agent according to any one of claims 1 to 12, wherein the component (B) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C).

A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13.

A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13 and using an inkjet method.

A liquid crystal display element comprising the liquid crystal alignment film of claim 14 or 15.

17. The liquid crystal alignment film according to claim 14 or 15, which is useful in

A liquid crystal layer is provided between a pair of substrates having electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes. A liquid crystal display element produced by polymerizing the above polymerizable compound.

[14] A liquid crystal display device comprising the liquid crystal alignment film of claim 17.

19. The liquid crystal alignment film according to claim 14 or claim 15, which is usable in

A liquid crystal layer is provided between a pair of substrates having electrodes, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes. A liquid crystal display element produced by polymerizing the above polymerizable group.

A liquid crystal display element comprising the liquid crystal alignment film of claim 19.

According to the present invention, a liquid crystal alignment treatment agent containing at least one polymer selected from the group consisting of a compound having a specific structure and a polyimine precursor and a polyimide composition can form a sealant and a liquid crystal alignment film. The adhesion is improved, and even in a high-temperature and high-humidity condition, occurrence of display unevenness in the vicinity of the front edge of the liquid crystal display element is suppressed, and a liquid crystal alignment film having a lowered voltage holding ratio can be suppressed. In other words, 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 preferably used for a large-screen, high-definition liquid crystal television or the like.

[Best Mode for Carrying Out the Invention]

The invention will be described in detail below.

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

Component (A): a compound represented by the following formula [1] (also referred to as a specific isocyanate compound).

Component (B): a compound represented by the following formula [2] (also referred to as a specific amine compound).

(C) component: at least one polymer (also referred to as a specific polymer) selected from the group consisting of a polyimine precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimine.

(X ¹ is a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms; or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is represented by the following formula [ 1-1]~ The structure selected by [1-6]).

(A ¹ is a hydrogen atom or a benzene ring, A ² is a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and A ³ is an alkane having 1 to 18 carbon atoms. The group is a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

(W ¹ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. W ² is a single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, - N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO _{2 -.} W ³ is a single bond, a benzene ring or Cyclohexane ring. W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO -, -CONH-, -CON(CH ₃ )-, -S- or -SO _{2 -.} W ⁵ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and n is 1 to 5 Integer).

In the liquid crystal alignment treatment agent of the present invention, it is considered that a primary amine group in a specific amine compound forms a salt with a carboxyl group in a specific polymer, or a carboxyl group or a carboxyl group in a specific polymer is accompanied by water or an alcohol. The cleavage of the guanamine bond, or the ring-opening bond reaction with the oxime imine group in the specific polymer. That is, it is considered that a specific amine compound is salt-formed or chemically bonded to a specific polymer through a 1-stage amine group to a specific polymer.

Further, it is considered that the OCN group (also referred to as an isocyanate group) of the specific isocyanate compound contained in the liquid crystal alignment treatment agent is specific to the polymer, and The terminal OH group (also known as a hydroxyl group) of a specific amine compound subjected to salt formation or chemical bonding is chemically bonded. That is, it is considered that the preparation of the liquid crystal alignment treatment agent is not limited to a simple method of mixing in an organic solvent, and the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent transmits a specific amine compound, and the specific isocyanate compound and the specific polymer are excellently bonded. Knot.

Further, it is known that the double bond portion of the formula [1- 1] to the formula [1-6] of X ² in the specific isocyanate compound is reacted by irradiation with heat or ultraviolet rays. Further, these double bond sites are also included in the compound contained in the sealant.

Therefore, when the liquid crystal alignment treatment agent of the present invention is used, the double bond portion in the liquid crystal alignment film and the sealant are used in the curing step of the sealant when the liquid crystal display element is produced, that is, the ultraviolet irradiation step or the baking step. The compound undergoes a chemical reaction, and the sealant is chemically bonded to the liquid crystal alignment film to improve the adhesion.

As described above, the liquid crystal alignment treatment agent containing the specific isocyanate compound, the specific amine compound, and the specific polymer of the present invention has high adhesion to the sealant, and can form a front edge capable of suppressing the liquid crystal display element even under high temperature and high humidity conditions. The display unevenness in the vicinity is generated, and the liquid crystal alignment film having a lowered voltage holding ratio can be suppressed.

<Specific isocyanate compound>

The specific isocyanate compound of the present invention is a compound represented by the following formula [1].

(X ¹ and X ² are synonymous with the above definition).

(A ¹ , A ² and A ³ are synonymous with the above definition).

In the formula [1], X ¹ is a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring. Among them, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 5 carbon atoms is more preferred.

In the formula [1], X ² is a structure selected from the formula [1-1] to the formula [1-6].

In the formula [1-3], A ¹ is a hydrogen atom or a benzene ring. Among them, a hydrogen atom is preferred.

In the formula [1-6], A ² is a monovalent or bivalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. Among them, a single bond, a benzene ring, a cyclohexane ring or a biphenyl ring is preferred.

In the formula [1-6], A ³ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms is preferred.

In the formula [1], X ² is preferably a structure represented by the formula [1-1], the formula [1-2], the formula [1-4] or the formula [1-6].

More specifically, the structure is represented by the following formula [1a] to formula [1e].

(X ³ is an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring, and X ⁴ is an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring).

(X ⁵ is an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring, X ⁶ is an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring, and X ⁷ is a carbon number of 1~ An alkyl group, a benzene ring or a cyclohexane ring of 5, X ⁸ is a single bond, a benzene ring, a cyclohexane ring or a biphenyl ring, and X ⁹ is an alkyl group having 1 to 9 carbon atoms or a carbon number of 1 to 9 Alkoxy).

The specific isocyanate compound may be used in combination of one type or two types or more in combination with characteristics such as liquid crystal alignment property, voltage maintenance ratio, and charge accumulation when the liquid crystal alignment film is formed.

<specific amine compound>

The specific amine compound of the present invention is a compound represented by the following formula [2].

In the formula [2], W ¹ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group in order to form a salt or a bonding reaction with a specific polymer in a specific amine compound.

Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, a branched alkyl group, or a hydrocarbon group having an unsaturated bond. Among them, a linear or branched alkyl group having a carbon number of 1 to 20 is preferred. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 15, and preferably a linear or branched alkyl group having a carbon number of 1 to 10.

Specific examples of the non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, and a ring oxime. Alkane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Cyclodecane ring, cyclohexadecane Ring, tricyclohexadecane ring, tricyclotetracosane ring, bicyclohexyl ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. Among them, a ring composed of 3 to 20 carbon atoms is preferred. More preferably, it is a ring composed of 3 to 15 carbon atoms, and more preferably a ring composed of 6 to 12 carbon atoms and a non-aromatic cyclic hydrocarbon group. Specifically, it is a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a cyclohexane ring.

In the formula [2], W ² is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ ) CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO- is preferred. More preferably, it is a single bond, -O-, -NH-, -OCO- or -NHCO-, and particularly preferably a single bond, -O- or -OCO-.

In the formula [2], W ³ is a single bond, a benzene ring or a cyclohexane ring. More preferably a single bond or a benzene ring.

In the formula [2], W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ ) CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO- is preferred. More preferably, it is a single bond, -O-, -NH-, -OCO- or -CONH-, and particularly preferably a single bond, -O-, -NH- or -CONH-.

In the formula [2], W ⁵ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group and the non-aromatic cyclic hydrocarbon group include the above. Among them, a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms is preferred. More preferably, it is a single bond, a linear or branched alkyl group having 1 to 15 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 15 carbon atoms. Further preferably, it is a single bond, a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a single bond or a linear or branched carbon number of 1 to 10. An alkyl or cyclohexane ring is formed.

In the formula [2], n is an integer of 1 to 5. Among them, an integer from 1 to 4 is preferred. More preferably, it is an integer of 1 to 3.

Preferred combinations of W ¹ , W ² , W ³ , W ⁴ , W ⁵ and n in the formula [2] are shown in Tables 1 to 14.

When the above specific amine compound is formed into a liquid crystal alignment film The characteristics of the liquid crystal alignment property, the voltage maintenance ratio, and the storage charge can be used in combination of one type or two types or more.

<specific polymer>

The specific polymer of the component (C) of the present invention is at least one polymer selected from the group consisting of a polyimine precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimine.

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

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each of which may be the same or different, and A ³ and A ⁴ are A hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethyl fluorenyl group may each be the same or different, and n is a positive integer).

In terms of the aforementioned diamine component, there are two grades 1 in the molecule. Or a dibasic amine diamine compound, and a tetracarboxylic acid component, for example, 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.

