JP6729740B2 - Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display device - Google Patents

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, and a liquid crystal display device.

Liquid crystal display devices are widely used in televisions, mobile devices, various monitors, and the like. Further, in a liquid crystal display element, a liquid crystal alignment film is used to control the alignment of liquid crystal molecules in a liquid crystal cell. As a method for obtaining an organic film having a liquid crystal alignment regulating force, 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 a photosensitive organic film have been used. A method of irradiating a film with light (a 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 can also precisely control the liquid crystal alignment direction. Is being promoted (see, for example, Patent Document 1). Patent Document 1 discloses that a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a polyimide precursor having a cinnamoyl group in the main chain, polyimide or polyamide.

International Publication No. 2013/161984

In recent years, high-definition liquid crystal televisions with large screens are mainly used, and small display terminals such as smartphones and tablet PCs have become widespread, and the demand for high-definition liquid crystal panels is further increasing. Specifically, it is important for improving the display quality of the liquid crystal display element that afterimages are hard to occur (afterimage characteristics) and good contrast (contrast characteristics), and these various characteristics are further improved. Is required.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a liquid crystal aligning agent that can obtain a liquid crystal display device having good afterimage characteristics and contrast characteristics.

As a result of intensive studies to achieve the above-mentioned problems of the conventional techniques, the present inventors have found that the above-mentioned problems can be solved by containing a compound having a specific structure in the liquid crystal aligning agent. The invention was completed. Specifically, the following liquid crystal aligning agent, liquid crystal aligning film, method for producing a liquid crystal aligning film, and liquid crystal display device are provided.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、ハロゲン原子、シアノ基又は１価の有機基であり、Ｒ^３は置換基である。ただし、Ｒ^１及びＲ^２の少なくとも一方は、ハロゲン原子、シアノ基又は１価の有機基である。Ｘ^１は酸素原子又は−ＮＲ^４−（ただし、Ｒ^４は水素原子、水酸基又は１価の有機基であり、Ｒ^４が他の基に結合して窒素原子と共に環構造を形成してもよい。）である。Ｒ^３は、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。ｎは０〜４の整数である。ｎが２以上の場合、複数のＲ^３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 a polymer having a partial structure represented by the following formula (1) in the main chain.

(In the formula (1), ^{R 1} and ^{R 2} are each independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, ^{R 3} is a substituent. However, ^{R 1} and ^{R 2} At least one of them is a halogen atom, a cyano group or a monovalent organic group, X ¹ is an oxygen atom or —NR ⁴ — (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ is R ³ may be bonded to another group to form a ring structure together with a nitrogen atom.) R ³ may be bonded to another group to form at least a part of the ring, and n is 0. Is an integer from 4 to 4. When n is 2 or more, a plurality of R ³ 's may be the same or different. "*" represents a bond.

（式（２−１）中、Ａ^１は下記式（１−１）で表される基又は下記式（１−２）で表される基であり、Ａ^２は単結合、下記式（１−１）で表される基又は下記式（１−２）で表される基である。Ｒ^５は、Ａ^１が下記式（１−１）で表される基の場合に２価の有機基であり、Ａ^１が下記式（１−２）で表される基の場合に単結合又は２価の有機基である。Ｒ^７は、Ａ^２が下記式（１−１）で表される基の場合に２価の有機基であり、Ａ^２が下記式（１−２）で表される基又は単結合の場合に単結合又は２価の有機基である。Ｒ^６は２価の有機基である。ただし、下記式（１−１）及び式（１−２）中の「＊１」は、Ｒ^６に結合している。）

（式（１−１）及び式（１−２）中、Ｒ^１，Ｒ^２，Ｒ^３，Ｘ^１及びｎは上記式（１）と同義である。「＊１」は結合手を示す。） [1-1] In the above-mentioned [1], one preferable embodiment is that the polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and It has a partial structure derived from the compound represented by formula (2-1).

(In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1 -1) or a group represented by the following formula (1-2): R ⁵ is a divalent organic group when A ¹ is a group represented by the following formula (1-1). a group, .R ^{7 a 1} is a single bond or a divalent organic group in the case of a group represented by the following formula (1-2), ^{a 2} is represented by the following formula (1-1) Is a divalent organic group, and A ² is a group represented by the following formula (1-2) or a single bond or a divalent organic group when A ² is a single bond: R ⁶ is divalent (However, “*1” in the following formulas (1-1) and (1-2) is bonded to R ⁶ ).

(In the formula (1-1) and the formula ^{(1-2), R 1, R} 2, R 3, X 1 and n are as defined in the above formula (1). "* 1" represents a bond. )

（式（５−１）中、Ａ^３は下記式（１−１）で表される基又は下記式（１−２）で表される基であり、Ａ^４は単結合、下記式（１−１）で表される基又は下記式（１−２）で表される基である。Ｒ^１５及びＲ^１７は、それぞれ独立に芳香族環基、脂環式基又は複素環基であり、Ｒ^１６は２価の有機基であり、Ｘ^３及びＸ^４は、それぞれ独立に単結合又は２価の連結基である。ただし、下記式（１−１）及び式（１−２）中の「＊１」は、Ｒ^１６に結合する。）

（式（１−１）及び式（１−２）中、Ｒ^１，Ｒ^２，Ｒ^３，Ｘ^１及びｎは上記式（１）と同義である。「＊１」は結合手を示す。）

（式（５−２）中、Ｒ^１８は２価の有機基であり、Ｒ^１９は、芳香族環基、脂環式基又は複素環基である。Ｒ^１，Ｒ^２及びＸ^１は上記式（１）と同義である。） [1-2] In the above [1] and [1-1], one preferable embodiment is that the polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. And a partial structure derived from a specific acid dianhydride that is at least one selected from the group consisting of a compound represented by the following formula (5-1) and a compound represented by the following formula (5-2) Have.

(In the formula (5-1), A ³ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ is a single bond, and the following formula (1) -1) or a group represented by the following formula (1-2): R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group; R ¹⁶ is a divalent organic group, and X ³ and X ⁴ are each independently a single bond or a divalent linking group, provided that in the formulas (1-1) and (1-2) below. "*1" binds to R ^16. )

(In the formula (1-1) and the formula ^{(1-2), R 1, R} 2, R 3, X 1 and n are as defined in the above formula (1). "* 1" represents a bond. )

(In the formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group or a heterocyclic group. R ¹ , R ² and X ¹ are the above. It is synonymous with Formula (1).)

[2] A method for producing a liquid crystal alignment film, comprising the steps of applying the liquid crystal alignment agent of [1] above to a substrate to form a coating film, and irradiating the coating film with light.
[3] A liquid crystal alignment film formed using the liquid crystal alignment agent according to [1] above.
[4] A liquid crystal display device including the liquid crystal alignment film according to the above [3].

According to the liquid crystal aligning agent containing the polymer having the partial structure represented by the above formula (1) in the main chain as the compound (X) having the partial structure represented by the above formula (1), an afterimage (particularly an AC voltage It is possible to obtain a liquid crystal display element in which an afterimage) is less likely to occur and which has a good contrast.

The schematic block diagram of a FFS type liquid crystal display element. FIG. 3 is a schematic plan view of a top electrode used for manufacturing a liquid crystal display element by optical alignment processing. (A) is a top view of a top electrode, (b) is a partial enlarged view 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 the present disclosure and other components optionally blended as necessary will be described.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、ハロゲン原子、シアノ基又は１価の有機基であり、Ｒ^３は置換基である。ただし、Ｒ^１及びＲ^２の少なくとも一方は、ハロゲン原子、シアノ基又は１価の有機基である。Ｘ^１は酸素原子又は−ＮＲ^４−（ただし、Ｒ^４は水素原子、水酸基又は１価の有機基であり、Ｒ^４が他の基に結合して窒素原子と共に環構造を形成してもよい。）である。Ｒ^３は、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。ｎは０〜４の整数である。ｎが２以上の場合、複数のＲ^３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 the present disclosure contains a compound having a partial structure represented by the following formula (1) (hereinafter, also referred to as “compound (X)”).

