JP2017040721A - Liquid crystal aligning agent, liquid crystal alignment film, production method of liquid crystal alignment film, liquid crystal display element, polymer and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent that can give a liquid crystal display element having good reliability to backlight irradiation and good contrast characteristics.SOLUTION: A compound (X) having a partial structure represented by formula (1) below is incorporated into a liquid crystal aligning agent. In formula (1), Rrepresents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group; Rrepresents a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group; Rand Reach independently represent a substituent and may be bonded to another group to form at least a part of a ring; and n1 and n2 each independently represent an integer of 0 to 4.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a method for producing a liquid crystal alignment film, a liquid crystal display element, a polymer, and a compound.

  Liquid crystal display elements are widely used in televisions, mobile devices, various monitors, and the like. In such a liquid crystal display element, a liquid crystal alignment film is used to control alignment of liquid crystal molecules in the liquid crystal cell. As a method for obtaining an organic film having alignment regulating ability of liquid crystal molecules, conventionally, a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long chain alkyl group, and photosensitivity A method of irradiating the organic film with light (photo-alignment method) is known.

  The photo-alignment method can give uniform liquid crystal alignment to a photosensitive organic film while suppressing the generation of static electricity and dust, and also allows precise control of the liquid crystal alignment direction. (See, for example, Patent Document 1). Patent Document 1 discloses that a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a polyimide precursor having a cinnamoyl group in the main chain, polyimide or polyamide.

International Publication No. 2013/161984

  In recent years, large-screen high-definition liquid crystal televisions are mainly used, and small display terminals such as smartphones and tablet PCs are becoming popular, and the demand for higher quality for liquid crystal panels is increasing. For example, a liquid crystal television has a long replacement cycle of several years to several tens of years, and is premised on being exposed to backlight for a long time. In addition, a small display terminal is likely to be subjected to light stress due to the backlight, for example, the backlight brightness is set high in order to increase the visibility and the display terminal is driven for a long time in that state. A liquid crystal display device is required to have high reliability and little deterioration in electrical characteristics even after long-time backlight irradiation. Further, in order to improve the quality of the liquid crystal display element, it is important that the contrast is good (contrast characteristics), and further improvement of these various characteristics is required.

  The present invention has been made in view of the above problems, and provides a liquid crystal aligning agent capable of obtaining a liquid crystal display element having good reliability for backlight irradiation and good contrast characteristics. Objective.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors have found that the above-described problems can be solved by including a component having a specific structure in the liquid crystal aligning agent. The invention has been completed. Specifically, the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal alignment film manufacturing method, liquid crystal display element, polymer, and compound are provided.

（式（１）中、Ｒ^１は、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基であり、Ｒ^２は、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基である。Ｒ^３及びＲ^４は、それぞれ独立に置換基であり、他の基に結合して環の少なくとも一部を構成していてもよい。ｎ１及びｎ２は、それぞれ独立に０〜４の整数である。ｎ１が２以上の場合、複数のＲ^３は同じでも異なってもよく、ｎ２が２以上の場合、複数のＲ^４は同じでも異なってもよい。「＊」は結合手を示す。） [1] A liquid crystal aligning agent containing compound (X) having a partial structure represented by the following formula (1).

(In Formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group, and R ² is a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group. R ³ and R ⁴ are each independently a substituent, and may be bonded to another group to form at least a part of the ring, and n1 and n2 are each independently an integer of 0 to 4. When n1 is 2 or more, the plurality of R ³ may be the same or different, and when n2 is 2 or more, the plurality of R ⁴ may be the same or different, “*” indicates a bond. )

（式（２−１）中、Ｒ^５及びＲ^８は、それぞれ独立に３価の有機基であり、Ｒ^６及びＲ^７は、それぞれ独立に、単結合又は２価の連結基である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｎ１及びｎ２は、上記式（１）と同義である。）

（式（２−２）中、Ｒ^１５は、２価の有機基であり、ｎ４は０又は１である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｎ１及びｎ２は、上記式（１）と同義である。ｎ４＝１の場合、複数のｎ２は同じでも異なっていてもよい。） [2] A method for producing a liquid crystal alignment film, comprising: a step of applying the liquid crystal aligning agent of [1] above on a substrate to form a coating film; and a step of irradiating the coating film with light.
[3] A liquid crystal alignment film formed using the liquid crystal aligning agent of [1].
[4] A liquid crystal display device comprising the liquid crystal alignment film according to [3].
[5] A polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, and poly (meth) acrylate, and having a partial structure represented by the above formula (1).
[6] A tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, wherein the compound is represented by the following formula (2-1) and the following formula: A tetracarboxylic acid derivative which is a tetracarboxylic dianhydride selected from the group consisting of the compound represented by (2-2) or a derivative thereof.

(In Formula (2-1), R ⁵ and R ⁸ are each independently a trivalent organic group, and R ⁶ and R ⁷ are each independently a single bond or a divalent linking group. ¹ , R ² , R ³ , R ⁴ , n1 and n2 are as defined in the above formula (1).

(In the formula (2-2), R ¹⁵ is a divalent organic group, and n4 is 0 or 1. R ¹ , R ² , R ³ , R ⁴ , n1 and n2 are represented by the above formula (1 When n4 = 1, a plurality of n2s may be the same or different.)

  According to the liquid crystal aligning agent containing the said compound (X), there is little deterioration of the electrical property by backlight irradiation, and a highly reliable liquid crystal display element can be obtained. Moreover, the obtained liquid crystal display element has good contrast characteristics and excellent display quality.

The schematic block diagram of a FFS type liquid crystal display element. The plane schematic diagram of the top electrode used for manufacture of the liquid crystal display element by a photo-alignment process. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode. The figure which shows the drive electrode of 4 systems.

Below, each component contained in the liquid crystal aligning agent of this indication and the other component arbitrarily mix | blended as needed are demonstrated.
In the present specification, the “hydrocarbon group” means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group that are composed only of a chain structure without including a cyclic structure in the main chain. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. “Organic group” means a group containing a hydrocarbon group, and the structure may contain a hetero atom.

（式（１）中、Ｒ^１は、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基であり、Ｒ^２は、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基である。Ｒ^３及びＲ^４は、それぞれ独立に置換基であり、他の基に結合して環の少なくとも一部を構成していてもよい。ｎ１及びｎ２は、それぞれ独立に０〜４の整数である。ｎ１が２以上の場合、複数のＲ^３は同じでも異なってもよく、ｎ２が２以上の場合、複数のＲ^４は同じでも異なってもよい。「＊」は結合手を示す。） <Compound (X)>
The liquid crystal aligning agent of this indication contains the compound (henceforth "compound (X)") which has the partial structure represented by following formula (1).

(In Formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group, and R ² is a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group. R ³ and R ⁴ are each independently a substituent, and may be bonded to another group to form at least a part of the ring, and n1 and n2 are each independently an integer of 0 to 4. When n1 is 2 or more, the plurality of R ³ may be the same or different, and when n2 is 2 or more, the plurality of R ⁴ may be the same or different, “*” indicates a bond. )

In the above formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an epoxy group, an alkylsilyl group, and an alkoxysilyl group.
Here, the alkyl group having 1 to 20 carbon atoms may be linear or branched, and specifically includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group; examples of the fluoroalkyl group having 1 to 20 carbon atoms include a perfluoromethyl group and a perfluoroethyl group. Group, 2,2,2-trifluoroethyl group and the like; examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopentyl group, cyclohexyl group and methylcyclohexyl group; and examples of the aryl group having 6 to 20 carbon atoms Examples thereof include a phenyl group and a tolyl group; examples of the aralkyl group having 6 to 20 carbon atoms include a benzyl group; Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

From the viewpoint of obtaining a coating film that has high reliability for backlight irradiation and exhibits high liquid crystal alignment regulating power by photo-alignment treatment, R ¹ is hydrogen atom, halogen atom, hydroxyl group, cyano group, carbon, among these. It is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom or 1 to 1 carbon atom. More preferably, it is an alkyl group of 3. For the same reason, R ² is preferably a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, and having 1 to 6 carbon atoms. It is more preferably an alkyl group, and further preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the substituent for R ³ and R ⁴ include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a carboxyl group, a cyano group, an alkylsilyl group, an alkoxysilyl group, and an ester group. Is mentioned. R ³ and R ⁴ may be bonded to other groups to form at least a part of a ring such as an imide ring or an aromatic ring. n1 and n2 are each preferably 0 or 1. “*” In formula (1) may be bonded to a hydrogen atom or may be bonded to an organic group.