The specific polymer is represented by the following formula [D] by using the tetracarboxylic dianhydride represented by the following formula [B] and the diamine compound represented by the following formula [C] as a raw material, which can be easily obtained. It is preferred that the polyamine of the structural formula of the repeating unit or the polyimine which is imidized with the polyphosphonium amide.

(In the formula [B] and the formula [C], R ¹ and R ² are synonymous with the definition of the formula [A]).

(R ¹ and R ² are synonymous with the formula [A]).

Further, in the above-mentioned polymer of the formula [D], the alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and the formula [A] can be introduced by a usual synthesis method. The alkyl group or the ethylidene group having 1 to 5 carbon atoms of A ³ and A ⁴ represented.

<Diamine component>

A conventional diamine compound can be used for the production of the diamine component for the specific polymer of the component (C).

Among them, a diamine compound (also referred to as a specific diamine compound) having at least one of the structures represented by the following formula [3] is preferably used.

(Y is a substituent selected by the following formula [3-1] to formula [3-6], and m is an integer of 1 to 4).

In the formula [3-1], a is an integer of 0 to 4. Among them, the raw material acquisition or the ease of synthesis is preferably 0 or 1.

In the formula [3-2], b is an integer of 0 to 4. Among them, the raw material acquisition or the ease of synthesis is preferably an integer of 0 or 1.

In the formula [3-3], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred from the viewpoint of availability of raw materials or ease of synthesis. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [3-3], Y ² is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

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

In the formula [3-3], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the cyclic group may be a carbon number of 1 to 3. The alkyl group, the alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Further, Y ⁴ may be a divalent organic group selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. Among them, from the point of synthesis difficulty, an organic group having a benzene ring, a cyclohexane ring or a carbon number of 12 to 25 having a steroid skeleton is preferred.

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

In the formula [3-3], n is an integer of 0 to 4. Among them, the raw material acquisition or the ease of synthesis is preferably 0 to 3. More preferably 0~2.

In the formula [3-3], Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [3-3], for example, is disclosed in International Publication No. WO2011/132751 (2011.10.27). The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of the page on page 34. Further, each of Y1 to Y6 in each table of the international publication corresponds to Y ¹ to Y ^{6 of the} present invention.

In the formula [3-4], Y ⁷ is -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Among them, -O-, -CH ₂ O-, -COO- or -CONH- is preferred. More preferably -O-, -COO- or -CONH-.

In the formula [3-4], Y ⁸ is an alkyl group having 8 to 22 carbon atoms.

In the formula [3-5], Y ⁹ and Y ¹⁰ are each independently a hydrocarbon group having 1 to 12 carbon atoms.

In the formula [3-6], Y ¹¹ is an alkyl group having 1 to 5 carbon atoms.

The method for producing the specific diamine compound represented by the formula [3] is not particularly limited, and a preferred method is, for example, the following.

In one aspect, the specific diamine compound represented by the formula [3] can be obtained by synthesizing a dinitro compound represented by the following formula [3-A], and then converting the nitro group into an amine group.

(Y is a substituent selected by the above formula [3-1] to formula [3-6], and m is an integer of 1 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [3-A] is not particularly limited, and it is usually in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method of reacting under hydrogen gas, helium or hydrogen chloride using a catalyst such as palladium-carbon, oxidized platinum, Raney nickel, platinum black, lanthanum-alumina or sulfurized platinum carbon.

The specific structure of the specific diamine compound represented by the following formula [3] is not limited to these examples.

In terms of specific diamine compounds, in addition to 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diamino benzoin Acid, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamine Examples of the benzenediol include a diamine compound having a structure represented by the following formula [3-7] to formula [3-47].

(A ¹ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(R ¹ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group Or a fluorine-containing alkoxy group).

(R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, and R ⁴ is an alkyl group having 1 to 22 carbon atoms , alkoxy, fluoroalkyl or fluoroalkoxy).

(R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ⁶ is a fluorine group, cyanide Base, trifluoromethyl, nitro, azo, formyl, ethyl, ethoxy or hydroxy).

(R ⁷ is an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomer of the 1,4-cyclohexyl group is preferably a trans isomer).

(R ⁸ is an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomer of the 1,4-cyclohexyl group is preferably a trans isomer).

(B ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ is a 1,4-cyclohexyl group or a 1,4-phenylene group, and B ² is an oxygen atom or -COO-* (however, Note "*" is bonded to bond to B ³ are bonded), B ¹ is an oxygen atom or -COO -. * (However, note on "*" is bonded to bond with (CH ^₂₎ a ₂ bonded) and, a ¹ is an integer of 0 or 1, a ² is an integer of 2 to 10, and a ³ is an integer of 0 or 1.

Used in the specific diamine compound represented by the above formula [3] When the liquid crystal alignment treatment agent obtained by using the specific polymer of the diamine compound of the formula represented by the formula [3-3] in the formula [3] to form a liquid crystal alignment film, the pretilt angle of the liquid crystal can be obtained. improve. In order to increase the pretilt angle, it is preferred to use the diamine compound represented by the formula [3-29] to the formula [3-40] or the formula [3-43] to the formula [3-47] in the above diamine compound. More preferably, it is a diamine compound represented by the formula [3-25] to the formula [3-40] or the formula [3-43] to the formula [3-47].

The amount of the diamine compound used to increase the pretilt angle is preferably 5 mol% or more and 80 mol% or less of the entire diamine component. The coating property of the liquid crystal alignment treatment agent or the electrical property of the liquid crystal alignment film is more preferably 5 mol% or more and 60 mol% of the entire diamine component.

a specific diamine compound represented by the formula [3], in response to a specific poly The solubility in the solvent, the coating property, the alignment property of the liquid crystal in the case of the liquid crystal alignment film, the voltage maintenance ratio, and the charge accumulation may be used in combination of one type or two types or more.

In the case of producing a diamine component for a specific polymer, a diamine compound (also referred to as another diamine compound) other than the specific diamine compound represented by the formula [3] can be used as the diamine component. Specific examples of other diamine compounds are listed below, but are not limited thereto.

M-phenylene diamine, 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'-diaminobiphenyl , 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane , 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl Diphenylamine, 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'-diaminodiphenyl Amine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-A (3,3'-Diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4'-diaminobenzophenone, 1,4-diamine, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5 -diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-Diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminobenzene) Propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminobenzene) Methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene , 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4 '-[1,4-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-stretch Phenyl bis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylene bis[(4-aminobenzene) Methyl ketone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1, 3-phenylphenylbis[(3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), 1,4-phenylphenylbis(3-amine) Benzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-amine Phenylphenyl) terephthalate, bis(3-aminophenyl)terephthalic acid , bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis (4) -aminobenzamide, N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene) double (3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl) Benzylguanamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxyl) Diphenyl hydrazine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminobenzene) 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-bis(3-aminophenoxy)butane, 1, 5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1 ,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1 , 8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)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-diamine Propane, 1,4-diaminobutane, 1,5- Aminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-di Aminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

Further, as another diamine compound, for example, a diamine side chain can be mentioned. Any of those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring, and further, a large cyclic substituent having such a group. Specifically, for example, a diamine compound represented by the following formulas [DA1] to [DA7] can be mentioned.

(A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ² is a linear chain having a carbon number of 1 to 22 or A branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(p is an integer from 1 to 10).

The diamine compound represented by the following formula [DA8] to formula [DA13] can also be used as the other diamine compound without impairing the effects of the present invention.

(m is an integer from 0 to 3, and n is an integer from 1 to 5).

Further, without impairing the effects of the present invention, it is also possible to The diamine compound represented by the following formula [DA14] to formula [DA17] is used.

(A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N ( CH ₃ )CO-, m ¹ and m ² are each an integer of 0 to 4, and m ¹ + m ² is an integer of 1 to 4, m ³ and m ⁴ are each an integer of 1 to 5, and A ² is a carbon number. a linear or branched alkyl group of 1 to 5, m ⁵ is an integer of 1 to 5, and A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m ⁶ is an integer from 1 to 4).

Further, as other diamine compounds, it is also possible to use The diamine compound represented by the formula [DA18] and the formula [DA19].

Further, without impairing the effects of the present invention, it is also possible to The diamine compound represented by the following formula [DA20] is used.

(A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )-, and -N(CH ₃ ) A divalent organic group selected by a group consisting of CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is a single bond, - O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and -O (CH ₂ ) _m - (m is an integer of 1 to 5) The divalent group selected by the group, A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).