(In the formula (1), ^{R 1} and ^{R 2} are each independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, ^{R 3} is a substituent. However, ^{R 1} and ^{R 2} At least one of them is a halogen atom, a cyano group or a monovalent organic group, X ¹ is an oxygen atom or —NR ⁴ — (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ is R ³ may be bonded to another group to form a ring structure together with a nitrogen atom.) R ³ may be bonded to another group to form at least a part of the ring, and n is 0. Is an integer from 4 to 4. When n is 2 or more, a plurality of R ³ 's may be the same or different. "*" represents 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, a fluoroalkyl group having 1 to 20 carbon atoms, Examples thereof include 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, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , Heptyl group, octyl group, nonyl group, decyl group and the like. The alkoxy group having 1 to 20 carbon atoms includes, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and the like; and the fluoroalkyl group having 1 to 20 carbon atoms includes, for example, perfluoromethyl group, peroxymethyl group Fluoroethyl group, 2,2,2-trifluoroethyl group and the like; Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopentyl group, cyclohexyl group and methylcyclohexyl group; 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 and the like.
Examples of the halogen atom of R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

At least one of R ¹ and R ² is a halogen atom, a cyano group or a monovalent organic group, but at least R ² is a halogen from the viewpoint of sufficiently expressing the alignment control force of the liquid crystal by light irradiation. It is preferably an atom, a cyano group or a monovalent organic group. Specifically, R ¹ is preferably a hydrogen atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably a hydrogen atom. More preferable. Further, R ² is preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms, more preferably a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group. Among them, a combination in which R ¹ is a hydrogen atom and R ² is a methyl group is particularly preferable.

R ^{4 in} —NR ⁴ — is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a protecting group. Examples of the protecting group include a carbamate protecting group, an amide protecting group, an imide protecting group, a sulfonamide protecting group and the like. Preferred is a carbamate-based protecting group, and specific examples thereof include t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1-dimethyl-2-. Examples thereof include a cyanoethyloxycarbonyl group, a 9-fluorenylmethylcarbonyl group, an allyloxycarbonyl group and a 2-(trimethylsilyl)ethoxycarbonyl group. A t-butoxycarbonyl group is preferable because it is easily deprotected by heat and the released compound is easily discharged as a gas out of the membrane.
Of these, R ⁴ is preferably a hydrogen atom, a methyl group, a hydroxyl group or a t-butoxycarbonyl group, and more preferably a hydrogen atom or a methyl group. R ⁴ may combine with another group to form a ring structure with the nitrogen atom. Examples of such a ring structure include piperidine and piperazine. X ¹ is preferably an oxygen atom.
Examples of the substituent of R ³ include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, an alkylsilyl group, an alkoxysilyl group and an ester. Groups and the like. Examples of the ring formed by combining R ³ with another group include an imide ring. 0-2 are preferable and, as for n, 0 or 1 is more preferable. “*” in the formula (1) may be bonded to a hydrogen atom, may be bonded to an organic group, or may be bonded to R ³ to form a ring structure (for example, an imide ring). May be.

The compound (X) may be a polymer component that can be a main component of the liquid crystal alignment film, or an additive component that is blended separately from the polymer component. Among these, it is preferable that the liquid crystal aligning agent is contained as at least a part of the polymer component from the viewpoint of high anisotropy expressing effect by the photo-alignment method, and the partial structure represented by the above formula (1) is It is particularly preferable to have it in the main chain of the polymer.
Here, the “main chain” of the polymer in the present specification refers to a “stem” portion composed of the longest chain of atoms in the polymer. It should be noted that this "stem" portion is allowed to include 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 is not excluded that the partial structure represented by the above formula (1) is also present in a portion other than the main chain, for example, a side chain (a portion branched from the “stem” of the polymer). The “organic group” means a group containing a hydrocarbon group, and may contain a hetero atom in the structure.

The main skeleton when the compound (X) is a polymer is not particularly limited, and examples thereof include polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenyl). Examples of the main skeleton include maleimide) derivatives and poly(meth)acrylates.
Among these, 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. It is preferably a polymer (hereinafter, also referred to as “polymer (A)”), and more preferably at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane. It is more preferably at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester. The polymer used for preparing the liquid crystal aligning agent may be only one kind or two or more kinds. (Meth)acrylate is meant to include acrylates and methacrylates.

[Polyamic acid]
The polyamic acid as the compound (X) is a polyamic acid having a partial structure represented by the above formula (1), and can be obtained, for example, by reacting a tetracarboxylic dianhydride and a diamine. Specifically, [1] a method of polymerizing a monomer containing a tetracarboxylic acid dianhydride having a partial structure represented by the above formula (1) (hereinafter, also referred to as "specific acid-free dihydrate"), [ 2] A method of polymerizing a monomer containing a diamine having a partial structure represented by the above formula (1) (hereinafter also referred to as "specific diamine"), [3] containing the specific acid-free dihydrate and the specific diamine. The method of polymerizing a monomer, etc. are mentioned. Among these, it is preferable to use the specific diamine because the monomer is relatively easy to synthesize, and specifically, the method [2] is preferable.

（式（５−１）中、Ａ^３は下記式（１−１）で表される基又は下記式（１−２）で表される基であり、Ａ^４は単結合、下記式（１−１）で表される基又は下記式（１−２）で表される基である。Ｒ^１５及びＲ^１７は、それぞれ独立に芳香族環基、脂環式基又は複素環基であり、Ｒ^１６は２価の有機基であり、Ｘ^３及びＸ^４は、それぞれ独立に単結合又は２価の連結基である。ただし、下記式（１−１）及び式（１−２）中の「＊１」は、Ｒ^１６に結合している。）

（式（１−１）及び式（１−２）中、Ｒ^１，Ｒ^２，Ｒ^３，Ｘ^１及びｎは上記式（１）と同義である。「＊１」は結合手を示す。）

（式（５−２）中、Ｒ^１８は２価の有機基であり、Ｒ^１９は、芳香族環基、脂環式基又は複素環基である。Ｒ^１，Ｒ^２及びＸ^１は上記式（１）と同義である。） (Tetracarboxylic acid dianhydride)
The specific acid dianhydride used in the synthesis of the polyamic acid is not particularly limited as long as it has a partial structure represented by the above formula (1), but as a preferred specific example, the following formula (5-1) ), a compound represented by the following formula (5-2), and the like.

(In formula (5-1), A ³ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ is a single bond, and the following formula (1) -1) or a group represented by the following formula (1-2): R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group; R ¹⁶ is a divalent organic group, and X ³ and X ⁴ are each independently a single bond or a divalent linking group, provided that each of the following formulas (1-1) and (1-2) "*1" is bonded to R ^16. )

(In the formula (1-1) and the formula ^{(1-2), R 1, R} 2, R 3, X 1 and n are as defined in the above formula (1). "* 1" represents a bond. )

(In the formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic ring group, an alicyclic group or a heterocyclic group. R ¹ , R ² and X ¹ are the above. It is synonymous with Formula (1).)