The compound (X) may be a polymer component that is a main component of the liquid crystal alignment film, or may be an additive component that is blended separately from the polymer component. Among these, the compound (X) is preferably a polymer component in that the effect of anisotropy when the photo-alignment method is applied is high. The compound (X) as a polymer may have a partial structure represented by the above formula (1) in the main chain or in the side chain, but is anisotropic by light. It is particularly preferable to have it in the main chain from the viewpoint of sufficiently expressing.
Here, the “main chain” of the polymer in the present disclosure refers to a “trunk” portion composed of the longest chain of atoms in the polymer. It is allowed that the “trunk” portion includes a ring structure. Therefore, “having the partial structure represented by the above formula (1) in the main chain of the polymer” means that the partial structure constitutes a part of the main chain. However, it does not exclude that the partial structure represented by the above formula (1) exists also in a portion other than the main chain, for example, a side chain (a portion branched from the “trunk” of the polymer).

The main skeleton in the case where the compound (X) is a polymer is not particularly limited. For example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene- Main skeletons such as phenylmaleimide) derivatives and poly (meth) acrylates.
Among these, it is at least one selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane, and poly (meth) acrylate from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystal, and the like. Preferably, it is at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester. Among these, the structural unit is derived from a monomer having at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester and having a partial structure represented by the above formula (1). It is particularly preferable to use a polymer whose monomer is at least one selected from the group consisting of diamine, tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dihalide.
In addition, the polymer used for preparation of a liquid crystal aligning agent may be only 1 type, and 2 or more types may be sufficient as it. (Meth) acrylate is meant to include acrylate and methacrylate. Hereinafter, preferable examples when the compound (X) is a polymer will be described.

[Polyamic acid]
The polyamic acid as the compound (X) is a polyamic acid having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific polyamic acid”), for example, tetracarboxylic dianhydride and diamine. It can obtain by making it react. Specifically, the following methods [1] to [3] are exemplified.
[1] A method of polymerization using a tetracarboxylic dianhydride having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific acid dianhydride”).
[2] A method of polymerizing using a diamine having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific diamine”).
[3] A method of polymerizing using the specific acid dianhydride and the specific diamine.

（式（２−１）中、Ｒ^５及びＲ^８は、それぞれ独立に３価の有機基であり、Ｒ^６及びＲ^７は、それぞれ独立に、単結合又は２価の連結基である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｎ１及びｎ２は、上記式（１）と同義である。）

（式（２−２）中、Ｒ^１５は、２価の有機基であり、ｎ４は０又は１である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｎ１及びｎ２は、上記式（１）と同義である。ｎ４＝１の場合、複数のｎ２は同じでも異なっていてもよい。） (Tetracarboxylic dianhydride)
The specific acid dianhydride used for the synthesis of the polyamic acid is not particularly limited as long as it has the partial structure represented by the above formula (1). Preferred specific examples include, for example, Examples thereof include a compound represented by the formula (2-1) and a compound represented by the following formula (2-2).

(In Formula (2-1), R ⁵ and R ⁸ are each independently a trivalent organic group, and R ⁶ and R ⁷ are each independently a single bond or a divalent linking group. ¹ , R ² , R ³ , R ⁴ , n1 and n2 are as defined in the above formula (1).

(In the formula (2-2), R ¹⁵ is a divalent organic group, and n4 is 0 or 1. R ¹ , R ² , R ³ , R ⁴ , n1 and n2 are represented by the above formula (1 When n4 = 1, a plurality of n2s may be the same or different.)

In the above formula (2-1), the trivalent organic group of R ⁵ and R ⁸ is preferably a chain hydrocarbon group, an alicyclic group, an aromatic ring group, or a heterocyclic group. An alicyclic group or an aromatic ring group is more preferable, and a group obtained by removing three hydrogen atoms from a ring portion of a cyclopentane ring, a cyclohexane ring or a benzene ring is particularly preferable. In the case R ⁵ and R ⁸ is an alicyclic group or an aromatic ring group, substituents in the ring portion may be introduced. Examples of the substituent include a halogen atom, an alkyl group, and a fluoroalkyl group.
Examples of the divalent linking group for R ⁶ and R ⁷ include —O—, —CO—, —COO—, —CONR ^a — (R ^a is a hydrogen atom or a monovalent carbon atom having 1 to 10 carbon atoms. ^.. it is a hydrogen radical or less the ^{same), - NR a -, -} NR a CONR a -, - OCONR a -, - S -, - COS -, - OCOO -, - SO 2 - heteroatom-containing groups, such as; A divalent hydrocarbon group having 1 to 20 carbon atoms; a group containing the heteroatom-containing group between carbon-carbon bonds of the hydrocarbon group; a group in which the hydrocarbon group and the heteroatom-containing group are linked; A group in which at least one hydrogen atom of a hydrocarbon group is substituted with a substituent; a group having a heterocyclic structure, and the like.
In the above formula (2-2), examples of the divalent organic group represented by R ¹⁵ include a divalent hydrocarbon group having 1 to 20 carbon atoms; the above hetero atom-containing group between the carbon-carbon bonds of the hydrocarbon group. A group containing a group; a group in which the hydrocarbon group and the heteroatom-containing group are linked; a group in which at least one hydrogen atom of the hydrocarbon group is replaced with a substituent, and the like.
For specific examples and preferred examples of R ¹ , R ² , R ³ , R ⁴ , n1 and n2 in the above formulas (2-1) and (2-2), the description of the above formula (1) is applied. be able to.

Preferable specific examples of the specific acid dianhydride include compounds represented by the following formulas (d-1) to (d-21). In addition, specific acid dianhydride can be used individually by 1 type or in combination of 2 or more types.

  The specific acid dianhydride can be synthesized by appropriately combining conventional methods of organic chemistry. For example, the compound represented by the above formula (d-1) is represented by the above formula (1) by reacting 1,4-diisopropenylbenzene with a dicarboxylic acid derivative such as 4-bromophthalic acid dimethyl ester. The tetracarboxylic acid having a partial structure to be synthesized can be synthesized, and then the resulting tetracarboxylic acid can be obtained by acid anhydride formation. However, the synthesis procedure of the specific acid dianhydride is not limited to the above method.

  In the case of the above method [1] and method [3], the tetracarboxylic dianhydride used for the synthesis of the specific polyamic acid may be only the specific acid dianhydride, but is represented by the above formula (1). A tetracarboxylic dianhydride having no partial structure (hereinafter, also referred to as “other acid dianhydrides”) may be used in combination. In the above method [2], other acid dianhydrides are used as tetracarboxylic dianhydrides in the synthesis of the specific polyamic acid.

  Examples of such other acid dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and ethylenediaminetetraacetic acid dianhydride;

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan- 1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro- 3-furanyl)- -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0 ] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3 , 5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (am Hydrotrimellitate), 1,3-propylene Glycol bis (anhydrotrimellitate) etc .;
Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 4,4′-oxydiphthalic anhydride, ethylene glycol bisanhydrotri Mate, propylene glycol bisanhydrotrimate, 1,4-butylene glycol bisanhydrotrimate, diethylene glycol bisanhydrotrimate, p-phenylenebis (trimellitic acid monoester anhydride), and the like. .

As other acid dianhydrides, a group consisting of aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides in that a liquid crystal display device having higher reliability with respect to backlight irradiation can be obtained. It is preferable to use at least one acid dianhydride selected from the group consisting of aliphatic tetracarboxylic dianhydrides.
As at least one preferred specific example selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, for example, butanetetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3 , 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6 : It is preferable to contain at least one compound selected from the group consisting of 8-dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride.

  When using at least one selected from the group consisting of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride as the other acid dianhydride, the use ratio is used for the synthesis of a specific polyamic acid. It is preferable to set it as 10 mol% or more with respect to the whole quantity of the tetracarboxylic dianhydride to be used, It is more preferable to set it as 20 mol% or more, It is still more preferable to set it as 30 mol% or more. In addition, about the upper limit of the usage-amount of the said acid dianhydride, it can set suitably according to the said method [1]-[3]. Other acid dianhydrides can be used singly or in combination of two or more.