The other diamine compound may be one type or two depending on the solubility of the specific polymer in the solvent, the coating property of the liquid crystal alignment agent, the alignment property of the liquid crystal in the case of the liquid crystal alignment film, the voltage retention ratio, and the charge accumulation. Mix and use more than one type.

<tetracarboxylic acid component>

In the tetracarboxylic acid component for producing a specific polymer of the component (C) of the present invention, a tetracarboxylic acid dianhydride represented by the following formula [4] or a tetracarboxylic acid or tetracarboxylic acid derivative thereof is used. The acid dihalide compound, the dicarboxylic acid dialkyl ester compound or the dicarboxylic acid dialkyl ester dihalide compound (all also collectively referred to as a specific tetracarboxylic acid component) is preferred.

In the formula [4], Z ¹ is a group of the structure selected by the following formula [4a] to formula [4j].

In the formula [4a], Z ² to Z ⁵ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [4g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [4] of the specific tetracarboxylic acid component, Z ^{1 is} represented by the formula [4a], the formula [4c], and the formula of the ease of synthesis or the degree of polymerization reactivity when the polymer is produced. The structure represented by [4d], formula [4e], formula [4f] or formula [4g] is preferred. More preferably, the structure represented by the formula [4a], the formula [4e], the formula [4f] or the formula [4g] is preferably a formula [4e], a formula [4f] or a formula [4g].

The specific tetracarboxylic acid component is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and more preferably 10 mol% or more. Among them, 15 to 100 mol% is better.

Further, when a specific tetracarboxylic acid component having a structure of the formula [4e], the formula [4f] or the formula [4g] is used, the amount thereof is preferably 20 mol% or more of the entire tetracarboxylic acid component. More preferably 30% by mole or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid having a structure of the formula [4e], the formula [4f] or the formula [4g]. Minute.

In the specific polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used without impairing the effects of the present invention.

Examples of the other 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 shown below. Dihalide compound.

That is, in terms of other tetracarboxylic acid components, for example, Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 - 蒽tetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid Acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic 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-dual (3,4 -Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridine four Carboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-nonanedicarboxylic acid Or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

Specific tetracarboxylic acid component and other tetracarboxylic acid component, depending on the solubility of a specific polymer in a solvent, the coating property of a liquid crystal alignment treatment agent, the alignment property of a liquid crystal as a liquid crystal alignment film, a voltage retention ratio, an accumulated charge, etc. The characteristics can be used in combination of 1 type or 2 types or more.

<Method of Manufacturing Specific Polymer>

The method of synthesizing a specific polymer is not particularly limited. Usually to make the diamine It is obtained by reacting with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component composed of one or more kinds of diamine compounds to obtain a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine compound of a 1st or 2nd stage to obtain a polyamic acid, and dehydrating polycondensation of a tetracarboxylic acid with a 1 or 2 grade diamine compound can be used. A method of obtaining a poly-proline by a reaction or a method of obtaining a poly-proline by polycondensing a tetracarboxylic acid dihalide with a first- or second-order diamine compound.

In order to obtain a polyalkyl phthalate, a carboxylic acid group can be used. A method of polycondensing a dialkyl esterified tetracarboxylic acid with a first or second stage diamine compound, a dicarboxylic acid dialkyl esterified tetracarboxylic acid dihalide, and a first or second order diamine A method in which a compound is subjected to polycondensation or a method in which a carboxyl group of polyproline is converted into an ester.

In order to obtain a polyimine, a method of ring-closing the polyamic acid or polyalkyl amide to form a polyimine can be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent containing a diamine component and a tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it is a polyimide precursor which is produced by dissolution. Specific examples of the organic solvent used in the following reaction are exemplified, but are not limited thereto.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, 1,3-dimethyl-imidazolidinone or the like. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, or a ring can be used. Pentanone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the following formula [D-1] to formula [D-3].

(D ¹ is an alkyl group having 1 to 3 carbon atoms, D ² is an alkyl group having 1 to 3 carbon atoms, and D ³ is an alkyl group having 1 to 4 carbon atoms).

These can be used alone or in combination. Further, even if the organic solvent which does not dissolve the polyimine precursor is in a range in which the produced polyimide intermediate precursor does not precipitate, it can be used in combination with the above organic solvent. Further, since the water in the solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried by dehydration. .

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a method of stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and dispersing or dissolving the tetracarboxylic acid component directly or in an organic solvent, On the other hand, any method such as a method of adding a diamine component to a solution in which an tetracarboxylic acid component is dispersed in an organic solvent or dissolved, a method of mutually adding a diamine component and a tetracarboxylic acid component, or the like can be used. Further, when a plurality of kinds of the diamine component or the tetracarboxylic acid component are used for the reaction, the reaction may be carried out in advance, or the individual reaction may be carried out in sequence, or the mixed polymer of the individual reaction may be used as a polymer. At this time, the polymerization temperature can be selected from any temperature of -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Wai. Further, the reaction can be carried out at any concentration. However, if the concentration is too low, it becomes 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 and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization of polyimine precursors, the diamine component The ratio of the total number of moles to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the general polycondensation reaction, 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 ring-closing the polyimine precursor. In the polyimine, the ring closure ratio of the proline group (also referred to as the ruthenium imidation ratio) is not necessarily It must be 100% and can be adjusted arbitrarily depending on the purpose or purpose.

The method for imidating the polyimine precursor ruthenium may, for example, be a hydrazine imidization in which a solution of a polyimide precursor is directly heated or a catalyst in a solution of a polyimide precursor. Media imidization.

Thermally imidization of a polyimide precursor in solution The temperature in the case is preferably from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, so that the water produced by the hydrazine imidization reaction is discharged to the outside of the system.

The ruthenium imide of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. get on. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. As an alkaline catalyst, For example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine can be mentioned, and among them, pyridine is preferably moderately alkaline during the progress of the reaction. The acid anhydride may, for example, be anhydrous acetic acid, anhydrous trimellitic acid or anhydrous pyromellitic acid. Among them, anhydrous acetic acid is used, and purification after completion of the reaction is easy, which is preferable. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Returned from the reaction solution of polyimine precursor or polyimine In the case of the produced polyimine precursor or polyimine, the reaction solution may be introduced into a solvent and then precipitated. The solvent used for the precipitation may, for example, be methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, pentane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After the solvent is added and the precipitated polymer is filtered and recovered, it can be dried under normal pressure or reduced pressure at normal temperature or under heating. Further, the polymer recovered by the precipitation is repeatedly dissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. The solvent in this case may, for example, be an alcohol, a ketone or a hydrocarbon. It is preferred to use three or more solvents selected in the above, and the efficiency of the purification is further improved.

The molecular weight of the above specific polymer is considered from In the case of the strength of the liquid crystal alignment film, the workability at the time of formation of the liquid crystal alignment film, and the film coating property, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and contains a specific isocyanate compound, a specific amine compound, a specific polymer, and a solvent.

The content of the specific isocyanate compound in the liquid crystal alignment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, 0.5 to 30 parts by mass is preferred, and particularly preferably 1 to 20 parts by mass.

The amount of introduction of the specific amine compound in the liquid crystal alignment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, 0.5 to 30 parts by mass is preferred, and particularly preferably 1 to 20 parts by mass.

Adding a specific isocyanate compound to a liquid crystal alignment agent The method of the specific amine compound is not particularly limited. Preferably, for example, the following method is used. That is, a specific amine compound is added to a polymer solution in which a specific polymer is dissolved in a solvent, and a solution of the specific polymer and a specific amine compound is heated and stirred. The temperature at this time is preferably 25 to 100 ° C, more preferably 25 to 80 ° C. Thereafter, a specific isocyanate compound is added to the solution, and a solution of a specific polymer, a specific amine compound, and a specific isocyanate compound is heated and stirred. The temperature at this time is preferably 25 to 100 ° C, more preferably 25 to 80 ° C. The solution thus obtained can be directly used for the liquid crystal alignment treatment agent, and further, other polymers, solvents, additives and the like shown below can be added.

All the polymer components in the liquid crystal alignment agent may be all of the specific polymers of the present invention, or may be mixed with other polymers. In this case, the content of the other polymer other than the polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polymer. Other than The other polymer may, for example, be a polyimine-based polymer in which the diamine compound represented by the above formula [3] and a specific tetracarboxylic acid component are not used. Further, specific examples of the polymer other than the polymer include a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine, polyoxyalkylene, and the like.

The solvent in the liquid crystal alignment treatment agent is formed by coating From the viewpoint of the uniform liquid crystal alignment film, the content of the solvent in the liquid crystal alignment treatment agent is preferably from 70 to 99.9% by mass, more preferably from 80 to 99% by mass. The content may be appropriately changed depending on the film thickness of the intended liquid crystal alignment film.