In the above formula (5-1), R ¹⁵ and R ¹⁷ are groups obtained by removing three hydrogen atoms from the ring portion of an aromatic ring, an aliphatic ring or a heterocycle. It is preferably an aromatic ring group or an alicyclic group, more preferably a group obtained by removing three hydrogen atoms from a ring portion of a benzene ring, a naphthalene ring, a cyclopentane ring or a cyclohexane ring, and a benzene ring or A group in which three hydrogen atoms have been removed from the ring portion of the cyclohexane ring is more preferable.
Regarding the divalent organic group of R ¹⁶ , the exemplary description of R ^{5 to} R ⁷ of the following formula (2-1) can be applied. From the viewpoint of further improving the afterimage characteristics and contrast characteristics of the liquid crystal display element, preferably a substituted or unsubstituted aromatic ring group or an alicyclic group, more preferably a substituted or unsubstituted aromatic ring group. Is.
As the divalent linking group for X ³ and X ⁴ , —O—, —CO—, —COO—, and —CONR ⁴ — (R ⁴ has the same meaning as in the above formula (1)) and the following formula (2). Examples thereof include the divalent organic groups exemplified as R ^{5 to} R ⁷ in -1).
With respect to R ¹ , R ² , R ³ and X ^{1 in the} formulas (1-1) and (1-2), the description of the formula (1) can be applied.
From the viewpoint of ease of synthesis, the compound represented by the above formula (5-1) is preferably a compound represented by the above formula (1-2) in A ³ , and further, A ⁴ is a single bond. More preferably.
In the above formula (5-2), with respect to the divalent organic group for R ¹⁸ , the exemplified explanations of R ^{5 to} R ^{7 in} the following formula (2-1) can be applied. As for R ¹⁹ , the explanation of the examples and preferred specific examples of R ¹⁵ and R ^{17 in} the above formula (5-1) can be applied. In the compound represented by the above formula (5-2), even if the partial structure represented by the above formula (1) is further formed by a structure in which at least a part of R ¹⁸ and R ¹⁹ are bonded. Good.

（式（ｔ−１）〜式（ｔ−４）及び式（ｔ−１１）〜式（ｔ−１５）中、Ｒは炭素数１〜５のアルキル基であり、ｋ及びｊは、それぞれ独立に０〜２の整数である。） Preferred specific examples of the specific acid dianhydride include, for example, compounds represented by the following formulas (t-1) to (t-31). The specific acid dianhydride may be used alone or in combination of two or more.

(In formula (t-1) to formula (t-4) and formula (t-11) to formula (t-15), R is an alkyl group having 1 to 5 carbon atoms, and k and j are each independent. Is an integer of 0 to 2.)

In the formulas (t-1) to (t-4) and formulas (t-11) to (t-15), the position of R bonded to the ring portion of the 1,4-phenylene group is particularly limited. Not done. Specifically, it can be 2-position, 3-position, 5-position or 6-position in the case of 1-substitution, and 2,4-position or 3,5-position in the case of 2-substitution. The position is preferred. R is preferably a methyl group.

The specific acid dianhydride can be synthesized by appropriately combining conventional methods of organic chemistry. For example, a compound having “—C(R ¹ )═C(R ² )—CO—X ¹ —” is reacted with a phthalic acid derivative to give a tetra structure having a partial structure represented by the above formula (1). It can be obtained by synthesizing a carboxylic acid and then subjecting the obtained tetracarboxylic acid to acid anhydride. However, the method of synthesizing the specific acid dianhydride is not limited to the above.

In the case of the above methods [1] and [3], the tetracarboxylic dianhydride used in the synthesis of the polyamic acid as the compound (X) may be only the specific acid dianhydride, but the above formula ( You may use together the tetracarboxylic dianhydride which does not have the partial structure represented by 1) (henceforth "the other acid dianhydride"). In the above method [2], when synthesizing the polyamic acid as the compound (X), another acid dianhydride is used as the tetracarboxylic acid dianhydride.

（式（ＡＮ−２）中、Ｘ^１３及びＸ^１４は、それぞれ独立にメチレン基から１個の水素原子を取り除いた基又は窒素原子であり、Ｒ^４１は炭素数１〜１０のアルカンジイル基である。式（ＡＮ−３）中、Ｘ^１５及びＸ^１６は、それぞれ独立にメチレン基から１個の水素原子を取り除いた基又は窒素原子であり、Ｂ^１及びＢ^２は、それぞれ独立にフェニレン基又はピリジニレン基であり、Ｒ^４２は炭素数１〜１０のアルカンジイル基であり、ｍは１〜３の整数である。ただし、ｍが２又は３の場合、複数のＲ^４２は互いに同じでも異なってもよい。）
で表される化合物などを；
脂環式テトラカルボン酸二無水物として、例えば１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，３−ジメチル−１，２，３，４−シクロブタンテトラカルボン酸二無水物、２，３，５−トリカルボキシシクロペンチル酢酸二無水物、５−（２，５−ジオキソテトラヒドロフラン−３−イル）−３ａ，４，５，９ｂ−テトラヒドロナフト［１，２−ｃ］フラン−１，３−ジオン、５−（２，５−ジオキソテトラヒドロフラン−３−イル）−８−メチル−３ａ，４，５，９ｂ−テトラヒドロナフト［１，２−ｃ］フラン−１，３−ジオン、３−オキサビシクロ［３．２．１］オクタン−２，４−ジオン−６−スピロ−３’−（テトラヒドロフラン−２’，５’−ジオン）、５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物、３，５，６−トリカルボキシ−２−カルボキシメチルノルボルナン−２：３，５：６−二無水物、ビシクロ［３．３．０］オクタン−２，４，６，８−テトラカルボン酸２：４，６：８−二無水物、ビシクロ［２．２．１］ヘプタン−２，３，５，６−テトラカルボン酸２：３，５：６−二無水物、４，９−ジオキサトリシクロ［５．３．１．０^２，６］ウンデカン−３，５，８，１０−テトラオン、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物、エチレンジアミン四酢酸二無水物、シクロペンタンテトラカルボン酸二無水物、エチレングリコールビス（アンヒドロトリメリテート）、１，３−プロピレングリコールビス（アンヒドロトリメリテート）、下記式（ＡＮ−４）

で表される化合物などを； Examples of other acid dianhydrides include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, the following formula (AN-2) or formula (AN-3).

(In formula (AN-2), X ¹³ and X ¹⁴ are each independently a group in which one hydrogen atom has been removed from a methylene group or a nitrogen atom, and R ⁴¹ is an alkanediyl group having 1 to 10 carbon atoms. In formula (AN-3), X ¹⁵ and X ¹⁶ are each independently a group in which one hydrogen atom has been removed from a methylene group or a nitrogen atom, and B ¹ and B ² are each independently a phenylene group. Or a pyridinylene group, R ⁴² is an alkanediyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3. However, when m is 2 or 3, a plurality of R ^42's are the same or different. You may.)
A compound represented by
As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-Tricarboxycyclopentyl acetic 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)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid 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-tetra carboxylic 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-Cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentane Tetracarboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), 1,3-propylene glycol bis (anhydro trimellitate), the following formula (AN-4)

A compound represented by

（式（ＡＮ−１）中、Ｘ^１１及びＸ^１２は、それぞれ独立に単結合、酸素原子、硫黄原子、−ＣＯ−、＊−ＣＯＯ−、＊−ＯＣＯ−、＊−ＣＯ−ＮＲ^２１−、＊−ＮＲ^２１−ＣＯ−（ただし、Ｒ^２１は水素原子又は炭素数１〜６の１価の炭化水素基である。「＊」は、Ｒ^２０との結合手を示す。）である。Ｒ^２０は、単結合、炭素数１〜２０の２価の炭化水素基、当該炭化水素基の炭素−炭素結合間に−Ｏ−を含む２価の基、又は窒素含有複素環を有する２価の基である。）
で表される化合物、下記式（ＡＮ−５−１）〜式（ＡＮ−５−４）

のそれぞれで表される化合物などを；それぞれ挙げることができるほか、特開２０１０−９７１８８号公報に記載のテトラカルボン酸二無水物を用いることができる。 As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, the following formula (AN-1)

(In formula (AN-1), X ¹¹ and X ¹² are each independently a single bond, an oxygen atom, a sulfur atom, —CO—, *—COO—, *—OCO—, *—CO—NR ²¹ —, * ^-NR 21 -CO- ^{(However, R 21} is a monovalent hydrocarbon group having 1 to 6 carbon hydrogen atom or a carbon. "*" ^indicates a bond to ^{R 20.)} is .R ²⁰ is a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent group containing —O— between carbon-carbon bonds of the hydrocarbon group, or a divalent group having a nitrogen-containing heterocycle. It is a base.)
A compound represented by the following formula (AN-5-1) to formula (AN-5-4)

In addition to the compounds represented by each of the above; and the like, tetracarboxylic dianhydrides described in JP-A-2010-97188 can be used.