  In the above method [1], the use ratio of the specific acid dianhydride is to increase the photosensitivity of the obtained coating film while increasing the reliability with respect to backlight irradiation, and the contrast of the obtained liquid crystal display element. From the viewpoint of enhancing the characteristics, it is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, based on the total amount of tetracarboxylic dianhydride used for the synthesis of the specific polyamic acid. More preferably, it is at least mol%.

（式（３）中、Ｒ^９〜Ｒ^１１は、それぞれ独立に、単結合又は２価の有機基である。Ｂ^１は、単結合、上記式（１）で表される基又は下記式（１−１）で表される基である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｎ１及びｎ２は、上記式（１）と同義である。）

（式（１−１）中、Ｒ^１２は、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基であり、Ｒ^１３は、ハロゲン原子、ヒドロキシル基、シアノ基又は１価の有機基である。Ｒ^１４は置換基であり、他の基に結合して環の少なくとも一部を構成していてもよい。ｎ３は０〜４の整数であり、ｎ３が２以上の場合、複数のＲ^１４は同じでも異なってもよい。「＊^１」及び「＊」は、結合手であることを示す。ただし、「＊^１」がＲ^１０に結合している。） (Diamine)
As long as the specific diamine used for the synthesis of the specific polyamic acid has a partial structure represented by the above formula (1), the remaining structure is not particularly limited. The compound etc. which are represented by (3) are mentioned.

(In Formula (3), R ^{9 to} R ¹¹ are each independently a single bond or a divalent organic group. B ¹ is a single bond, a group represented by the above formula (1), or a group represented by the following formula ( (1-1) R ¹ , R ² , R ³ , R ⁴ , n1 and n2 have the same meanings as in the above formula (1).

(In formula (1-1), R ¹² is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group, and R ¹³ is a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group. R ¹⁴ is a substituent, and may be bonded to another group to form at least a part of the ring, n3 is an integer of 0 to 4, and when n3 is 2 or more, a plurality of of R ¹⁴ may be the same or different. "* ^1" and "*" indicates that the bond. However, "* ^1" is attached to R ^10.)

In the above formula (3), R ⁹ and R ¹¹ are preferably a single bond or a divalent hydrocarbon group, and more preferably a single bond or a divalent aromatic ring group. R ¹⁰ is preferably a single bond or a divalent hydrocarbon group, and more preferably a single bond.
The description of R ¹ and R ^{2 in} the above formula (1) can be applied to R ¹² and R ^{13 in} the above formula (1-1), respectively. The explanation of R ^{3 in} the above formula (1) can be applied to R ¹⁴ .

Preferable specific examples of the specific diamine include compounds represented by the following formulas (b-1) to (b-18), for example. In addition, specific diamine can be used individually by 1 type or in combination of 2 or more types.

The specific diamine can be synthesized by appropriately combining organic chemistry methods. For example, instead of the two primary amino groups of a specific diamine, a dinitro intermediate having two nitro groups is synthesized, and then the nitro group of the obtained dinitro intermediate is converted into an appropriate reduction system. The method of amination using is mentioned.
The method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. For example, the compound represented by the above formula (b-1) can be obtained by performing a dimerization reaction of 4′-nitroacetophenone, preferably in the presence of a catalyst. The compound represented by the above formula (b-2) can be obtained by reacting 4′-nitroacetophenone and 4-nitrobenzaldehyde, preferably in the presence of a catalyst.
The reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel or the like. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, alcohols, and the like. However, the synthesis procedure of the specific diamine is not limited to the above method.

  When the specific polyamic acid is synthesized by the method [2] or the method [3], the specific diamine may be used alone, or the diamine having no partial structure represented by the above formula (1) , Also referred to as “other diamines”). In the above method [1], other diamines are used as diamines.

Examples of such other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples of these include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis (aminomethyl) cyclohexane. ;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine) and the like;

（式（Ｅ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−（ただし、「＊」はＸ^Ｉとの結合手を示す。）であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物などの側鎖導入型のジアミン： Examples of aromatic diamines include dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, and cholesteryloxydiaminobenzene. Cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostannyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4 -((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((amino Phenoxy Methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4 -(4-Heptylcyclohexyl) benzamide, the following formula (E-1)

(In Formula (E-1), X ^I and X ^II are each independently a single bond, —O—, * —COO— or * —OCO— (where “*” represents a bond with X ^I). R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, and b is 0 ) Is an integer of ˜2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.)
Side chain-introduced diamine such as a compound represented by:

p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4-aminophenyl-4′-aminobenzoate, 4,4′-diaminoazobenzene, 1,5-bis (4-amino) Phenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 3,5 -Diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 1,5-diaminonaphthalene, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'- Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1 , 4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, the following formula (N-1-1) to formula (N-1-8)

A side chain non-introducing diamine, such as a compound represented by each of
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP-A 2010-97188 can be used.

Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _d —” in the above formula (E-1) include alkanediyl groups having 1 to 3 carbon atoms, * —O—, * —COO— or * —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. Examples of the group “—C _c H _{2c + 1} ” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like, and these are preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups.

なお、特定ポリアミック酸の合成に使用するその他のジアミンとしては、これらの化合物の１種を単独で、又は２種以上を適宜選択して使用することができる。 Specific examples of the compound represented by the formula (E-1) include, for example, compounds represented by the following formulas (E-1-1) to (E-1-4).

In addition, as another diamine used for the synthesis | combination of a specific polyamic acid, 1 type of these compounds can be used individually or in combination of 2 or more types as appropriate.

  When synthesizing a specific polyamic acid by the above method [2], the proportion of the specific diamine used is more excellent in reliability with respect to backlight irradiation, photosensitivity of the obtained coating film, and contrast characteristics of the obtained liquid crystal display element. From the viewpoint of, it is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more, based on the total amount of diamine used for the synthesis of the specific polyamic acid. preferable. Moreover, when synthesizing a specific polyamic acid by the above method [3], the total amount of the specific tetracarboxylic dianhydride and the specific diamine should be 10 mol% or more based on the total amount of monomers used in the synthesis. Is more preferable, 20 mol% or more is more preferable, and 30 mol% or more is further preferable.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above tetracarboxylic dianhydride and diamine together with a molecular weight adjusting agent as necessary. The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.

のそれぞれで表される化合物などの酸一無水物、アニリン、シクロヘキシルアミン、ｎ−ブチルアミンなどのモノアミン化合物、フェニルイソシアネート、ナフチルイソシアネートなどのモノイソシアネート化合物等を挙げることができる。
また、分子量調整剤としては、上記式（１）で表される部分構造を有する単官能性の化合物を用いてもよい。当該化合物としては、例えば下記式（ｍ−１）〜式（ｍ−１６）のそれぞれで表される化合物などが挙げられる。

分子量調整剤の使用割合は、使用するテトラカルボン酸二無水物及びジアミンの合計１００重量部に対して、２０重量部以下とすることが好ましく、１０重量部以下とすることがより好ましい。 Examples of the molecular weight modifier include maleic anhydride, phthalic anhydride, itaconic anhydride, and the following formulas (F-1) to (F-4):

And acid monoanhydrides such as compounds represented by each of these, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate.
Moreover, as a molecular weight modifier, you may use the monofunctional compound which has the partial structure represented by the said Formula (1). Examples of the compound include compounds represented by the following formulas (m-1) to (m-16).

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.

  Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols is used as a solvent, or a mixture of one or more of these and another organic solvent is preferably used in the above range. The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Prefer

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to known methods.

[Polyamic acid ester]
The polyamic acid ester (hereinafter, also referred to as “specific polyamic acid ester”) as the compound (X) is, for example, [I] a polyamic acid having a partial structure represented by the above formula (1), an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester and a diamine, [III] a method of reacting a tetracarboxylic acid diester dihalide and a diamine, and the like.
In this specification, “tetracarboxylic acid diester” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are carboxyl groups. “Tetracarboxylic acid diester dihalide” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are halogenated.

  Examples of the esterifying agent used in Method [I] include hydroxyl group-containing compounds, acetal compounds, halides, epoxy group-containing compounds, and the like. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N N, diethylformamide diethyl acetal, etc .; as halides, for example methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane, chloromethyl methyl ether 2-chloromethoxy-1,1,1-trifluoroethane, chloromethyl isopropyl carbonate, chloromethyl pivalate, chloromethyl acetate, chloromethyl butyrate, chloromethyl methyl sulfide, etc .; And example, if propylene oxide, can be mentioned, respectively.