The solvent used for the liquid crystal alignment treatment agent is a solvent (also referred to as a good solvent) for dissolving a specific compound and a specific polymer, and is not particularly limited. Specific examples of the good solvent are exemplified below, but are not limited thereto.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ-butyl Lactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among them, to use N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone or γ-butyrolactone is preferred. Further, when the solubility of the specific compound and the specific polymer in the solvent is high, it is preferred to use the solvent represented by the above formula [D-1] to formula [D-3].

The good solvent in the liquid crystal alignment agent is preferably from 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 20 to 90% by mass is preferred. More preferably 30 to 80% by mass.

Liquid crystal alignment treatment agent without damaging the effects of the present invention A solvent (also referred to as a poor solvent) which improves the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. Specific examples of the poor solvent are exemplified below, but are not limited thereto.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propane Glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate 1-methylpentyl acetate 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxy Oxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto 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, tripropylene glycol monomethyl ether Ethylene glycol mono Ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl Ethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, three Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether , pyruvic acid methyl ester, ethyl pyruvate, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate A base ester, n-butyl lactate, isoamyl lactate, a solvent represented by the above formula [D-1] to formula [D-3], and the like.

Among them, 1-hexanol, cyclohexanol, 1,2-ethane two are used. The alcohol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or the solvent represented by the above formula [D-1] to formula [D-3] is preferred.

The amount of the poor solvent is preferably from 1 to 70% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 1 to 60% by mass is preferred. More preferably, it is 5 to 60% by mass.

The liquid crystal alignment treatment agent does not impair the effects of the present invention Further, at least one substitution selected from the group consisting of a hydroxyl group, an isocyanate group, an oxetanyl group or a cyclic carbonate group, and a group having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group may be introduced. A compound of a group, and further a compound having a polymerizable unsaturated bond (collectively referred to as a crosslinkable compound). These substituents or polymerizable unsaturated bonds need to have in the crosslinkable compound 2 or more.

In terms of a crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four Glycidylamino diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether Alkane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetam diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl -2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetrahydration Glyceryl-m-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxy)) Propyloxy)phenyl)ethyl)phenyl)propane, 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.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl 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 International Publication WO2011/132751 (2011.10.27).

In terms of a crosslinkable compound having a cyclic carbonate group, There are few crosslinkable compounds having 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) is mentioned.

At least 1 selected from the group consisting of a hydroxyl group and an alkoxy group Examples of the crosslinkable compound of the substituent, such as an amine-based resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, a guanamine resin, a glycoluril-formaldehyde resin, amber decyl amide-formaldehyde resin or ethylene Urea-formaldehyde resin, etc. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. The melamine derivative or the benzoguanamine derivative may also be present as a 2-mer or a 3-mer. It is preferred that each of the triazine rings has an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group.

Such a melamine derivative or a benzoguanamine derivative In one embodiment, for example, one triazine ring per commercially available product, methoxymethyl group is an average of 3.7 substituted MX-750, and each triazine ring, and methoxymethyl group is an average of 5.8 substitutions. Methoxymethylated melamine, Cymel 235, 236, such as MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butoxymethylated melamine of 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., carboxymethylated methylation of Cymel 1141 Isobutoxymethylated melamine, Cymel 1123-like methoxymethylated ethoxymethylated benzoguanamine, Cymel 1123-10-like methoxymethylated butoxymethylated benzo Indoleamine, Cymel 1128-like butoxymethylated benzoguanamine, Cymel 1125-80, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine (above, manufactured by Mitsui Cyanamid Co., Ltd.) . Further, examples of the glycoluril include, for example, a butoxymethylated glycoluril of Cymel 1170, a methylolated glycoluril such as Cymel 1172, and a methoxymethylolated glycoluril such as Powderlink 1174.

In the case of benzene having a hydroxyl group or an alkoxy group, or a phenolic compound, For example, 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1,4-bis(sec-butoxymethyl)benzene, 2,6-Dihydroxymethyl-p-tert-butylphenol and the like.

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 WO2011/132751. (2011.10.27).

Crosslinkable compound having a polymerizable unsaturated bond Surface, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(meth)acryloyloxyethoxy trishydroxyl a crosslinkable compound having three polymerizable unsaturated groups in a molecule such as methyl propane or glycerol polyglycidyl ether poly(meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol II (methyl) Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol II (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 di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, two Molecules such as ethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate a crosslinkable compound having two polymerizable unsaturated groups; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene decyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropane Base (meth)acrylic acid A monounsaturated unsaturated group such as glycerol mono(meth)acrylate, 2-(meth)acryloyloxyethyl phosphate or N-hydroxymethyl(meth)acrylamide. Crosslinkable compounds; and the like.

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

(E ₁ is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring, and E ₂ is as follows The group selected by the formula [7a] and the formula [7b], n is an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, and is not limited thereto. Moreover, the crosslinkable compound used for the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

The content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. In order to carry out the crosslinking reaction and to express the intended effect, it is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the total polymer component.

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

Examples of the compound which improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant, an anthrone-based surfactant, and a nonionic surfactant.

More specifically, for example, EFTOP EF301, EF303, EF352 (above, Thochem Products), MEGAFACE F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M) , Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment treatment agent, as a liquid crystal promotion The compound which shifts the charge in the alignment film and promotes the charge extraction of the element may be represented by the formula [M1]~[M156] disclosed in pages 69-73 of International Publication WO2011/132751 (2011.10.27 publication). A nitrogen-containing heterocyclic amine compound. The amine compound may be directly added to the liquid crystal alignment treatment agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, with a suitable solvent. The solvent to be used is not particularly limited as to dissolve the organic solvent of the above specific polymer.

In the liquid crystal alignment treatment agent, the poor solvent, the crosslinkable compound, the compound which improves the film thickness uniformity or surface smoothness of the resin film or the liquid crystal alignment film, and the compound which promotes charge extraction are not damaged. In the range of the effects of the invention, a dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added.

<Liquid alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied to a substrate and baked, and then subjected to an alignment treatment by rubbing treatment or light irradiation. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate to be used at this time is not particularly limited as long as the substrate having high transparency, and an acrylic group may be used in addition to the glass substrate. Plastic substrates such as plates and polycarbonate substrates. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate, and a material such as aluminum or the like can be used as the electrode in this case.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrial screen printing, offset printing, flexographic printing, and inkjet printing are common. Other coating methods include a dipping method, a roll coating method, a slit coating method, a rotator method, a spray method, and the like, and these may be used depending on the purpose.

After the liquid crystal alignment agent is applied onto the substrate, it can be heated at 30 to 300 ° C by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven, in accordance with the solvent used for the liquid crystal alignment agent. The temperature is 30 to 250 ° C to evaporate the solvent to produce a liquid crystal alignment film.

When the thickness of the liquid crystal alignment film after firing is too large, it becomes unfavorable on the power-consuming surface of the liquid crystal display element. When the thickness is too thin, the reliability of the device is lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 ~100nm. When the liquid crystal is aligned horizontally or obliquely, the liquid crystal alignment film after firing is treated by rubbing, polarized ultraviolet irradiation or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above method, and a liquid crystal cell is produced by a known method to form a liquid crystal display element.

In the method of fabricating a liquid crystal cell, for example, a pair of substrates of a liquid crystal alignment film are prepared, a spacer is spread on a liquid crystal alignment film of one substrate, and another substrate is bonded so that a liquid crystal alignment film surface is inside. A method of sealing after pressure-reducing injection, or a method of sealing a substrate after laminating a liquid crystal on a liquid crystal alignment film surface of a spacer, and sealing the substrate.

Further, the liquid crystal alignment treatment agent of the present invention is also preferably used A liquid crystal layer having a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between a pair of substrates, and a voltage is applied between the electrodes. A liquid crystal display element produced by polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray. Here, in terms of the active energy ray, ultraviolet rays are preferred. In terms of ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heating can be simultaneously performed.

The above liquid crystal display element is PSA (Polymer) Sustained Alignment), which controls the pretilt angle of liquid crystal molecules. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in the liquid crystal material, and after the liquid crystal cell is assembled, the photopolymerizable compound is irradiated with ultraviolet rays or the like by applying a predetermined voltage state to the liquid crystal layer. The pretilt angle of the liquid crystal molecules is controlled by the resulting polymer. That is, the alignment state of the liquid crystal molecules when the polymer is formed is memorized even after the voltage is removed, so that the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed by the liquid crystal layer or the like.