In the above formula (AN-2), examples of the alkanediyl group having 1 to 10 carbon atoms of R ⁴¹ and R ⁴² include a methylene group, an ethylene group, a propylene group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, Examples thereof include an octanediyl group, a nonanediyl group, and a decanediyl group, which may be linear or branched. B ¹ and B ² are preferably a 1,4-phenylene group or a 2,5-pyridinylene group.
Specific examples of the compound represented by the above formula (AN-2) include, for example, compounds represented by the following formula (a-2), and specific examples of the compound represented by the above formula (AN-3). Examples include, for example, compounds represented by the following formulas (AN-3-1) to (AN-3-28).

Specific examples of the divalent hydrocarbon group having 1 to ²⁰ carbon atoms of R ^{20 in} the above formula (AN-1) include, for example, methylene group, ethylene group, propylene group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl. Group, octanediyl group, nonanediyl group, decandiyl group and other alkanediyl groups; divalent alicyclic hydrocarbon groups such as cyclohexylene groups; divalent aromatic hydrocarbon groups such as phenylene groups and biphenylene groups; Can be mentioned. The number of oxygen atoms that may be introduced between the carbon-carbon bonds of the hydrocarbon group may be one, or may be two or more. When R ²⁰ is a divalent group having a nitrogen-containing heterocycle, examples of the nitrogen-containing heterocycle include a pyrrole ring, an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a piperidine ring, a piperazine ring and a pyrrolidine ring. Etc.

なお、ポリアミック酸の合成に際し、テトラカルボン酸二無水物は１種を単独で又は２種以上組み合わせて使用することができる。 Specific examples of the compound represented by the above formula (AN-1) include, for example, compounds represented by the following formulas (AN-1-1) to (AN-1-27), and the following formula (a- Examples thereof include compounds represented by 1) and compounds represented by the following formula (a-3).

When synthesizing the polyamic acid, one kind of tetracarboxylic dianhydride can be used alone or two or more kinds can be used in combination.

As the other acid dianhydride, from the viewpoint of electrical properties, it is preferable to include at least one selected from the group consisting of an aliphatic tetracarboxylic acid dianhydride and an alicyclic tetracarboxylic acid dianhydride. Is a compound represented by the above formula (a-2), 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-di Oxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[3.3.0]octane-2,4 , 6,8-Tetracarboxylic acid 2:4,6:8-dianhydride, and at least one compound selected from the group consisting of cyclohexanetetracarboxylic dianhydride. The amount of these preferable compounds used (the total amount when two or more kinds are used) is preferably 10 mol% or more with respect to the total amount of the other acid dianhydride used for the synthesis of the polyamic acid. Is more preferably 20 mol% or more, still more preferably 50 mol% or more.

The ratio of the specific dianhydride used in the above method [1] is the total amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid, from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics and the contrast characteristics of the liquid crystal display device. On the other hand, it is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more.

（式（２−１）中、Ａ^１は下記式（１−１）で表される基又は下記式（１−２）で表される基であり、Ａ^２は単結合、下記式（１−１）で表される基又は下記式（１−２）で表される基である。Ｒ^５は、Ａ^１が下記式（１−１）で表される基の場合に２価の有機基であり、下記式（１−２）で表される基の場合に単結合又は２価の有機基である。Ｒ^７は、Ａ^２が下記式（１−１）で表される基の場合に２価の有機基であり、下記式（１−２）で表される基又は単結合の場合に単結合又は２価の有機基である。Ｒ^６は２価の有機基である。）

（式（２−２）中、Ａ^１及びＡ^２は上記式（２−１）と同義である。Ｒ^８は、Ａ^１が下記式（１−１）で表される基の場合に１価の有機基であり、下記式（１−２）で表される基の場合に水素原子又は１価の有機基である。ただし、Ｒ^８が水素原子の場合、Ａ^１はジアミノフェニル基を有し、Ｒ^８が１価の有機基の場合、Ｒ^８はジアミノフェニル基を有する。Ｒ^１０は、Ａ^２が下記式（１−１）で表される基の場合に１価の有機基であり、下記式（１−２）で表される基又は単結合の場合に水素原子又は１価の有機基である。Ｒ^９は２価の有機基である。）

（式（１−１）及び式（１−２）中、「＊１」はＲ^９に結合する結合手を示す。Ｒ^１，Ｒ^２，Ｒ^３，Ｘ^１及びｎは上記式（１）と同義である。） (Diamine)
As the specific diamine used for synthesizing the polyamic acid, the other structure is not particularly limited as long as it has the partial structure represented by the above formula (1), but is represented by, for example, the following formula (2-1). And a compound represented by the following formula (2-2).

(In the formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1 −1) or a group represented by the following formula (1-2): R ⁵ is a divalent organic group when A ¹ is a group represented by the following formula (1-1). a group, a single bond or a divalent organic group in the case of a group represented by the following formula (1-2) .R ⁷ is a group a ² is represented by the following formula (1-1) In this case, it is a divalent organic group, a group represented by the following formula (1-2) or a single bond or a divalent organic group in the case of a single bond, and R ⁶ is a divalent organic group. )

(In the formula (2-2), A ¹ and A ² have the same meanings as the above formula (2-1). R ⁸ is ¹ when A ¹ is a group represented by the following formula (1-1). In the case of a group represented by the following formula (1-2), it is a hydrogen atom or a monovalent organic group, provided that when R ⁸ is a hydrogen atom, A ¹ is a diaminophenyl group. And R ⁸ is a monovalent organic group, R ⁸ has a diaminophenyl group, and R ¹⁰ is a monovalent organic group when A ² is a group represented by the following formula (1-1). Is a hydrogen atom or a monovalent organic group in the case of a group represented by the following formula (1-2) or a single bond, and R ⁹ is a divalent organic group.

(In the formula (1-1) and (1-2), "* 1" ^{.R 1, R 2, R 3} , X 1 and n are above formula represents a bond that binds to ^{R 9} (1) Is synonymous with.)

In the above formula (2-1), examples of the divalent organic group represented by R ^{5 to} R ⁷ include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a part of the methylene group contained in the hydrocarbon group. O -, - CO -, - COO- or ^{-NR 33} - ^(R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include a divalent group formed by replacing at, such a divalent heterocyclic group And these may have a substituent. Here, the “hydrocarbon group” in the present specification is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Among these, the “chain hydrocarbon group” means a straight chain hydrocarbon group or a branched chain hydrocarbon group that does not include a cyclic structure in the main chain and is composed of only a chain structure. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it does not need to be composed only of the structure of an alicyclic hydrocarbon, and a part thereof having a chain structure is also included. The “aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, the structure need not be composed of only the aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure.