The tetracarboxylic acid diester used in the method [II] is, for example, ring-opening the specific acid dianhydride and other acid dianhydrides exemplified in the synthesis of the polyamic acid with alcohols such as methanol and ethanol. Can be obtained. In the reaction, tetracarboxylic dianhydride may be used in combination with tetracarboxylic acid diester. Examples of the diamine to be used include the specific diamines exemplified in the synthesis of polyamic acid and other diamines. In the reaction, a specific polyamic acid ester can be obtained by using a monomer having a partial structure represented by the above formula (1).
The reaction of Method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, a phosphorus condensing agent, and the like. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

The tetracarboxylic acid diester dihalide used in Method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. In the reaction, tetracarboxylic dianhydride may be used in combination with tetracarboxylic acid diester dihalide. Examples of the diamine to be used include the specific diamines exemplified in the synthesis of polyamic acid and other diamines. In the reaction, a specific polyamic acid ester can be obtained by using a monomer having a partial structure represented by the above formula (1).
The reaction of Method [III] is preferably carried out in an organic solvent in the presence of a suitable base. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. As the base, for example, tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium can be preferably used. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

  The polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution formed by dissolving the specific polyamic acid ester may be used for the preparation of the liquid crystal aligning agent as it is, or the specific polyamic acid ester contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal aligning agent. Alternatively, the isolated specific polyamic acid ester may be purified and used for the preparation of the liquid crystal aligning agent. The isolation and purification of the specific polyamic acid ester can be performed according to a known method.

[Polyimide]
The polyimide as the compound (X) (hereinafter also referred to as “specific polyimide”) is obtained, for example, by dehydrating and ring-closing the polyamic acid as the compound (X) synthesized as described above to imidize. Can do.

  The specific polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an imide ring structure coexists. The specific polyimide preferably has an imidation ratio of 20% or more, more preferably 30 to 99%, and still more preferably 40 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a polyamic acid solution, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing the specific polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. You may use for preparation of a liquid crystal aligning agent, or you may use for preparation of a liquid crystal aligning agent, after refine | purifying the isolated specific polyimide. These purification operations can be performed according to known methods. In addition, specific polyimide can also be obtained by imidation of specific polyamic acid ester.

The polyamic acid, polyamic acid ester and polyimide as the compound (X) obtained as described above have a solution viscosity of 10 to 800 mPa · s when this is made into a 10% by weight solution. It is more preferable that it has a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). These are values measured at 25 ° C. using an E-type rotational viscometer (the same applies to the following polymers).
The polystyrene-equivalent weight average molecular weight (Mw) measured by polyamic acid, polyamic acid ester and polyimide gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000.

[polyamide]
The polyamide (hereinafter also referred to as “specific polyamide”) as the compound (X) can be obtained, for example, by a method of reacting a dicarboxylic acid and a diamine. The dicarboxylic acid is preferably subjected to a reaction with a diamine after acid chloride using an appropriate chlorinating agent such as thionyl chloride.

The dicarboxylic acid used for the synthesis of the specific polyamide is not particularly limited. Aliphatic dicarboxylic acids such as 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, fumaric acid, muconic acid;
Dicarboxylic acids having an alicyclic structure such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid;
Phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethane Dicarboxylic acid, 4,4′-diphenylpropane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3′- [4,4 ′-(methylenedi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dibutyric acid, 3,4-diphenyl-1,2- And dicarboxylic acids having an aromatic ring such as cyclobutanedicarboxylic acid. In addition, dicarboxylic acid can be used individually by 1 type or in combination of 2 or more types.
The diamine used when synthesizing the specific polyamide includes the specific diamine. Moreover, you may use other diamine together as needed. For the use ratio of the specific diamine, the description in the case of synthesizing the specific polyamic acid by the method [2] can be applied. In addition, a diamine can be used individually by 1 type or in combination of 2 or more types.

  The proportion of the dicarboxylic acid and diamine used in the synthesis reaction of the specific polyamide is preferably such that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine. The ratio which becomes -1.2 equivalent is more preferable.

The reaction between a dicarboxylic acid (preferably an acid-chloride dicarboxylic acid) and a diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably 0 ° C to 200 ° C, and more preferably 10 to 100 ° C. The reaction time is preferably 0.5 to 48 hours, and more preferably 1 to 36 hours.
As the organic solvent used for the reaction, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used. The amount of the organic solvent used is preferably 400 to 900 parts by weight and more preferably 500 to 700 parts by weight with respect to 100 parts by weight of the total amount of dicarboxylic acid and diamine.
As the base used in the above reaction, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine can be preferably used. The amount of the base used is preferably 2 to 4 mol and more preferably 2 to 3 mol with respect to 1 mol of the diamine.

  As described above, a reaction solution obtained by dissolving the specific polyamide is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after isolating the specific polyamide contained in the reaction solution, or the isolated specific polyamide is purified. You may use for preparation of a liquid crystal aligning agent. Isolation and purification of the specific polyamide can be performed according to a known method.

  The solution viscosity of the specific polyamide is preferably a solution viscosity of 10 to 800 mPa · s, preferably a solution viscosity of 15 to 500 mPa · s, when this is a 10% by weight solution. It is more preferable. Moreover, about the polyamide, the polystyrene conversion weight average molecular weight (Mw) measured by GPC becomes like this. Preferably it is 1,000-500,000, More preferably, it is 5,000-300,000.

[Polyorganosiloxane]
The polyorganosiloxane (hereinafter also referred to as “specific polyorganosiloxane”) as the compound (X) can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Specifically, the following [1] or [2]
[1] An epoxy group-containing polyorganosiloxane is synthesized by hydrolytic condensation of a hydrolyzable silane compound (ms-1) having an epoxy group or a mixture of the silane compound (ms-1) and another silane compound. And then reacting the obtained epoxy group-containing polyorganosiloxane with a carboxylic acid having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific carboxylic acid”),
[2] Hydrolyzing and condensing a hydrolyzable silane compound (ms-2) having a partial structure represented by the above formula (1) or a mixture of the silane compound (ms-2) and another silane compound. Method, etc. Among these, the method [1] is preferred because it is simple and can increase the introduction rate of the partial structure represented by the above formula (1) in the polyorganosiloxane.

  Specific examples of the hydrolyzable silane compound (ms-1) having an epoxy group include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxy. Silane, 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethyl Ethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4-glycidoxybutyl Dimethylethoxysilane Examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane. . As the silane compound (ms-1), one of these can be used alone, or two or more can be used in combination.

Other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds. For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Alkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane;
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3 -Cyclohexylamino) propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and other nitrogen / sulfur atom-containing alkoxysilanes;
3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, unsaturated hydrocarbon-containing alkoxysilanes such as p-styryltrimethoxysilane; in addition to trimethoxysilylpropyl succinic anhydride Can be mentioned. Other silane compounds can be used alone or in combination of two or more.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent.
In the method [1], a sufficient amount of the partial structure represented by the above formula (1) can be introduced into the side chain of the polymer, and a side reaction caused by an excessive amount of epoxy groups. From the viewpoint of inhibiting the epoxy group-containing polyorganosiloxane, the epoxy equivalent is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, in synthesizing the epoxy group-containing polyorganosiloxane, it is preferable to adjust the use ratio of the silane compound (ms-1) so that the epoxy equivalent of the obtained polyorganosiloxane is in the above range. In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. Examples of the catalyst include alkali metal compounds or organic bases among them in that side reactions such as ring opening of epoxy groups can be suppressed, the rate of hydrolysis condensation can be increased, and the storage stability is excellent. A tertiary or quaternary organic base is particularly preferable.
The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

Examples of the organic solvent used in the hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Specific examples thereof include hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and cyclopentanone; esters such as ethyl acetate. N-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; alcohols; For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether and the like; may be mentioned, respectively. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The use ratio of the organic solvent in the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds used in the reaction. .

  The hydrolysis / condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing this solution with an organic base and water, and heating the solution with, for example, an oil bath. In the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the polyorgano Siloxane can be obtained.

  In the method [1], the obtained epoxy group-containing polyorganosiloxane is then reacted with a specific carboxylic acid. As a result, the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain a polyorganosiloxane having a partial structure represented by the above formula (1) in the side chain.