Also, in the PSA mode, it is suitable for It is difficult to control the formation of the vertical alignment type liquid crystal layer of the pretilt angle by the rubbing treatment.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent by the above-described method, and a liquid crystal cell is produced, and at least one of ultraviolet irradiation and heating is used to polymerize the polymerizable compound to control the liquid crystal. The alignment of molecules.

For example, in the case of the liquid crystal cell production of the PSA system, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on the liquid crystal alignment film of one substrate, and the other film is bonded so that the liquid crystal alignment film surface is inside. The substrate is a method in which the liquid crystal is pressure-injected and then sealed, or a method in which the liquid crystal is dropped on the liquid crystal alignment film surface of the spacer, and the substrate is bonded and sealed.

Liquid crystal mixed with polymerizability due to heat or ultraviolet irradiation Compound. The polymerizable compound may, for example, be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment of the liquid crystal is not controlled. When the amount is more than 10 parts by mass, the unreacted polymerizable compound increases and the image sticking property of the liquid crystal display element decreases.

After the liquid crystal cell is produced, the polymerizable compound is polymerized by applying heat or ultraviolet light to the liquid crystal cell by applying an alternating current or a direct current voltage. Thereby, the alignment of the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment treatment agent of the present invention is also preferably used in a liquid crystal layer is formed between a pair of substrates having electrodes, and a polymer aggregated by at least one of an active energy ray and heat is disposed between the pair of substrates A liquid crystal alignment element produced by a step of applying a voltage between electrodes. Here, in terms of the active energy ray, ultraviolet rays are preferred. In terms of ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of heating polymerization, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heating can be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent or using a polymerizable property A method based on a polymer component. The liquid crystal alignment agent of the present invention contains a specific compound having a double bond site which is reacted by irradiation with heat or ultraviolet rays, and at least one of irradiation and heating of the ultraviolet rays can control the alignment of the liquid crystal molecules.

The preparation of the liquid crystal cell having the liquid crystal alignment film containing the polymerizable group and the control of the alignment of the liquid crystal molecules after the production of the liquid crystal cell can be carried out in the same manner as the liquid crystal cell of the PSA method.

A liquid crystal display element having a liquid crystal alignment film produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is preferably used in a large-screen and high-definition liquid crystal television.

[Examples]

The present invention will be described in more detail in the following examples, but is not limited thereto. The abbreviations in the synthesis examples, examples and comparative examples are as follows.

<Specific isocyanate compound>

P1: a compound represented by the following formula [P1]

P2: a compound represented by the following formula [P2]

P3: a compound represented by the following formula [P3]

<specific amine compound>

S1: Aminoethanol

S2: 3-amino-1-propanol

<Monomer for producing a polyimide-based polymer (specific polymer)> (specific diamine compound)

A1: 3,5-diamino benzoic acid

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

A3: 1,3-diamino-4-octadecyloxybenzene

A4: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy Benzobenzene

A5: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

A6: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A7: a diamine compound represented by the following formula [A7]

(other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylene diamine

(specific tetracarboxylic acid component)

C1:1,2,3,4-cyclobutanetetracarboxylic dianhydride

C2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride C3: tetracarboxylic dianhydride represented by the following formula [C3]

C4: tetracarboxylic dianhydride represented by the following formula [C4]

<solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

ECS: ethylene glycol monoethyl ether

EC: diethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

"Method for Measuring Molecular Weight of Polyimide Ion Polymers"

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

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (lithium bromide-hydrate (LiBr.H ₂ O) as an additive 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 sample for the production of calibration lines: TSK standard polyethylene oxide (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).

"Method for Measuring the Amidoximation Rate of Polyimine

20 mg of polyimine powder was placed in an NMR (Nuclear Magnetic Resonance) sample tube (NMR sampling tube stand, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and dimethyl-hydrazine (DMSO-d6, 0.05% by mass TMS (DMSO-d6) was added. Tetramethyl decane) Mixture) (0.53ml), apply ultrasonic waves to completely dissolve. This solution was measured for 500 MHz proton NMR by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Co., Ltd.). The sulfhydrylation rate is determined by using protons from a structure that has no change before and after imidization as a reference proton, and the peak value of the proton is used and the proton peak of the NH group from the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value is obtained by the following equation.

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

(x is the proton peak cumulative value of the NH group derived from proline, y is the peak cumulative value of the reference proton, and α is the relative amine of the proline in the case where the poly-proline (the imineization rate is 0%) The ratio of the number of reference protons of one matrix.

<Synthesis Example 1>

C1 (3.28 g, 16.7 mmol), A2 (0.69 g, 3.41 mmol) and B1 (1.46 g, 13.5 mmol) were mixed in NMP (16.3 g), and reacted at 40 ° C for 8 hours to obtain a resin solid concentration. 25 mass% polylysine solution (1). The polyamic acid had a number average molecular weight of 26,800 and a weight average molecular weight of 87,100.

<Synthesis Example 2>

C2 (3.64 g, 14.5 mmol), A2 (0.88 g, 4.35 mmol) and B2 (2.67 g, 24.7 mmol) were mixed in NEP (19.9 g), 50 ° C, The reaction was carried out for 2 hours. Thereafter, C1 (2.76 g, 14.1 mmol) and NEP (10.0 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 23,900 and a weight average molecular weight of 70,900.

<Synthesis Example 3>

In the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, after adding NEP to 6% by mass, anhydrous acetic acid (3.93 g) and pyridine (2.45 g) as a ruthenium catalyst were added. The reaction was carried out at 70 ° C for 3 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (3). The polyimine had a quinone imidization ratio of 69%, a number average molecular weight of 22,500, and a weight average molecular weight of 60,800.

<Synthesis Example 4>

C2 (4.25 g, 17.0 mmol), A1 (1.85 g, 12.2 mmol) and A4 (4.61 g, 12.1 mmol) were mixed in NEP (24.1 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, C1 (1.36 g, 6.93 mmol) and NEP (12.1 g) were added, and the mixture was reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (4) having a resin solid concentration of 25% by mass. The polyamine had a number average molecular weight of 23,000 and a weight average molecular weight of 68,000.

<Synthesis Example 5>

In the polyamic acid solution (4) (30.0 g) obtained in Synthesis Example 4, After the NEP was diluted to 6 mass%, anhydrous acetic acid (3.80 g) and pyridine (2.40 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 70 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazide conversion ratio of 60%, a number average molecular weight of 20,100, and a weight average molecular weight of 58,100.

<Synthesis Example 6>

C2 (4.85 g, 19.4 mmol), A1 (1.84 g, 12.1 mmol), A2 (0.49 g, 2.43 mmol), and A5 (3.82 g, 9.68 mmol) were mixed in NMP (23.8 g) at 80 ° C 5 hours reaction. Thereafter, C1 (0.88 g, 4.51 mmol) and NMP (11.9 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), anhydrous acetic acid (4.50 g) and pyridine (3.35 g) as a ruthenium amide catalyst were added, and the mixture was subjected to 3.5 ° C at a temperature of 3.5 ° C. Hour response. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried at reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had an oxime imidization ratio of 84%, a number average molecular weight of 16,800, and a weight average molecular weight of 51,300.

<Synthesis Example 7>

C2 (2.30g, 9.19mmol), A1 (2.45g, 16.1mmol) and A6 (2.98g, 6.89mmol) were mixed in NEP (20.8g), 80 ° C, The reaction was carried out for 5 hours. Thereafter, C1 (2.65 g, 13.5 mmol) and NEP (10.4 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyamidic acid solution (30.0 g), anhydrous acetic acid (4.45 g) and pyridine (3.31 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 80 ° C. Hour response. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 16,800, and a weight average molecular weight of 50,900.

<Synthesis Example 8>

C2 (4.10 g, 16.4 mmol), A1 (2.85 g, 18.7 mmol) and A7 (2.31 g, 4.68 mmol) were mixed in NMP (21.1 g), and the reaction was carried out at 80 ° C for 5 hours. Thereafter, C1 (1.30 g, 6.64 mmol) and NMP (10.6 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyamic acid solution (30.0 g), anhydrous acetic acid (3.88 g) and pyridine (2.53 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 60 ° C. Hour response. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a ruthenium iodide ratio of 55%, a number average molecular weight of 17,300, and a weight average molecular weight of 52,100.