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in R ^{5 to} R ⁷ include chain hydrocarbon groups such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group and hexanediyl. group, Heputanjiiru group, octane-diyl group, Nonanjiiru group, a decanediyl group or the like; alicyclic hydrocarbon groups such as a cyclohexylene ^{group, -R} 30 -R ³¹ - (provided ^{that, R 30} is a cyclohexylene group, R ³¹ is an alkanediyl group having 1 to 3 carbon atoms; and the like; as an aromatic hydrocarbon group, for example, a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a naphthylene group, —Ar ³ —R ³² — (however, , Ar ³ is a phenylene group, a biphenylene group or a naphthylene group, and R ³² is an alkanediyl group having a carbon number of 1 to 3 or a cyclohexylene group.) and the like;
Examples of the divalent heterocyclic group for R ^{5 to} R ⁷ include groups in which two hydrogen atoms have been removed from a nitrogen-containing heterocycle such as pyridine, piperazine and piperidine. Examples of the substituent that R ^{5 to} R ⁷ may have include a halogen atom, an alkoxy group, a hydroxyl group, a carboxyl group, and a cyano group.
Among R ⁵ to R ^7, examples of the divalent organic group for R ⁵ and R ^7, among the above, a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, a cyclohexylene group, pyridinylene group, or - Ar ⁴ —COO-* ³ (Ar ⁴ is a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group or cyclohexylene group, and “* ³ ” represents a bond with a benzene ring. ) Is preferable. R ⁶ is preferably an alkanediyl group having 1 to 6 carbon atoms, a cyclohexylene group, a phenylene group, a biphenylene group or a naphthylene group.

In the above formula (2-2), the monovalent organic group represented by R ⁸ and R ¹⁰ is, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a part of the methylene group contained in the hydrocarbon group. O -, - CO -, - COO- or ^{-NR 33} - ^(R 33 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include a monovalent group formed by replacing at, such as a monovalent heterocyclic group And these may have a substituent. Specific examples of the monovalent organic group represented by R ⁸ and R ¹⁰ include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, and phenyl. Group, tolyl group, benzyl group, biphenyl group, naphthyl group, pyridyl group, piperidyl group and the like.
For R ⁹ , the description of R ^{6 in} the above formula (2-1) can be applied. In the diaminophenyl group represented by the above formula (2-2), the two amino groups are preferably at the 2,4-position or the 3,5-position with respect to the other groups.
The description of the above formula (1) can be applied to the description of R ¹ , R ² , R ³ and X ^{1 in} the above formula (1-1) and the formula (1-2).

（式（４）中、Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換又は無置換のフェニレン基又はシクロヘキシレン基であり、Ｘ^２は単結合、−ＣＯＯ−又は−ＣＯＮＲ^２０−（Ｒ^２０は水素原子又は１価の有機基である。）である。ただし、Ａｒ^１が上記式（１）中のベンゼン環を構成していてもよい。ｔは１又は２である。ｔ＝２のとき、Ａｒ^２，Ｘ^２は各々独立に上記定義を有する。「＊」は結合手を示す。） The specific diamine is preferably a compound having a partial structure represented by the following formula (4) in the molecule. Having the partial structure represented by the following formula (4) is preferable in that the effect of reducing an afterimage (AC afterimage) due to an AC voltage in the liquid crystal display element can be enhanced.

(In formula (4), Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenylene group or a cyclohexylene group, X ² is a single bond, —COO— or —CONR ²⁰ — (R ²⁰ is A hydrogen atom or a monovalent organic group), provided that Ar ¹ may form the benzene ring in the above formula (1), t is 1 or 2. When t=2 , Ar ² and X ² each independently have the above definition. “*” represents a bond.)

（式中、「＊」は結合手を示す。） In the above formula (4), examples of the monovalent organic group represented by R ²⁰ include an alkyl group having 1 to 6 carbon atoms and a protective group. Specific examples of the protective group include a t-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, an allyloxycarbonyl group and the like.
X ² is preferably a single bond or —COO—.
The substituent of the ring portion of Ar ¹ and Ar ² is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom, more preferably a methyl group or a fluorine atom.
Specific preferred examples of the partial structure represented by the above formula (4) include, for example, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and the following formulas (4-1) to (4- The groups represented by each of 4), groups having a methyl group or a fluorine atom in the ring portion of these groups, and the like can be mentioned.

(In the formula, "*" indicates a bond.)

When an alignment controlling force is applied to a coating film formed by using a liquid crystal aligning agent by a photo-alignment method, the effect of reducing the AC afterimage of the liquid crystal display element and improving the contrast is high. It is preferable to use the compound represented by -1). By using the compound represented by the above formula (2-1) as the specific diamine, a polymer having the partial structure represented by the above formula (1) in the main chain can be obtained.

Specific examples of the specific diamine include compounds represented by the above formula (2-1), for example, the following formula (b-1) to formula (b-17) and formula (b-26) to formula (b-56). ), etc.; as the compound represented by the above formula (2-2), for example, compounds represented by the following formulas (b-18) to (b-59), Can be mentioned.

When synthesizing the polyamic acid, the specific diamine may be used alone or in combination of two or more. Among the formulas (b-1) to (b-59), formulas (b-1), (b-3), (b-5) to (b-7), (b-11), and formula (b-1). b-18), formula (b-20), formula (b-22) to (b-26), formula (b-28), formula (b-41) to formula (b-45), formula (b- 47), the formula (b-54), the formula (b-56) and the formula (b-57) correspond to the compound having the partial structure represented by the formula (4).

The specific diamine can be synthesized by appropriately combining conventional methods of organic chemistry. As an example thereof, a dinitro intermediate having a nitro group instead of the primary amino group of the compound represented by the formula (2-1) or the formula (2-2) is synthesized, and then the obtained dinitro intermediate is synthesized. An example is a method of aminating the nitro group of the body using an applicable reduction system.
The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. Specifically, a compound for example, represented by _{^{"O 2 N-R 5 -A 1}} -H ", and a compound represented by the ^{"HO-R 6 -A 2 -R 7} -NO 2 ", preferably Can be obtained by reacting in an organic solvent, if necessary, in the presence of a catalyst.
The reduction reaction of the dinitro intermediate can be carried out preferably in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin or nickel. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, alcohols and the like. However, the procedure for synthesizing the specific diamine is not limited to the above method.

When synthesizing the polyamic acid as the compound (X), the specific diamine may be used alone, or a diamine having no partial structure represented by the above formula (1) (other diamine) may be used in combination. May be.
Examples of such other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, and , 2-bis(2-aminoethoxy)ethane and the like;
Examples of the alicyclic diamine 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−、＊^４−ＣＯＯ−又は＊^４−ＯＣＯ−（ただし「＊^４」はベンゼン環に結合する結合手である。）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。ただし、ａ及びｂが同時に０になることはない。） As the aromatic diamine, for example, dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene. , Cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostanyl 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—, * ⁴ —COO— or * ⁴ —OCO— (where “* ⁴ ” is bonded to the benzene ring. Is a bond), 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, and a is 0 or 1, b is an integer of 0 to 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.)