（式（４）中、Ｒ^１５及びＲ^１６は、それぞれ独立に、単結合又は２価の有機基である。Ｂ^２は、単結合、上記式（１）で表される基又は上記式（１−１）で表される基である。ただし、式（１−１）中の「＊^１」は、式（４）中のＲ^１５に結合する結合手であることを示し、「＊」は、式（４）中のＲ^１６に結合する結合手であることを示す。ｎ４は０〜５の整数である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びｎ１は、上記式（１）と同義である。） Specific examples of the specific carboxylic acid include a compound represented by the following formula (4).

(In formula (4), R ¹⁵ and R ¹⁶ are each independently a single bond or a divalent organic group. B ² is a single bond, a group represented by the above formula (1) or the above formula ( 1-1) wherein “* ¹ ” in the formula (1-1) indicates a bond bonded to R ¹⁵ in the formula (4), and “*” Represents a bond bonded to R ¹⁶ in the formula (4), n4 is an integer of 0 to 5. R ¹ , R ² , R ³ , R ⁴ and n1 represent the above formula (1 Is synonymous with

Specific examples of such specific carboxylic acid include compounds represented by the following formulas (g-1) to (g-14). The specific carboxylic acid can be synthesized by appropriately combining organic chemistry methods. In the synthesis of the specific polyorganosiloxane, the specific carboxylic acid can be used alone or in combination of two or more.

  The content ratio of the partial structure represented by the above formula (1) in one molecule of the specific polyorganosiloxane is from the viewpoint of ensuring the reliability of backlight irradiation while improving the photosensitivity of the resulting coating film. It is preferable to set it as 5-90 mol% with respect to the silicon atom which specific polyorganosiloxane has, It is more preferable to set it as 10-85 mol%, It is further more preferable to set it as 15-80 mol%. Therefore, when synthesizing the specific polyorganosiloxane, it is preferable to select the use ratio of the specific carboxylic acid so that the content ratio of the partial structure represented by the formula (1) is within the above range.

（式中、ｊは０〜１２の整数であり、ｈは１〜１０の整数である。）
なお、その他のカルボン酸は、これらのうちから選択される１種を単独で又は２種以上を組み合わせて使用することができる。 In the synthesis of the specific polyorganosiloxane, the carboxylic acid used for the reaction with the epoxy group-containing polyorganosiloxane may be only the specific carboxylic acid, but other carboxylic acids other than the specific carboxylic acid may be used in combination. .
The other carboxylic acid is not particularly limited as long as it does not have the partial structure represented by the above formula (1), and examples thereof include carboxylic acid having the above liquid crystal alignment group. Specific examples of other carboxylic acids include fatty acids having 6 to 20 carbon atoms such as caproic acid, lauric acid, pentadecylic acid, palmitic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, and arachidic acid. And compounds represented by the following formulas (C-2-1) to (C-2-10).

(In the formula, j is an integer of 0 to 12, and h is an integer of 1 to 10.)
In addition, other carboxylic acid can be used individually by 1 type selected from these or in combination of 2 or more types.

  The proportion of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 mol, based on 1 mol of the total epoxy groups of the polyorganosiloxane, 0.01 to 1 More preferably, it is 0.0 mol. From the viewpoint of sufficiently obtaining the effects of the present invention, the proportion of other carboxylic acid used is preferably 80 mol% or less, based on the total amount of carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane, and is preferably 50 mol%. More preferably, it is as follows.

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent.
As the catalyst used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid, for example, an organic base or a compound known as a so-called curing accelerator that accelerates the reaction of the epoxy compound can be used. Examples of the organic base include primary and secondary organic amines such as ethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine and pyridine; quaternary organic amines such as tetramethylammonium hydroxide; Can do. Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines, imidazole compounds, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds such as tin octylate, quaternary ammonium salts, boron compounds, secondary chlorides. Examples thereof include metal halide compounds such as tin. Of these, quaternary ammonium salts are preferred, and specific examples include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride and the like.
The catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane. The

  Examples of the organic solvent used in the above reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Of these, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, and methyl. Examples thereof include isobutyl ketone and butyl acetate. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.

  The reaction temperature in the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Moreover, after completion | finish of reaction, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as necessary, and then the solvent is removed to obtain a specific polyorganosiloxane. The method for synthesizing the polyorganosiloxane is not limited to the hydrolysis / condensation reaction as described above. For example, a method in which a hydrolyzable silane compound is reacted in the presence of oxalic acid and alcohol may be employed.

  The specific polyorganosiloxane obtained as described above preferably has a solution viscosity of 1 to 500 mPa · s, and a solution of 3 to 200 mPa · s, when this is a 10% by weight solution. More preferably, it has a viscosity. For the specific polyorganosiloxane, the polystyrene-reduced weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, More preferably, it is 000-20,000.

[Poly (meth) acrylate]
The poly (meth) acrylate (hereinafter also referred to as “specific poly (meth) acrylate”) as the compound (X) is, for example, a (meth) acrylic monomer (n-1) having an epoxy group, or After polymerizing a mixture of the (meth) acrylic monomer (n-1) and other (meth) acrylic monomers in the presence of a polymerization initiator, the resulting polymer (hereinafter, “ It is also referred to as “epoxy group-containing poly (meth) acrylate”) and a specific carboxylic acid.

  Examples of the (meth) acrylic monomer (n-1) include unsaturated carboxylic acid esters having an epoxy group. Specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate. Α-ethyl acrylate 3,4-epoxybutyl, (meth) acrylate 3,4-epoxycyclohexylmethyl, (meth) acrylate 6,7-epoxyheptyl, α-ethyl acrylate 6,7-epoxyheptyl, Examples include 4-hydroxybutyl glycidyl ether of acrylic acid, (meth) acrylic acid (3-ethyloxetane-3-yl) methyl, and the like. In addition, a (meth) acrylic-type monomer (n-1) can be used individually by 1 type in the above or in combination of 2 or more types.

Examples of other (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α -Unsaturated carboxylic acids such as n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinylbenzoic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, ( (Meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid trimethoxysilylpropyl, (meth) acrylic acid methoxyethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meta ) Acrylic acid-N, N-diethylaminoethyl, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid octoxypolyethylene glycol, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl ( (Meth) acrylic acid ester: α-meth Shiakuriru methyl, alpha-ethoxy alpha-alkoxy acrylate ester of methyl acrylate: methyl crotonate, crotonic acid esters such as ethyl crotonate: unsaturated carboxylic acid esters and the like;
And unsaturated polyvalent carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride; and the like. In addition, as another (meth) acrylic-type monomer, it can be used individually by 1 type or in combination of 2 or more types.

In the synthesis of poly (meth) acrylate, the total amount (number of moles) of epoxy groups per gram of epoxy group-containing poly (meth) acrylate is preferably 5.0 × 10 ⁻⁵ or more, and 1.0 × 10 ^{-4 to} 1.0 × 10 ⁻² mol / g is more preferable, and 5.0 × 10 ^{−4 to} 5.0 × 10 ⁻³ mol / g is still more preferable. Therefore, the use ratio of the (meth) acrylic monomer (n-1) is adjusted so that the total number of moles of epoxy groups per 1 g of the epoxy group-containing poly (meth) acrylate is within the above numerical range. It is preferable.
In the polymerization, a monomer other than the (meth) acrylic monomer may be used. Examples of other monomers include conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene. The proportion of other monomers used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total amount of monomers used for the synthesis of poly (meth) acrylate.

The polymerization reaction using the (meth) acrylic monomer is preferably performed by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators usually used in radical polymerization. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4 -Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis ( Examples thereof include organic peroxides such as t-butylperoxy) cyclohexane; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. Of these, azo compounds are preferable, and 2,2′-azobis (isobutyronitrile) is more preferable. As a polymerization initiator, these can be used individually by 1 type or in combination of 2 or more types.
The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of all monomers used in the reaction.

  The polymerization reaction of the (meth) acrylic monomer is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred examples thereof include diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate. In addition, as an organic solvent, these can be used individually by 1 type or in combination of 2 or more types.

  In the polymerization reaction of the (meth) acrylic monomer, the reaction temperature is preferably 30 to 120 ° C, more preferably 60 to 110 ° C. The reaction time is preferably 1 to 36 hours, and more preferably 2 to 24 hours. The amount of organic solvent used (a) is such that the total amount (b) of monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount of reaction solution (a + b). It is preferable to do.