<Synthesis Example 9>

C3 (5.13 g, 22.9 mmol), A1 (2.31 g, 15.2 mmol), A2 (0.48 g, 2.34 mmol) and A7 (2.87 g, 5.82 mmol) were mixed in NMP (32.4 g), and carried out at 40 ° C After 8 hours of reaction, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g), and diluting it to 6% by mass, anhydrous acetic acid (4.00 g) and pyridine (2.55 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 60 ° C. Hour response. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a quinone imidization ratio of 55%, a number average molecular weight of 18,000, and a weight average molecular weight of 51,400.

<Synthesis Example 10>

C3 (5.11 g, 22.8 mmol), A1 (2.11 g, 13.9 mmol) and A5 (3.65 g, 9.25 mmol) were mixed in NMP (32.6 g), and reacted at 40 ° C for 8 hours to obtain a resin solid concentration. It is a 25% by mass polylysine solution.

NMP was added to the obtained polyamic acid solution (30.0 g), and after diluting to 6% by mass, anhydrous acetic acid (4.00 g) and pyridine (2.50 g) as a ruthenium amide catalyst were added, and the solution was carried out at 70 ° C. Hour response. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The gathering The imine has a ruthenium iodide ratio of 60%, a number average molecular weight of 17,500, and a weight average molecular weight of 52,000.

<Synthesis Example 11>

C4 (3.31 g, 11.0 mmol), A1 (1.01 g, 6.62 mmol), A2 (0.89 g, 4.39 mmol), and A3 (4.14 g, 11.0 mmol) were mixed in NEP (22.9 g) at 40 ° C 6 hours reaction. Thereafter, C1 (2.09 g, 10.7 mmol) and NEP (11.4 g) were added, and the mixture was reacted at 25 ° C for 8 hours to obtain a polyamic acid solution having a lipid solid content concentration of 25% by mass.

To the obtained polyaminic acid solution (30.5 g), NEP was added thereto, and after diluting to 6 mass%, anhydrous acetic acid (7.20 g) and pyridine (2.35 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 40 ° C. 1.5 hours reaction. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazide conversion ratio of 70%, a number average molecular weight of 18,900, and a weight average molecular weight of 45,300.

The polyimine polymer was prepared in Table 15.

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

The liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and evaluation of inkjet coating properties was performed. HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used for the inkjet coater. The coating was applied to an ITO (Indium Indium Oxide) vapor-deposited substrate washed with pure water and IPA (isopropyl alcohol) to have a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, and a scanning pitch of 0.5 mm. The coating speed was 40 mm/sec, the time until application to dryness was 60 seconds, and the temporary drying was carried out on a hot plate at 70 ° C for 5 minutes.

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

"Evaluation of display unevenness characteristics near the front edge of liquid crystal cell after high temperature and high humidity storage (normal cell)"

The liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell (normally a unit cell). The solution was spin-coated on an ITO surface of a 100×100 mm ITO electrode substrate (length 100 mm×width 100 mm, thickness 0.7 mm) washed with pure water and IPA, and heated on a hot plate at 100° C. for 5 minutes. The heat treatment was carried out in a heat cycle type clean oven at 230 ° C for 30 minutes to obtain an ITO substrate of an agglomerated iridium imine liquid crystal alignment film having a film thickness of 100 nm. The coating film surface of the ITO substrate was subjected to a rubbing treatment using a rayon cloth using a rayon cloth with a roller rotation number of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on the liquid crystal alignment film surface of the substrate to which the liquid crystal alignment film was attached. Thereafter, an ultraviolet curable sealant was drawn around the substrate, and liquid crystal was injected by an ODF (One Drop Filling) method to obtain a liquid crystal cell. Then, in order to cure the ultraviolet curable sealant, a liquid crystal cell having an illuminance of 60 mW was used for the liquid crystal cell, and a wavelength of 310 nm or less was blocked, and ultraviolet rays of 5 J/cm ² in terms of 365 nm were irradiated. Thereafter, in a heat cycle type clean oven, heat treatment was performed at 120 ° C for 60 minutes to obtain a liquid crystal cell (normal cell).

Moreover, the liquid crystal alignments obtained in Examples 1 to 3 were used. In the liquid crystal cell of the liquid crystal alignment treatment agents (21) to (26) obtained by the treatment agents (1) to (3) and Comparative Examples 1 to 6, a nematic liquid crystal (MLC-2003) was used (Merck. Japan) system).

Further, the liquid crystal alignment treatment agents (4) to (6) obtained in Examples 4 to 6, the liquid crystal alignment treatment agent (8) obtained in Example 8, and the liquid crystal alignment treatment agent obtained in Example 9 (9) were used. The liquid crystal alignment treatment agents (11) to (15) obtained in Examples 11 to 15 and the liquid crystal alignment treatment agents (17) to (20) obtained in Examples 17 to 20 and Comparative Examples 7 to 12 were obtained. The liquid crystal cell of the liquid crystal alignment agents (27) to (32) was a nematic liquid crystal (MLC-6608) (manufactured by Merck. Japan).

The liquid crystal cell (usually a unit cell) obtained was evaluated for the liquid crystal alignment in the vicinity of the sealant by visual observation using a polarizing plate and a backlight, and any of the liquid crystal cells obtained in the examples and the comparative examples showed uniform liquid crystal. Orientation.

Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% RH for 72 hours, and the liquid crystal alignment property in the vicinity of the sealant was evaluated under the same conditions as above. Specifically, the messy liquid crystal alignment is less visible in the vicinity of the sealant, and the evaluation is superior.

In Tables 19 to 21, the disorder of the liquid crystal alignment was ○, and the disorder of the liquid crystal alignment was ×.

"Evaluation of voltage maintenance rate after high temperature and high humidity storage (usually unit cell)"

The liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell (normally a unit cell). Apply the solution to The ITO surface of a 30×40 mm ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) washed with pure water and IPA was spin-coated on a hot plate at 100 ° C for 5 minutes in a heat cycle type. The film was heat-treated at 230 ° C for 30 minutes in a clean oven to obtain an ITO substrate of an agglomerated iridium imine liquid crystal alignment film having a film thickness of 100 nm. The coating film surface of the ITO substrate was subjected to a rubbing treatment using a rayon cloth using a rayon cloth with a roller rotation number of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and a spacer having a liquid crystal alignment film surface of 6 μm inside was laminated, and an ultraviolet curing type sealing agent was printed. Then, after the other substrate is bonded to the liquid crystal alignment film surface, the ultraviolet curing type sealing agent is cured to obtain an empty cell. Specifically, a metal halide lamp having an illuminance of 60 mW is used, and a wavelength of 310 nm or less is blocked, and ultraviolet rays of 5 J/cm ² in terms of 365 nm are irradiated, and then heated at 120 ° C for 60 minutes in a heat cycle type clean oven. Obtain an empty unit cell. In the empty cell, liquid crystal is injected by a vacuum injection method, and the injection port is sealed to obtain a liquid crystal cell (normal cell).

In addition, the liquid crystal used for the production of the liquid crystal cell of each of the examples and the comparative examples is the same as the evaluation of the display unevenness characteristic (normal cell) in the vicinity of the front edge of the liquid crystal cell after high temperature and high humidity storage. .

The obtained liquid crystal cell was applied with a voltage of 1 V for 60 μs at a temperature of 80 ° C, and the voltage after 50 ms was measured, and the voltage was maintained as a voltage holding ratio (also referred to as VHR). Again, the measurement system uses voltage maintenance rate The measurement device (VHR-1) (manufactured by TOYO Corporation) was set at a setting of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

Further, the liquid crystal cell in which the voltage maintenance ratio was measured was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% RH for 96 hours, and the voltage maintenance ratio was measured again under the same conditions as above.

In the evaluation, the value of the voltage holding ratio just prepared by the liquid crystal cell is preferably as small as the decrease in the value of the voltage holding ratio after storage in the high-temperature and high-humidity bath (Tables 19 to 20).

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

The liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and production of a liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell) were performed. The solution was placed on an ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and a center 10×40 mm ITO electrode substrate (length 40 mm) separated by 20 μm in a pattern of 10×10 mm in the center of pure water and IPA. The ITO surface of ×30 mm in width and 0.7 mm in thickness was spin-coated, and heat-treated in a heat-cycling type clean oven at 230 ° C for 30 minutes on a hot plate to obtain a film having a thickness of 100 nm.醯 imine coating.

The substrate on which the liquid crystal alignment film was attached was placed on the inner side of the liquid crystal alignment film surface, and the spacers of 6 μm were sandwiched, and the surrounding cells were bonded with a sealant to prepare an empty cell. Into the empty cell, 100% by mass of the nematic liquid crystal (MLC-6608) was mixed with 0.3% by mass of the liquid crystal mixture of the polymerizable compound (1) represented by the following formula, and the injection port was injected under reduced pressure injection. Sealed to obtain a liquid crystal cell.