で表される化合物などの配向性基含有ジアミン：
ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルアミン、４，４’−ジアミノジフェニルスルフィド、４−アミノフェニル−４’−アミノベンゾエート、４，４’−ジアミノアゾベンゼン、１，５−ビス（４−アミノフェノキシ）ペンタン、１，７−ビス（４−アミノフェノキシ）ヘプタン、ビス[２−（４−アミノフェニル）エチル]ヘキサン二酸、Ｎ，Ｎ−ビス（４−アミノフェニル）メチルアミン、１，５−ジアミノナフタレン、２，２’−ジメチル−４，４’−ジアミノビフェニル、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、４，４’−ジアミノジフェニルエーテル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、９，９−ビス（４−アミノフェニル）フルオレン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−（ｐ−フェニレンジイソプロピリデン）ビスアニリン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、２，６−ジアミノピリジン、２，４−ジアミノピリミジン、３，６−ジアミノアクリジン、３，６−ジアミノカルバゾール、Ｎ−メチル−３，６−ジアミノカルバゾール、Ｎ，Ｎ’−ビス（４−アミノフェニル）−ベンジジン、Ｎ，Ｎ’−ビス（４−アミノフェニル）−Ｎ，Ｎ’−ジメチルベンジジン、１，４−ビス−（４−アミノフェニル）−ピペラジン、３，５−ジアミノ安息香酸、下記式（ｄａ−３）〜式（ｄａ−１７）

のそれぞれで表される化合物などを；
ジアミノオルガノシロキサンとして、例えば、１，３−ビス（３−アミノプロピル）−テトラメチルジシロキサンなどを；それぞれ挙げることができるほか、特開２０１０−９７１８８号公報に記載のジアミンを用いることができる。 A compound represented by the following formula (da-1) or formula (da-2)

An orienting group-containing diamine such as a compound represented by:
p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1 ,5-bis(4-aminophenoxy)pentane, 1,7-bis(4-aminophenoxy)heptane, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, N,N-bis(4-amino) Phenyl)methylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 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, 1,4-bis(4-aminophenoxy)benzene, 4 ,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diamino Carbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl) -Piperazine, 3,5-diaminobenzoic acid, the following formula (da-3) to formula (da-17)

A compound represented by each of
Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; and diamines described in JP 2010-97188 A can be used.

In the above formula (E-1) ^{"-X I - (R I -X II} ) d - " Examples of the divalent group represented by the alkanediyl group having 1 to 3 carbon atoms, * - O -, * It is preferably —COO— or *—O—C ₂ H ₄ —O— (however, the bond marked with “*” bonds to the diaminophenyl group). Examples of the group “—C _c H _2c+1 ” include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group. Examples thereof include a group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group, and these are preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

なお、ポリアミック酸の合成に使用するジアミンとしては、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 compounds represented by the following formulas (E-1-1) to (E-1-4).

As the diamine used for synthesizing the polyamic acid, one kind of these compounds may be used alone, or two or more kinds may be appropriately selected and used.

When applied to a liquid crystal aligning agent for a TN type, STN type or vertical alignment type liquid crystal display element, a functional group (liquid crystal alignment property) capable of expressing a liquid crystal alignment regulating force on a side chain of a polyamic acid without depending on light irradiation. Group) may be introduced. Examples of such a liquid crystal aligning group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, and Examples thereof include a group having a ring structure (for example, a group having a partial structure represented by the above formula (4)). The polyamic acid having a liquid crystal aligning group can be obtained, for example, by polymerization including the above-mentioned diamine containing an aligning group in the monomer composition. When using the orientation group-containing diamine, the compounding ratio thereof is preferably 3 mol% or more, and 5 to 70 mol% based on all diamines used in the synthesis from the viewpoint of improving the liquid crystal alignment property. Is more preferable.

When synthesizing the polyamic acid by the above method [2], the proportion of the specific diamine used is the total amount of the diamine used for synthesizing the polyamic acid, from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display device. On the other hand, it is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more.
When the polyamic acid is synthesized by the above method [3], the total amount of the specific acid dianhydride and the specific diamine is 10 mol% with respect to the total amount of the tetracarboxylic dianhydride and the diamine used for the synthesis. The amount is preferably the above, more preferably 20 mol% or more, still more preferably 30 mol% or more.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic dianhydride and diamine together with a molecular weight modifier, if necessary. The ratio of the tetracarboxylic dianhydride and the diamine used for the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 with respect to 1 equivalent of the amino group of the diamine. The equivalent ratio is preferable, and the 0.3-1.2 equivalent ratio 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モノアミン化合物及び酸一無水物を好ましく使用することができる。具体的には、例えば下記式（ｍａ−１）〜式（ｍａ−１５）のそれぞれで表される化合物、下記式（ｍｔ−１）〜式（ｍｔ−１０）のそれぞれで表される化合物などが挙げられる。

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 the above, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate.
As the molecular weight modifier, a monofunctional compound having a partial structure represented by the above formula (1) may be used. As the compound, a monoamine compound and an acid monoanhydride can be preferably used. Specifically, for example, a compound represented by each of the following formulas (ma-1) to (ma-15), a compound represented by each of the following formulas (mt-1) to (mt-10), and the like. Is mentioned.

The proportion of the molecular weight modifier used is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total tetracarboxylic dianhydride and diamine used. The molecular weight modifier may be used alone or in combination of two or more.

The synthesis reaction of polyamic acid 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 0.1 to 24 hours, more preferably 0.5 to 12 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (organic solvent of the first group), or one or more selected from the organic solvent of the first group. And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvent of the second group). In the latter case, the use ratio of the second group organic solvent is preferably 50% by weight or less, and more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. It is below, more preferably 30% by weight or less.

Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. It is preferable to use one or more selected from the group consisting of and halogenated phenol as a solvent, or to use a mixture of one or more of these with other organic solvents in the range of the above ratio. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 to 50% by weight based on the total amount (a+b) of the reaction solution. Is preferred.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be subjected to the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid is purified. Alternatively, the liquid crystal aligning agent may be prepared. When the polyamic acid is dehydrated and ring-closed to form a polyimide, the reaction solution may be subjected to the dehydration ring-closing reaction as it is, or may be subjected to the dehydration ring-closing 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 as the compound (X) includes, for example, [I] a method of reacting a polyamic acid having a partial structure represented by the above formula (1) with an esterifying agent, and [II] a tetracarboxylic acid diester. It can be obtained by a method of reacting with a diamine, a method of reacting [III] tetracarboxylic acid diester dihalide with a diamine, or the like.
In the present specification, the “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. The “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 the method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, and an epoxy group-containing compound. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol, phenols such as cresol and phenols; acetal compounds such as N,N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal or the like; as a halide, 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, chloromethylisopropyl carbonate, chloromethyl pivalate, chloromethyl acetate, chloromethyl butyrate, chloromethylmethyl sulfide, etc.; as an epoxy group-containing compound, for example, propylene oxide, etc. Can be mentioned respectively.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the above polyamic acid using alcohols such as methanol and ethanol. Examples of the diamine to be used include the diamines exemplified in the synthesis of polyamic acid. The reaction of the method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. Examples of the organic solvent include the organic solvents exemplified as those used for the synthesis of polyamic acid. Examples of the dehydration catalyst include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, and a phosphorus-based condensing agent. The reaction temperature at this time is preferably −20 to 150° C., more preferably 0 to 100° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. Examples of the diamine to be used include the diamines exemplified in the synthesis of polyamic acid. The reaction of the method [III] is preferably carried out in an organic solvent in the presence of a suitable base. Examples of the organic solvent include the organic solvents exemplified as those used for the synthesis of polyamic acid. 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 0.1 to 24 hours, more preferably 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 partial esterified product having both an amic acid structure and an amic acid ester structure. The reaction solution obtained by dissolving the polyamic acid ester may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. Alternatively, the isolated polyamic acid ester may be purified and then used for the preparation of the liquid crystal aligning agent. Isolation and purification of the polyamic acid ester can be performed according to known methods.

[Polyimide]
The polyimide as the compound (X) can be obtained, for example, by subjecting the polyamic acid as the compound (X) synthesized as described above to dehydration ring closure to imidize.

The polyimide may be a complete imidized product obtained by dehydration ring closure of all of the amic acid structure of the precursor polyamic acid, dehydration ring closure of only a portion of the amic acid structure, amic acid structure and imide It may be a partial imidized product having a ring structure. The imidation ratio of the polyimide used in the reaction is preferably 20% or more, more preferably 30 to 99%, further preferably 40 to 99%. This imidization ratio is a percentage of the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, and by adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as necessary. .. Of these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used for 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 polyimide is obtained. This reaction solution may be directly used 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 dehydration ring-closing catalyst from the reaction solution. The liquid crystal aligning agent may be prepared, or the isolated polyimide may be purified and then used for preparing the liquid crystal aligning agent. These purification operations can be performed according to known methods. In addition, the polyimide can also be obtained by imidization of polyamic acid ester.