The epoxy group-containing poly (meth) acrylate obtained by the above reaction is then reacted with a specific carboxylic acid. Specific examples of the specific carboxylic acid include the compounds exemplified in the description of the specific polyorganosiloxane. In the reaction, the specific carboxylic acid may be used alone, or other carboxylic acids other than the specific carboxylic acid may be used in combination.
The use ratio of the carboxylic acid to be reacted with the epoxy group-containing poly (meth) acrylate may be 0.001 to 0.95 mol with respect to a total of 1 mol of epoxy groups contained in the epoxy group-containing poly (meth) acrylate. preferable. More preferably, it is 0.01-0.9 mol, and it is still more preferable to set it as 0.05-0.8 mol.

  The reaction between the epoxy group-containing poly (meth) acrylate and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. Here, as a catalyst used for reaction, the compound illustrated as a catalyst which can be used by the synthesis | combination of specific polyorganosiloxane can be mentioned, for example. Among these, a quaternary ammonium salt is preferable. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy group-containing poly (meth) acrylate. It is.

  As the organic solvent used in the reaction, examples of the organic solvent that can be used in the polymerization of the (meth) acrylic monomer can be applied, and among them, an ester is preferable. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  Thus, a solution containing the specific poly (meth) acrylate can be obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after the specific poly (meth) acrylate contained in the reaction solution is isolated or isolated. You may use for preparation of a liquid crystal aligning agent, after refine | purifying specific poly (meth) acrylate. The isolation and purification of the specific poly (meth) acrylate can be performed according to a known method.

  In addition, the synthesis method of specific poly (meth) acrylate is not limited to the said method. For example, a (meth) acrylic monomer having a partial structure represented by the above formula (1), or a mixture of the (meth) acrylic monomer and another (meth) acrylic monomer, It can also be obtained by a method of polymerizing in the presence of a polymerization initiator.

  The number average molecular weight (Mn) in terms of polystyrene measured by GPC for a specific poly (meth) acrylate improves the liquid crystal alignment of the liquid crystal alignment film to be formed and ensures the stability of the liquid crystal alignment over time. From the viewpoint of doing, it is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Other ingredients>
The liquid crystal aligning agent of this indication may contain other components other than compound (X) in the range which does not prevent the objective and effect of this indication.
[Other polymers]
Examples of the other component include a polymer having no partial structure represented by the above formula (1) (hereinafter also referred to as “other polymer”). Other polymers can be used to improve solution properties and electrical properties. Specific examples of such other polymers include, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meta ) A polymer having an acrylate or the like as a main skeleton can be mentioned. Among these, at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate, and polyamide is preferable.
When other polymers are blended in the liquid crystal aligning agent, the blending ratio is preferably 80 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it as 70 weight part, and it is still more preferable to set it as 0.5-60 weight part.

  As other components, in addition to the above, for example, a compound having at least one epoxy group in the molecule, a functional silane compound, a surfactant, a filler, a pigment, an antifoaming agent, a photosensitizer, a photopolymerizable group Examples thereof include a containing compound, a dispersant, an antioxidant, an adhesion assistant, an antistatic agent, a leveling agent, and an antibacterial agent. In addition, these mixing | blending ratios can be suitably set in the range which does not prevent the effect of this invention according to each compound to mix | blend.

<Solvent>
The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which compound (X) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.

  Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether , Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Recall diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. be able to. These can be used individually or in mixture of 2 or more types.

The liquid crystal aligning agent of this indication may contain only 1 type of polymer as a polymer component, and may contain 2 or more types of polymers. Preferable embodiments of the polymer component include, for example, the following [1] and [2].
[1] The polymer component is a polymer as the compound (X) (hereinafter also referred to as “specific polymer”), and the specific polymer is polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane. And at least one selected from the group consisting of poly (meth) acrylates.
[2] The polymer component is a specific polymer and other polymers, and the specific polymer and other polymers are polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane, and poly (meth). An embodiment that is at least one selected from the group consisting of acrylates.
In the embodiment of [2], the specific polymer is a polymer having a fluorine atom or a silicon atom, so that the specific polymer having a fluorine atom or a silicon atom has a fluorine atom and a silicon atom in the upper layer. It is presumed that other polymers that are not present are unevenly distributed in the lower layer, and that the distribution of polymers in the liquid crystal alignment film can be biased. In this case, even if the content ratio of the specific polymer in the liquid crystal aligning agent is reduced, it is preferable in that a liquid crystal display device having high photosensitivity of the obtained coating film and excellent reliability for backlight irradiation can be obtained. is there.

  When the specific polymer as the compound (X) is at least one selected from polyamic acid, polyamic acid ester, and polyimide, the compound (X) is an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic acid dicarboxylic acid. It is preferable to further have a structural unit derived from at least one acid dianhydride selected from the group consisting of anhydrides. By having such a structural unit, it is preferable in that a liquid crystal display element having higher reliability with respect to backlight irradiation can be obtained.

  Although the reason why the liquid crystal aligning agent containing the compound (X) is used to improve the reliability of the liquid crystal display element for backlight irradiation is not clear, one hypothesis is that the stilbene structure It is conceivable that by introducing a substituent into the heavy bond portion, the planarity of the double bond is lowered, and the ultraviolet absorption band of the obtained coating film is shifted by a short wavelength.

  The solid content concentration in the liquid crystal aligning agent of the present disclosure (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of this indication is apply | coated to the substrate surface so that it may mention later, Preferably the coating film which becomes a liquid crystal aligning film or a coating film used as a liquid crystal aligning film is formed by heating. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.

  The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature when preparing the liquid crystal aligning agent according to the present invention is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.

<Liquid crystal alignment film and liquid crystal display element>
A liquid crystal alignment film can be produced by using the liquid crystal aligning agent of the present disclosure described above. Moreover, the liquid crystal display element of this indication comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present disclosure is not particularly limited. It can be applied to the operation mode.

  The liquid crystal display element of this indication can be manufactured by the method of including the following processes 1-3, for example. In step 1, the substrate to be used varies depending on the desired operation mode. Step 2 and step 3 are common to each operation mode.

[Step 1: Formation of coating film]
First, the liquid crystal aligning agent of this indication is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.
(1-A) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, a pair of two substrates provided with patterned transparent conductive films is formed, and each transparent conductive film is formed. On the surface, the liquid crystal aligning agent of the present disclosure is preferably applied by an offset printing method, a spin coating method, a roll coater method, or an ink jet printing method, respectively. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  (1-B) When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. The liquid crystal aligning agent of this indication is each apply | coated to one surface of the counter substrate which is not carried out, Then, a coating film is formed by heating each application surface. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed Same as (1-A). As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (1-A) and (1-B), a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film is formed by applying a liquid crystal aligning agent on the substrate and then removing the organic solvent. Is done. At this time, when the liquid crystal aligning agent contains at least one of polyamic acid, polyamic acid ester, and polyimide, by further heating after forming the coating film, the polyamic acid, polyamic acid ester, and polyimide in the liquid crystal aligning agent It is good also as a more imidized coating film by making the dehydration ring-closing reaction proceed.

[Step 2: Orientation ability imparting treatment]
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the alignment ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment in which the coating film is irradiated with polarized or non-polarized radiation. Processing. In particular, since a coating film formed using the liquid crystal aligning agent of the present disclosure has high photosensitivity, the photo-alignment treatment can be preferably applied. On the other hand, when manufacturing a VA type liquid crystal display element, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to alignment ability imparting treatment.

  The light irradiation in the photo-alignment treatment is [1] a method of irradiating the coating film after the post-baking process, [2] a method of irradiating the coating film after the pre-baking process and before the post-baking process, [3 ] It can carry out by the method of irradiating with respect to a coating film during the heating of a coating film in at least any one of a prebaking process and a post-baking process.