A metal halide lamp having an illuminance of 60 mW was applied to the obtained liquid crystal cell, and a wavelength of 350 nm or less was blocked, and ultraviolet rays were irradiated at 20 J/cm ² in terms of 365 nm to obtain a alignment direction of the liquid crystal. Controlled liquid crystal cell (PSA unit cell). The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

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

The PSA unit cell obtained in the examples was found to have a faster reaction rate after ultraviolet irradiation than before ultraviolet irradiation, and it was confirmed that the alignment direction of the liquid crystal was controlled. Moreover, the liquid crystal cell of the Example was observed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by NIKON Co., Ltd.), and it was confirmed that the liquid crystal was uniformly aligned.

<Example 1>

NMP (20.9 g) and BCS (12.3 g) were added to a polyamic acid solution (1) (10.5 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 1, and stirred at 25 ° C for 2 hours. After that, add in the solution S1 (0.132 g) was stirred at 25 ° C for 4 hours. Thereafter, P2 (0.263 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (1). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (1), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 2>

NEP (9.90 g) and PB (7.50 g) were added to a polyamic acid solution (2) (5.50 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 2, and stirred at 25 ° C for 2 hours. Thereafter, S1 (0.097 g) was added to the solution, and the mixture was stirred at 25 ° C for 4 hours. Thereafter, P2 (0.097 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (2). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (2), "Evaluation of display unevenness characteristics (normal cell) in the vicinity of the front edge of the liquid crystal cell after high temperature and high humidity storage" and "Voltage retention rate after high temperature and high humidity storage" Assessment (usually a unit cell).

<Example 3>

In the polyimine powder (3) (1.35 g) obtained in Synthesis Example 3, NEP (14.8 g) and PB (6.30 g) were added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. Thereafter, S2 (0.095 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P2 (0.095 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (3) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (3), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 4>

NEP (9.90 g) and PB (7.50 g) were added to a polyamic acid solution (4) (5.50 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 4, and stirred at 25 ° C for 2 hours. Thereafter, S1 (0.097 g) was added to the solution, and the mixture was stirred at 25 ° C for 4 hours. Thereafter, P2 (0.097 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (4) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (4), "Evaluation of display unevenness characteristics in the vicinity of the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humid storage" Assessment (usually a unit cell).

<Example 5>

NEP (9.00 g), EC (2.20 g), and PB (6.60 g) were added to the polyamic acid solution (4) (5.60 g) of the resin having a solid concentration of 25% by mass obtained in Synthesis Example 4. Stir at 2 °C for 2 hours. Thereafter, S2 (0.14 g) was added to the solution, and the mixture was stirred at 25 ° C for 4 hours. Thereafter, P1 (0.21 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (5) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (5), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 6>

NEP (13.5 g) and PB (7.30 g) were added to the polyimine powder (5) (1.33 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.093 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P2 (0.093 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (6) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (6), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Evaluation (usually unit cell) and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 7>

NEP (24.2 g) and PB (13.0 g) were added to the polyimine powder (5) (1.15 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.081 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P2 (0.115 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (7). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (7).

<Example 8>

NMP (11.6 g), EC (2.10 g), and BCS (7.40 g) were added to the polyimine powder (5) (1.35 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.135 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P3 (0.203 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (8). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (8), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high temperature and high humidity storage (normal cell)" and "Voltage retention rate after high temperature and high humidity storage" Assessment (usually a unit cell).

<Example 9>

In the polyimine powder (6) (1.30 g) obtained by the synthetic method of Synthesis Example 6, NEP (13.2 g) and PB (7.10 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.195 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.221 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (9). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (9), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage retention rate after high-temperature and high-humidity storage" Evaluation (usually unit cell) and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 10>

In the polyimine powder (6) (1.10 g) obtained by the synthesis method of Synthesis Example 6, NEP (23.1 g) and PB (12.4 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.165 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.187 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (10). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (10).

<Example 11>

To the polyimine powder (7) (1.32 g) obtained in Synthesis Example 7, NEP (8.30 g), γ-BL (4.10 g) and BCS (8.30 g) were added, and the mixture was stirred at 70 ° C for 24 hours. Dissolved. Thereafter, S2 (0.026 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P2 (0.066 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (11) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (11), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 12>

NMP (12.7 g), ECS (2.10 g), and BCS (6.30 g) were added to the polyimine powder (7) (1.35 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.095 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.068 g) and P2 (0.135 g) were added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (12). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Evaluation of display unevenness characteristics near the frontal edge of the liquid crystal cell after high temperature and high humidity storage using the obtained liquid crystal alignment agent (12) (usually "Unit cell" and "Evaluation of voltage maintenance rate after high temperature and high humidity storage (normal cell)".

<Example 13>

To the polyimine powder (8) (1.30 g) obtained in Synthesis Example 8, NEP (13.2 g) and PB (7.10 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.091 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P2 (0.13 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (13) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (13), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage retention rate after high-temperature and high-humidity storage" Evaluation (usually unit cell) and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 14>

To the polyimine powder (8) (1.30 g) obtained in Synthesis Example 8, NEP (13.2 g) and PB (7.10 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.065 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.039 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (14). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Use the obtained liquid crystal alignment treatment agent (14) for "high temperature and high humidity protection" Evaluation of display unevenness characteristics (normal cell) near the front edge of the liquid crystal cell after the tube and "evaluation of the voltage maintenance rate after high temperature and high humidity storage (normal cell)".

<Example 15>

In the polyimine powder (9) (1.35 g) obtained in Synthesis Example 9, NEP (10.6 g), γ-BL (2.10 g) and PB (8.50 g) were added, and the mixture was stirred at 70 ° C for 24 hours. Dissolved. Thereafter, S1 (0.135 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P3 (0.135 g) was added, and after stirring at 60 ° C for 6 hours, a liquid crystal alignment treatment agent (15) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (15), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high temperature and high humidity storage (normal cell)" and "voltage maintenance rate after high temperature and high humidity storage" Assessment (usually a unit cell).

<Example 16>

NEP (17.8 g), γ-BL (3.60 g), and PB (14.2 g) were added to the polyimine powder (9) (1.10 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours. Dissolved. Thereafter, S1 (0.077 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P3 (0.11 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (16). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was uniformly dissolved. liquid.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (16).

<Example 17>

NMP (13.2 g) and PB (7.10 g) were added to the polyimine powder (10) (1.30 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.13 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.195 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (17). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (17), "Evaluation of display unevenness characteristics in the vicinity of the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 18>

NEP (13.2 g) and PB (7.10 g) were added to the polyimine powder (10) (1.30 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.091 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P1 (0.091 g) and P2 (0.091 g) were added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (18). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (18), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage retention rate after high-temperature and high-humidity storage" Evaluation (usually unit cell) and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 19>

γ-BL (11.6 g), EC (2.10 g) and BCS (7.40 g) were added to the polyimine powder (11) (1.35 g) obtained in Synthesis Example 11, and stirred at 70 ° C for 24 hours. Dissolved. Thereafter, S2 (0.068 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. Thereafter, P3 (0.135 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (19). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (19), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Example 20>

NMP (12.2 g), ECS (2.00 g) and BCS (6.10 g) were added to the polyimine powder (11) (1.30 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S1 (0.065 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours. After joining P1 (0.065 g) and P2 (0.065 g) were stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (20). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (20), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 1>

NEP (10.1 g) and PB (7.70 g) were added to a polyamic acid solution (2) (5.60 g) having a solid content concentration of 25% by mass of the resin obtained in Synthesis Example 2, and stirred at 25 ° C for 2 hours. A liquid crystal alignment treatment agent (21) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (21), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 2>

NEP (9.90 g) and PB (7.50 g) were added to a polyamic acid solution (2) (5.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2, and carried out at 25 ° C. Stir for hours. Then, P2 (0.097 g) was added to the solution, and after stirring at 60 ° C for 6 hours, liquid crystal alignment was obtained. Treatment agent (22). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (22), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 3>

NEP (9.90 g) and PB (7.50 g) were added to a polyamic acid solution (2) (5.50 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 2, and stirred at 25 ° C for 2 hours. Thereafter, S1 (0.097 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (23). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (23), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 4>

NEP (14.3 g) and PB (6.10 g) were added to the polyimine powder (3) (1.30 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved to obtain a liquid crystal alignment treatment agent ( twenty four). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (24), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 5>

NEP (14.3 g) and PB (6.10 g) were added to the polyimine powder (3) (1.30 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P2 (0.091 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (25). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (25), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 6>

NEP (14.3 g) and PB (6.10 g) were added to the polyimine powder (3) (1.30 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.091 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (26). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Evaluation of display unevenness characteristics near the frontal edge of the liquid crystal cell after high temperature and high humidity storage using the obtained liquid crystal alignment agent (26) (usually "Unit cell" and "Evaluation of voltage maintenance rate after high temperature and high humidity storage (normal cell)".