The polyamic acid, polyamic acid ester, and polyimide as the compound (X) obtained as described above are selected from the group consisting of partial structures represented by the following formulas (6-1) to (6-10). It is preferable to have at least one of

（式（６−１）及び式（６−２）中、Ａ^３、Ａ^４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｘ^３及びＸ^４は、それぞれ上記式（５−１）と同義である。Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は１価の有機基である。）

（式（６−３）及び式（６−４）中、Ｒ^１、Ｒ^２及びＸ^１は、それぞれ上記式（１）と同義であり、Ｒ^１８及びＲ^１９は、それぞれ上記式（５−２）と同義である。Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は１価の有機基である。）

（式（６−５）及び式（６−６）中、Ａ^１、Ａ^２、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ上記式（２−１）と同義である。Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^２２及びＲ^２３は、それぞれ独立に、３価の有機基である。）

（式（６−７）〜式（６−１０）中、Ａ^１、Ａ^２、Ｒ^９及びＲ^１０は、それぞれ上記式（２−２）と同義である。Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^２２及びＲ^２３は、それぞれ独立に、３価の有機基である。） In the synthesis of compound (X), when a compound represented by the above formula (5-1) is used among the above specific acid dianhydrides, a partial structure represented by the following formula (6-1) and the following A polymer having at least one partial structure selected from the group consisting of partial structures represented by formula (6-2) is obtained. When the compound represented by the above formula (5-2) is used among the specific acid dianhydrides, it is represented by the partial structure represented by the following formula (6-3) and the following formula (6-4). A polymer having at least one partial structure selected from the group consisting of partial structures can be obtained. Moreover, when using the compound represented by the said Formula(2-1) among the said specific diamine, it is represented by the partial structure represented by the following formula (6-5), and the following formula (6-6). A polymer having at least one partial structure selected from the group consisting of partial structures is obtained. When the compound represented by the above formula (2-2) is used among the above specific diamines, it is selected from the group consisting of partial structures represented by the following formulas (6-7) to (6-10). A polymer having at least one selected partial structure is obtained.

(In the formula (6-1) and formula ^{(6-2), A 3, A} 4, R 15, R 16, R 17, X 3 and ^{X 4} are each the equation (5-1) synonymous R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group.)

(In the formula (6-3) and the formula (6-4), R ¹ , R ² and X ¹ are respectively synonymous with the above formula (1), and R ¹⁸ and R ¹⁹ are respectively the above formula (5- (Synonymous with 2) R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group.)

(In the formula (6-5) and formula ^{(6-6), A 1, A} 2, R 5, R 6 and ^{R 7} are each as defined in the above formula (2-1) ^{.R 20} and ^{R 21} Are each independently a hydrogen atom or a monovalent organic group, and R ²² and R ²³ are each independently a trivalent organic group.)

(In the formulas (6-7) to (6-10), A ¹ , A ² , R ⁹ and R ¹⁰ are respectively synonymous with the above formula (2-2). R ²⁰ and R ²¹ are respectively represented. Independently, it is a hydrogen atom or a monovalent organic group, and R ²² and R ²³ are each independently a trivalent organic group.)

In the formulas (6-1) to (6-8), examples of the monovalent organic group represented by R ²⁰ and R ²¹ include a monovalent hydrocarbon group having 1 to 10 carbon atoms and a cinnamic acid structure. Groups and the like. Examples of the trivalent organic group of R ²² and R ²³ include a chain hydrocarbon group, an alicyclic group, an aromatic ring group and a heterocyclic group. It is preferably an alicyclic group or an aromatic ring group, and the description of R ¹⁵ and R ^{17 in} the above formula (5-1) can be applied to specific examples thereof.

The polyamic acid, polyamic acid ester, and polyimide as the compound (X) preferably have a solution viscosity of 10 to 800 mPa·s when the solution has a concentration of 10% by weight, and preferably 15 to 500 mPa·s. More preferably, it has a solution viscosity of s. The solution viscosity (mPa·s) of the above-mentioned polymer is the concentration of the polymer solution prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) at a concentration of 10% by weight. , And a value 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 gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to. It is 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good alignment and stability of the liquid crystal display element can be secured.

[polyamide]
The polyamide as the compound (X) can be obtained by, for example, a method of reacting a dicarboxylic acid with a diamine. Here, the dicarboxylic acid is preferably subjected to reaction with a diamine after acid chloride formation using a suitable chlorinating agent such as thionyl chloride.

The dicarboxylic acid used for synthesizing the polyamide is not particularly limited, and examples thereof include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, and 2 Aliphatic dicarboxylic acids such as 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, fumaric acid, and muconic acid;
A dicarboxylic acid 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'-diphenylpropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylenediacrylic 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 a dicarboxylic acid having an aromatic ring such as cyclobutanedicarboxylic acid. In addition, the dicarboxylic acid can be used individually by 1 type or in combination of 2 or more types.

The diamine used when synthesizing the polyamide as the compound (X) includes a specific diamine. Moreover, you may use together other diamines as needed. The use ratio of the specific diamine is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more with respect to the total amount of diamine used for synthesizing the polyamide. preferable. In addition, diamine can be used individually by 1 type or in combination of 2 or more types.

The ratio of the dicarboxylic acid and the diamine used for the synthesis reaction of the polyamide is preferably such that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine, and 0.3 to A ratio of 1.2 equivalents is more preferable.

The reaction of dicarboxylic acid (preferably acid chloride-dicarboxylic acid) with diamine is preferably carried out in the presence of a base in an organic solvent. The reaction temperature at this time is preferably 0°C to 200°C, more preferably 10 to 100°C. The reaction time is preferably 0.5 to 48 hours, more preferably 1 to 36 hours.
As the organic solvent used in the reaction, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 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, based on 100 parts by weight of the total amount of the dicarboxylic acid and the diamine.
As the base used in the above reaction, for example, tertiary amines such as pyridine, triethylamine and 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, based on 1 mol of the diamine.

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

The solution viscosity of the polyamide as the compound (X) preferably has a solution viscosity of 10 to 800 mPa·s when the solution has a concentration of 10% by weight, and a solution viscosity of 15 to 500 mPa·s. It is more preferable that the The polystyrene-equivalent weight average molecular weight (Mw) of the polyamide measured by GPC is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

[Polyorganosiloxane]
The polyorganosiloxane (hereinafter, also referred to as “polymer (S)”) as the compound (X) can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Specifically, the following [1] or [2]
[1] A hydrolyzable silane compound (ms-1) having an epoxy group or a mixture of the silane compound (ms-1) and another silane compound is hydrolyzed and condensed to synthesize an epoxy group-containing polyorganosiloxane. 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] 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 is hydrolytically condensed. Method, and the like. Of these, the method [1] is preferable because it is simple and the introduction rate of the partial structure represented by the above formula (1) in the polymer (S) can be increased. In the method [1], a reaction product of a polyorganosiloxane having an epoxy group and a carboxylic acid is used as the compound (X).