As the radiation applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the direction of irradiation is an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The radiation dose is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

  Note that the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays, A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. A liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step 3: Construction of liquid crystal cell]
(3-A) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates facing each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the seal are bonded. A liquid crystal cell is manufactured by injecting and filling liquid crystal into the cell gap partitioned by the agent and then sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. . Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

(3-B) When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound (polymer or additive) having a photopolymerizable group, a liquid crystal cell is prepared in the same manner as (3-A) above. Then, a method of manufacturing a liquid crystal display element may be adopted by performing a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. Here, the applied voltage can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The irradiation dose of light, preferably less than 1,000 J / ^{m 2} or more 200,000 J / ^{m 2,} more preferably from 1,000~100,000J / ^{m 2.}

  And the liquid crystal display element of this indication can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

  The liquid crystal display element of the present disclosure can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, cellular phones, smartphones, The present invention can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw and epoxy equivalent of the polymer were measured by the following methods. Hereinafter, the compound represented by Formula A may be simply referred to as “Compound A”.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene equivalent value measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²

<Synthesis of compounds>
[Example 1-1: Synthesis of compound (b-1)]
Compound (b-1) was synthesized according to the following scheme 1.

To 400 ml of 1,2-dimethoxyethane, 63.2 g of titanium tetrachloride and 50.9 g of zinc powder were added and refluxed. A 100 ml solution of 1,2-dimethoxyethane to which 10.0 g of 4′-nitroacetophenone was added was slowly added dropwise over 2 hours. After completion of dropping, the mixture was stirred for 12 hours while refluxing. Thereafter, the reaction solution was allowed to cool to room temperature, 500 ml of ethyl acetate was added, and this was separated with pure water. Then, this was concentrated and the intermediate body (b-1-1) was obtained with 15.0 g of pale yellow solids, and purity 99%.
14.0 g of the obtained intermediate (b-1-1) and 61.0 g of zinc powder were added to 200 ml of tetrahydrofuran, and 30.0 g of acetic acid was further added. Then, it stirred at 60 degreeC for 5 hours. The reaction solution was allowed to cool to room temperature, 300 ml of ethyl acetate was added, and the mixture was separated with pure water.

[Example 1-2: Synthesis of compound (b-2)]
In the first stage of Scheme 1 in Example 1-1, instead of using 4′-nitroacetophenone alone, 4′-nitroacetophenone and 4-nitrobenzaldehyde were added in an equivalent amount, and purification was performed by column chromatography ( The compound (b-2) was obtained in the same manner as in Example 1-1 except that silica gel / hexane / ethyl acetate mixed solvent (volume ratio 1: 1)) was used.

[Example 1-3: Synthesis of compound (d-1)]
Compound (d-1) was synthesized according to the following scheme 2.

10 ml of 4-bromophthalic acid dimethyl ester, 2.9 g of 1,4-diisopropenylbenzene, 0.08 g of palladium acetate, 0.22 g of tri (o-tolyl) phosphine, and 7.4 g of triethylamine were added to 50 ml of N, N-dimethylacetamide. Added to. Then, it stirred at 60 degreeC for 12 hours. The reaction solution was allowed to cool to room temperature, 200 ml of ethyl acetate was added, and the solution was partitioned between hydrochloric acid and pure water. Then, this was concentrated and the intermediate body (d-1-1) was obtained by pale yellow solid 8.0g, purity 99%.
Next, 8.0 g of the intermediate (d-1-1) and 3.0 g of sodium hydroxide were added to 50 g of water and refluxed for 12 hours, and then the by-produced methanol was distilled off under reduced pressure. Thereafter, 20 ml of concentrated hydrochloric acid was added dropwise with stirring, and the produced solid was filtered and dried to obtain 6.5 g of a light yellow solid (purity 99%) as an intermediate (d-1-2).
6.5 g of the obtained intermediate (d-1-2) was added to 20 g of acetic anhydride, and then stirred at 80 ° C. for 12 hours. The reaction solution was allowed to cool to room temperature, and then the precipitated solid was filtered, washed with hexane and dried to obtain compound (d-1) as a pale yellow solid (4.5 g).

<Synthesis of polymer>
[Example 2-1: Synthesis of polymer (A-1)]
100 mol parts of 4,4′-oxydiphthalic anhydride as tetracarboxylic dianhydride and 100 mol parts of compound (b-1) as diamine are dissolved in N-methyl-2-pyrrolidone (NMP), and 60 ° C. The solution was reacted for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The obtained polyamic acid (hereinafter referred to as “polymer (A-1)”) had a weight average molecular weight Mw of 40,000.

[Examples 2-2 to 2-6 and Synthesis Examples 1-1 to 1-2]
A polyamic acid (polymers (A-2) to (A-6) was obtained in the same manner as in Example 2-1 except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below. ), Polymer (B-1) and polymer (B-2)) were synthesized respectively.

In Table 1, the numbers in parentheses of tetracarboxylic dianhydride and diamine represent the usage ratio [mole part] with respect to a total of 100 parts by mole of tetracarboxylic dianhydride used for the synthesis of the polymer. Abbreviations in Table 1 have the following meanings, respectively.
<Tetracarboxylic dianhydride>
a-1: 4,4'-oxydiphthalic anhydride a-2: ethylenediaminetetraacetic acid dianhydride a-3: propylene glycol bisanhydrotrimate a-4: 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydride a-5: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride <diamine>
b-1: Compound represented by the above formula (b-1) b-2: Compound represented by the above formula (b-2) c-1: 1,4-bis (4-aminophenyl) piperazine c- 2: 1,4-bis (4-aminophenoxy) butane c-3: 4,4′-diaminostilbene c-4: p-phenylenediamine c-5: bis (4-aminophenyl) amine d-1: above Compound represented by formula (d-1)

[Example 3-1]
1. Preparation of liquid crystal aligning agent As a polymer component, NMP and butyl cellosolve (BC) are added to the solution containing the polymer (A-1) obtained in Example 2-1 above, and the mixture is sufficiently stirred. : BC = 70: 30 (weight ratio), a solid content concentration of 3.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 0.45 μm.

2. Production of Optical FFS Type Liquid Crystal Display Element The FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape are formed in this order, and an electrode The counter glass substrate 11b not provided with a pair of the glass substrate 11a and the surface of the glass substrate 11a having a transparent electrode and one surface of the counter glass substrate 11b are respectively 1. The liquid crystal aligning agent prepared in (1) was applied using a spinner to form a coating film.
A schematic plan view of the used top electrode 13 is shown in FIG. 2A is a top view of the top electrode 13, and FIG. 2B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2A. In this example, the line width d1 of the electrodes was 4 μm, and the distance d2 between the electrodes was 6 μm. Further, as the top electrode 13, four systems of drive electrodes of electrode A, electrode B, electrode C, and electrode D were used (FIG. 3). The bottom electrode 15 functions as a common electrode that acts on all of the four systems of drive electrodes, and each of the four systems of drive electrodes serves as a pixel area.
After the coating film was formed by the spinner, the coating film was pre-baked for 1 minute on an 80 ° C. hot plate. Next, each surface of the coating film was irradiated with polarized ultraviolet light 5,000 J / m ² using a Hg—Xe lamp and a Grand Taylor prism to obtain a pair of substrates having a liquid crystal alignment film. At this time, the irradiation direction of the polarized ultraviolet rays is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment in which the polarization plane of the polarized ultraviolet rays is projected onto the substrate is the direction of the double-headed arrow in FIG. The light irradiation process was performed after setting. After light irradiation, the film was heated (post-baked) at 230 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having an average film thickness of 0.1 μm.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are then applied. It was made to oppose and it piled up and crimped | bonded so that the direction which the polarization plane of polarized ultraviolet rays projected on the board | substrate might become parallel, and the adhesive was thermoset at 150 degreeC over 1 hour. Next, after filling the substrate gap from the liquid crystal injection port with liquid crystal “MLC-7028” manufactured by Merck, the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature.
Next, an FFS type liquid crystal display element was manufactured by attaching polarizing plates to both outer surfaces of the substrate. At this time, one of the polarizing plates is stuck so that the polarization direction thereof is parallel to the direction of projection of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film onto the substrate surface, and the other one has the polarization direction first. The polarizing plate was stuck so as to be orthogonal to the polarization direction of the polarizing plate.
In addition, by performing the above series of operations by changing the ultraviolet irradiation amount before post-baking within the range of 100 to 10,000 J / m ² , three or more liquid crystal display elements having different ultraviolet irradiation amounts can be obtained. Manufactured.