<Comparative Example 7>

NEP (10.1 g) and PB (7.70 g) were added to a polyamic acid solution (4) (5.60 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 4, and stirred at 25 ° C for 2 hours. A liquid crystal alignment treatment agent (27) was obtained. It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (27), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high temperature and high humidity storage (normal cell)" and "Voltage retention rate after high temperature and high humidity storage" Assessment (usually a unit cell).

<Comparative Example 8>

NEP (10.1 g) and PB (7.70 g) were added to a polyamic acid solution (4) (5.60 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 4, and stirred at 25 ° C for 2 hours. Thereafter, P2 (0.098 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (28).

Using the obtained liquid crystal alignment agent (28), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 9>

NEP (10.1 g) and PB (7.70 g) were added to a polyamic acid solution (4) (5.60 g) having a resin solid concentration of 25% by mass obtained in Synthesis Example 4, and stirred at 25 ° C for 2 hours. Thereafter, S1 (0.098 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (29).

Using the obtained liquid crystal alignment agent (29), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "voltage maintenance rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 10>

NEP (13.7 g) and PB (7.40 g) were added to the polyimine powder (5) (1.35 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved to obtain a liquid crystal alignment treatment agent ( 30). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (30), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

<Comparative Example 11>

In the polyimine powder (5) (1.35 g) obtained in Synthesis Example 5, NEP (13.7 g) and PB (7.40 g) were added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. Thereafter, P2 (0.095 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (31). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (31), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high temperature and high humidity storage (normal cell)" and "Voltage retention rate after high temperature and high humidity storage" Assessment (usually a unit cell).

<Comparative Example 12>

NEP (13.7 g) and PB (7.40 g) were added to the polyimine powder (5) (1.35 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, S2 (0.095 g) was added to the solution, and the mixture was stirred at 50 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (32). It was confirmed that no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was a uniform solution.

Using the obtained liquid crystal alignment agent (32), "Evaluation of display unevenness characteristics near the front edge of the liquid crystal cell after high-temperature and high-humidity storage (normal cell)" and "Voltage retention rate after high-temperature and high-humidity storage" Assessment (usually a unit cell).

From the above results, the liquid crystal alignment treatment agent of the example is known. Compared with the liquid crystal alignment treatment agent of the comparative example, even when the liquid crystal cell is stored for a long period of time in the high-temperature and high-humidity bath, a liquid crystal alignment film having no liquid crystal alignment property in the vicinity of the sealing agent of the liquid crystal cell can be obtained. Further, even when the liquid crystal cell is stored for a long period of time in the high-temperature and high-humidity bath, a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio can be obtained. In other words, the liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film which can suppress the occurrence of display unevenness in the vicinity of the front edge of the liquid crystal display element and lower the voltage maintenance ratio even under high temperature and high humidity conditions.

Specifically, it is the embodiment 2 and the comparative example 1, the embodiment 3 and Comparative Example 4, Example 4 and Comparative Example 7 and Example 6 and Comparative Example 10 are specific polymers of the component (C) which are the same as the examples, and do not contain the specific isocyanate compound of the component (A). A comparison of comparative examples of specific amine compounds to which component (B) was not introduced. When the liquid crystal alignment agent of the comparative example is used, the liquid crystal cell is stored in the high-temperature and high-humidity bath for a long period of time, and the liquid crystal alignment property is disordered in the vicinity of the sealing agent of the liquid crystal cell and the central portion of the unit cell, and further, the voltage maintenance ratio is maintained. significantly reduce.

Next, Example 2 and Comparative Example 2, Example 3 and ratio Comparing Example 5, Example 4 with Comparative Example 8 and Example 6 with Comparative Example 11, that is, using the specific polymer of the component (C) and the specific isocyanate compound of the component (A), which are the same as the examples, A comparison of comparative examples of the specific amine compound of the component (B) was introduced. When the liquid crystal alignment agent of the comparative example is used, when the liquid crystal cell is stored in the high-temperature and high-humidity bath for a long period of time, the disorder of the liquid crystal alignment in the liquid crystal cell or the decrease in the voltage maintenance ratio is suppressed, but the embodiment is suppressed. The ratio is greatly deteriorated.

[industrial use]

A liquid crystal display element having a liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention is excellent in reliability, and is preferably used in a large-screen and high-definition liquid crystal television, and can be used as a TN element, an STN element, a TFT liquid crystal element, or the like. Vertical alignment type liquid crystal display element.

The specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2013-096469, filed on May 1, 2013, is hereby incorporated by reference.

Claims (20)

A liquid crystal alignment treatment agent characterized by containing the following components (A), (B) and (C), (A) a compound represented by the following formula [1], and (B) component: a compound represented by the formula [2], a component (C): a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimine. , (X ¹ is a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms; or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is represented by the following formula [ 1-1]~Structure selected by [1-6] (A ¹ is a hydrogen atom or a benzene ring, A ² is a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and A ³ is an alkane having 1 to 18 carbon atoms. Base, fluorine-containing alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or fluorine-containing alkoxy group having 1 to 18 carbon atoms) (W ¹ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and W ² is a single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, - N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, W ³ is a single bond, a benzene ring or a cyclohexane ring, W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO -, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, W ⁵ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and n is 1 to 5 Integer). The liquid crystal alignment treatment agent according to claim 1, wherein X ¹ of the above formula [1] is an alkylene group having 1 to 10 carbon atoms. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ² of the above formula [1] is a structure selected from the formula [1-1], the formula [1-2], and the formula [1-4]. The liquid crystal alignment treatment agent according to the above formula (2), wherein W ¹ of the above formula [2] is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring or a bicyclohexyl ring. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein W ² of the above formula [2] is a single bond, -O- or -OCO-. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein W ³ of the above formula [2] is a single bond or a benzene ring. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein W ⁴ of the above formula [2] is a single bond, -O-, -NH- or -CONH-. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein W ⁵ of the above formula [2] is a single bond or a linear or branched alkyl group having a carbon number of 1 to 10 or a cyclohexane ring. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the diamine component of the polymer of the component (C) contains at least one or more diamine compounds having a structure represented by the following formula [3]. (Y is a substituent selected by the following formula [3-1] to formula [3-6], and m is an integer of 1 to 4) (a is an integer from 0 to 4, b is an integer from 0 to 4, Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c - (c is 1 to 15) An integer), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a bivalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a steroid skeleton a divalent organic group having 12 to 25 carbon atoms, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 to 3 a fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and these ring groups are Any of the hydrogen atoms may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Atom substitution, n is an integer from 0 to 4, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 fluorine-containing group, Y ⁷ is _{-O -, - CH 2 O -} , - COO -, - OCO -, - CONH- or -NHCO-, Y ⁸ is alkyl having 8 to 22, Y ⁹ Y ¹⁰ each independently is a hydrocarbon group having 1 to 12 carbon atoms, Y ¹¹ is alkyl having 1 to 5). The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the tetracarboxylic acid component of the polymer of the component (C) contains a compound represented by the following formula [4]. (Z ¹ is a base of the structure selected by the following formula [4a] to formula [4j]) (Z ² to Z ⁵ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and Z ⁶ and Z ⁷ may each be a hydrogen atom or a methyl group, and each may be the same or different). The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the polymer of the component (C) is a polyimine obtained by dehydrating and ring-closing polylysine. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C). The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the component (B) is 0.1 to 30 mass based on 100 parts by mass of the component (C). Quantities. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13 and using an inkjet method. A liquid crystal display element characterized by comprising the liquid crystal alignment film of claim 14 or 15. The liquid crystal alignment film according to claim 14 or 15, wherein the liquid crystal layer is provided between the pair of substrates including the electrodes, and the polymerizable property is polymerized by at least one of the active energy ray and the heat between the pair of substrates. A liquid crystal display device produced by polymerizing the polymerizable compound while applying a voltage between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film of claim 17. The liquid crystal alignment film according to claim 14 or claim 15, wherein the liquid crystal alignment layer is provided between the pair of substrates including the electrodes, and the liquid crystal layer is disposed between the pair of substrates and is polymerized by at least one of an active energy ray and heat. A liquid crystal display element produced by polymerizing the polymerizable group while applying a voltage between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film of claim 19.