3. Evaluation of liquid crystal display element 2. The following (1) was evaluated using the liquid crystal display device manufactured in (1). Further, the above 2. except that the polarizing plate was not bonded. A liquid crystal display element (a liquid crystal cell in which a polarizing plate was not bonded) was manufactured by performing the same operation as described above, and the following (2) was evaluated. As for the evaluation results, the best results were selected from three or more liquid crystal display elements with different ultraviolet irradiation amounts.

(1) Evaluation of contrast after driving stress The liquid crystal display device manufactured in (1) is driven at an AC voltage of 10 V for 30 hours, and then a device in which a polarizer and an analyzer are arranged between the light source and the light amount detector is used. The transmittance (%) was measured.
Minimum relative transmittance (%) = (β−B ⁰ ) / (B ¹⁰⁰ −B ⁰ ) × 100 (1)
(In Formula (1), B ⁰ is the transmission amount of light under the crossed Nicols in the blank. B ¹⁰⁰ is the transmission amount of the light in the blanks and under the Paranicol. Β is the polarizer under the crossed Nicols. (The liquid crystal display element is sandwiched between the analyzers, and this is the minimum light transmission amount.)
The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state, the better the contrast. A sample with a minimum relative transmittance of less than 0.5% is defined as “Good (◯)”, a sample having a minimum relative transmittance of less than 0.5% and less than 1.0% is defined as “Available” (△), “Bad (×)”. As a result, the contrast evaluation of this liquid crystal display element was determined to be “good”.
(2) Evaluation of VHR reliability The change rate (ΔVHR) of the voltage holding ratio after 200 hours had passed under the backlight irradiation for a liquid crystal display element manufactured by the same method as above (however, a liquid crystal cell without a polarizing plate bonded) It was measured. The voltage holding ratio was measured by applying a voltage of 1 V to the liquid crystal display element for 60 microseconds with a span of 16.7 milliseconds, and then measuring the voltage holding ratio after 16.7 milliseconds from the release of application. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The change rate ΔVHR (%) was obtained by the following mathematical formula (2).
ΔVHR = ((VHR _BF −VHR _AF ) ÷ VHR _BF ) × 100 (2)
(In Formula (2), VHR _BF is a voltage holding ratio measured before backlight irradiation, and VHR _AF is a voltage holding ratio measured after backlight irradiation.)
The evaluation of reliability is “good (◯)” when the change rate ΔVHR is less than 2.0%, and “good (Δ)” when the change rate ΔVHR is 2.0% or more and less than 3.0%. The case where it was 0.0% or more was defined as “defective (×)”. As a result, the liquid crystal display element of this example had “good” reliability.

[Examples 3-2 to 3-5 and Comparative Example 1]
A liquid crystal aligning agent was prepared at the same solvent ratio and solid content concentration as in Example 3-1, except that the type of polymer used was changed as shown in Table 2 below. In addition, a liquid crystal display element was produced using each liquid crystal aligning agent in the same manner as in Example 3-1, and various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below. In Table 2, the numerical value in parentheses in the polymer column indicates the blending ratio [parts by weight] of each polymer with respect to 100 parts by weight in total of the polymer components used for preparing the liquid crystal aligning agent.

[Example 3-6]
A liquid crystal aligning agent was prepared with the same solvent ratio and solid content concentration as in Example 3-1, except that the type of polymer used was changed to polymer (A-4). Moreover, while manufacturing the liquid crystal display element similarly to the said Example 3-1, the point which used the liquid crystal aligning agent prepared in the present Example, and the point which implemented the photo-alignment process by a polarized ultraviolet ray after post-baking. Various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below.

  As for the liquid crystal display element manufactured using the liquid crystal aligning agent containing compound (X), the evaluation of contrast and VHR reliability was “good” or “good” in any of the examples. (Example 3-1 to Example 3-6). On the other hand, the liquid crystal display element manufactured using the liquid crystal aligning agent of the comparative example which does not contain compound (X) was inferior to the example of the VHR reliability evaluation.

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11a, 11b ... Board | substrate, 12 ... Liquid crystal aligning film, 13 ... Top electrode, 14 ... Insulating layer, 15 ... Bottom electrode, 16 ... Liquid crystal layer

Claims (10)

The liquid crystal aligning agent containing the compound (X) which has the partial structure represented by following formula (1).

(In Formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group, and R ² is a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group. R ³ and R ⁴ are each independently a substituent, and may be bonded to another group to form at least a part of the ring, and n1 and n2 are each independently an integer of 0 to 4. When n1 is 2 or more, the plurality of R ³ may be the same or different, and when n2 is 2 or more, the plurality of R ⁴ may be the same or different, “*” indicates a bond. )   The liquid crystal aligning agent according to claim 1, wherein the compound (X) is at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane, and poly (meth) acrylate. . The compound (X) is at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and has a structural unit derived from a monomer having a partial structure represented by the above formula (1). And
3. The liquid crystal aligning agent according to claim 1, wherein the monomer is at least one selected from the group consisting of diamine, tetracarboxylic dianhydride, tetracarboxylic diester, and tetracarboxylic diester dihalide. The monomer includes a tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide, and the tetracarboxylic acid derivative is represented by the following formula (2-1): The liquid crystal aligning agent of Claim 3 which is at least 1 type of tetracarboxylic dianhydride or its derivative (s) chosen from the group which consists of the compound represented by this, and the compound represented by following formula (2-2).

(In Formula (2-1), R ⁵ and R ⁸ are each independently a trivalent organic group, and R ⁶ and R ⁷ are each independently a single bond or a divalent linking group. ¹ , R ² , R ³ , R ⁴ , n1 and n2 are as defined in the above formula (1).

(In the formula (2-2), R ¹⁵ is a divalent organic group, and n4 is 0 or 1. R ¹ , R ² , R ³ , R ⁴ , n1 and n2 are represented by the above formula (1 When n4 = 1, a plurality of n2s may be the same or different.) The liquid crystal aligning agent of Claim 3 or 4 in which the said monomer contains the diamine represented by following formula (3).

(In Formula (3), R ^{9 to} R ¹¹ are each independently a single bond or a divalent organic group. B ¹ is a single bond, a group represented by the above formula (1), or a group represented by the following formula ( (1-1) R ¹ , R ² , R ³ , R ⁴ , n1 and n2 have the same meanings as in the above formula (1).

(In formula (1-1), R ¹² is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group, and R ¹³ is a halogen atom, a hydroxyl group, a cyano group or a monovalent organic group. R ¹⁴ is a substituent, and may be bonded to another group to form at least a part of the ring, n3 is an integer of 0 to 4, and when n3 is 2 or more, a plurality of of R ¹⁴ may be the same or different. "* ^1" and "*" indicates that the bond. However, "* ^1" is attached to R ^10.)   The manufacturing method of the liquid crystal aligning film including the process of apply | coating the liquid crystal aligning agent as described in any one of Claims 1-5 on a board | substrate, and forming the coating film, and the process of irradiating the said coating film with light.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-5.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 7. A polymer having a partial structure selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, and poly (meth) acrylate and represented by the following formula (1).

(In Formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group, and R ² is a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group. R ³ and R ⁴ are each independently a substituent, and may be bonded to another group to form at least a part of the ring, and n1 and n2 are each independently an integer of 0 to 4. When n1 is 2 or more, the plurality of R ³ may be the same or different, and when n2 is 2 or more, the plurality of R ⁴ may be the same or different, “*” indicates a bond. ) A tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, wherein the compound is represented by the following formula (2-1) and the following formula (2- A tetracarboxylic acid derivative which is a tetracarboxylic dianhydride or a derivative thereof selected from the group consisting of compounds represented by 2).

(In Formula (2-1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group, and R ² is a halogen atom, a hydroxyl group, a cyano group, or a monovalent organic group. R ³ and R ⁴ are each independently a substituent, and may be bonded to another group to form at least a part of the ring, and n1 and n2 are each independently 0 to 4 When n1 is 2 or more, the plurality of R ³ may be the same or different, and when n2 is 2 or more, the plurality of R ⁴ may be the same or different, and R ⁵ and R ⁸ are Each is independently a trivalent organic group, and R ⁶ and R ⁷ are each independently a single bond or a divalent linking group.)

(In the formula (2-2), R ¹⁵ is a divalent organic group, and n4 is 0 or 1. R ¹ , R ² , R ³ , R ⁴ , n1 and n2 are represented by the formula (2 -1) and when n4 = 1, a plurality of n2 may be the same or different.

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