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, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, etc. Can be mentioned. As the silane compound (ms-1), one of these may be used alone or two or more of them may 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, etc., alkoxysilane containing nitrogen and sulfur atoms;
3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3- (Meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and other unsaturated hydrocarbon-containing alkoxysilanes; trimethoxysilylpropylsuccinic anhydride, etc. Can be mentioned. Other silane compounds may 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 silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent.
In the above method [1], it is possible to introduce a sufficient amount of the partial structure represented by the above formula (1) into a side chain of the polymer, and at the same time, to cause an excess amount of an epoxy group. From the viewpoint of suppressing the reaction, the epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 100 to 10,000 g/mol, and more preferably 150 to 1,000 g/mol. Therefore, when 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 amount of water used is preferably 0.5 to 100 mol, and more preferably 1 to 30 mol, based on 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 and zirconium compounds. Examples of the catalyst include alkali metal compounds and organic bases among them in that side reactions such as ring-opening of epoxy groups can be suppressed, hydrolysis condensation rate can be increased, and storage stability is excellent. A tertiary or quaternary organic base is particularly preferred.
The amount of the organic base used varies depending on the type of the organic base, reaction conditions such as temperature and the like, and should be appropriately set, but is preferably 0.01 to 3 times by mole with respect to the total silane compound, More preferably, it is 0.05 to 1 times mol.

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; and esters such as ethyl acetate. , N-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; as ethers, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; as alcohols, For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono. Examples thereof include ethyl ether and propylene glycol mono-n-propyl ether. 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 proportion of the organic solvent used in the hydrolysis condensation reaction is preferably 10 to 10,000 parts by weight, and more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of all the 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 the solution with an organic base and water, and heating with an oil bath or the like. During 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, more preferably 1 to 8 hours. During heating, the mixed solution may be stirred or may be placed under reflux. After completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction solution with water. In this washing, it is preferable to wash with water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight) because the washing operation becomes easy. Washing is performed until the water 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 solvent is removed to remove the polyorgano Siloxane can be obtained.

In the above method [1], the epoxy group-containing polyorganosiloxane obtained by the above reaction 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 polymer (S) as a polyorganosiloxane having a partial structure represented by the above formula (1) in the side chain. be able to.

（式（３）中、Ａ^１及びＡ^２は、それぞれ上記式（２−１）と同義である。ただし、上記式（１−１）及び式（１−２）中の「＊１」は、Ｒ^１２に結合する結合手を示す。Ｒ^１１は、Ａ^１が下記式（１−１）で表される基の場合に１価の有機基であり、Ａ^１が下記式（１−２）で表される基の場合に水素原子又は１価の有機基である。Ｒ^１２は２価の有機基である。Ｒ^１３は、Ａ^２が下記式（１−１）で表される基である場合に２価の有機基であり、Ａ^２が下記式（１−２）で表される基である場合に単結合又は２価の有機基である。ｓ及びｒは、それぞれ独立に０又は１である。ただし、式（３）中にカルボキシル基を１個有する。） Specific examples of the specific carboxylic acid include compounds represented by the following formula (3).

(In the formula (3), A ¹ and A ² are respectively synonymous with the above formula (2-1). However, “*1” in the above formula (1-1) and the formula (1-2) is , ^.R represents a bond that binds to ^{R 12 11} is a monovalent organic group when the ^{group a 1} is represented by the following formula (1-1), ^{a 1} is represented by the following formula (1-2 ) Is a hydrogen atom or a monovalent organic group, R ¹² is a divalent organic group, and R ¹³ is a group in which A ² is represented by the following formula (1-1). Is a divalent organic group, and A ² is a single bond or a divalent organic group when A ² is a group represented by the following formula (1-2): s and r are each independently. 0 or 1. However, the formula (3) has one carboxyl group.)

In the above formula (3), the description of R ⁸ and R ^{10 in} the above formula (2-2) can be applied to the examples of the monovalent organic group for R ¹¹ . Moreover, the description of R ^{5 to} R ^{7 in} the above formula (2-1) can be applied to the examples of the divalent organic group of R ¹² and R ¹³ . The description of the above formula (1) can be applied to the description of R ¹ , R ² , R ³ and X ¹ of A ¹ and A ² .

From the viewpoint of enhancing the effect of reducing the AC afterimage, the specific carboxylic acid preferably further has, in the molecule, the partial structure represented by the above formula (1) and the partial structure represented by the above formula (4). Note that the description of the specific diamine can be applied to the preferred specific examples of the partial structure represented by the above formula (4). Further, the benzene ring in the above formula (1) may be a part of the structure represented by the above formula (4), which is the same as the specific diamine.

なお、重合体（Ｓ）の合成に際し、特定カルボン酸は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。上記式（ｇ−１）〜式（ｇ−１３）のうち、式（ｇ−１）、（ｇ−２）、（ｇ−４）〜（ｇ−８）、及び式（ｇ−１１）〜式（ｇ−１３）が、上記式（４）で表される部分構造を有する化合物に相当する。 Specific examples of the specific carboxylic acid include compounds represented by the following formulas (g-1) to (g-13).

In the synthesis of the polymer (S), the specific carboxylic acids may be used alone or in combination of two or more. Among the formulas (g-1) to (g-13), formulas (g-1), (g-2), (g-4) to (g-8), and formulas (g-11) to The formula (g-13) corresponds to the compound having the partial structure represented by the formula (4).

The content ratio of the partial structure represented by the above formula (1) in one molecule of the polymer (S) is from the viewpoint of improving the sensitivity to light with respect to the silicon atom of the polymer (S). The amount is preferably 3 to 100 mol %, more preferably 5 to 95 mol %, further preferably 10 to 90 mol %. Therefore, when synthesizing the polymer (S), it is preferable to select the usage ratio of the specific carboxylic acid so that the content ratio of the partial structure represented by the above formula (1) falls within the above range.

The specific carboxylic acid can be synthesized by appropriately combining conventional methods of organic chemistry. As an example thereof, for example, a compound represented by "R ¹¹ -A ¹ -H" and a compound represented by "HO-R ¹² -A ² -R ¹³ -COOM (where M is a protecting group of a carboxyl group)" are represented. The compound can be obtained by, for example, a method of reacting with a compound, preferably in an organic solvent, if necessary in the presence of a catalyst, and then performing deprotection. However, the procedure for synthesizing the specific carboxylic acid is not limited to the above method.

（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 polymer (S), the carboxylic acid used for the reaction with the epoxy group-containing polyorganosiloxane may be only the specific carboxylic acid, or other carboxylic acid other than the specific carboxylic acid may be used in combination. ..
The other carboxylic acid is not particularly limited as long as it is a carboxylic acid having no partial structure represented by the above formula (1), and examples thereof include a carboxylic acid having the above liquid crystal aligning group. Specific examples of other carboxylic acids include fatty acids having 6 to 20 carbon atoms such as caproic acid, lauric acid, pentadecyl acid, palmitic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid and arachidic acid. The compound etc. which are each represented by a following formula (C-2-1)-a formula (C-2-10) can be mentioned.

(In the formula, j is an integer of 0 to 12, and h is an integer of 1 to 10.)
In addition, other carboxylic acids can be used alone or in combination of two or more selected from these.

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

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be carried out preferably 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, a compound known as a so-called curing accelerator that accelerates the reaction of the epoxy compound, or the like 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. You can Of these, a tertiary organic amine or a quaternary organic amine is preferable 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, and secondary chlorides. Examples thereof include metal halogen compounds such as tin. Of these, quaternary ammonium salts are preferable, and specific examples thereof include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.
The above catalyst is used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing polyorganosiloxane. It

Examples of the organic solvent used in the above reaction include hydrocarbon, ether, ester, ketone, amide, alcohol and the like. Of these, ethers, esters, and ketones are preferable from the viewpoint of solubility of raw materials and products, and ease of purification of products, and 2-butanone, 2-hexanone, and methyl are specific examples of particularly preferable solvents. Examples thereof include isobutyl ketone and butyl acetate. The organic solvent is preferably used in such a proportion that the solid content concentration (the total weight of the components other than the solvent in the reaction solution occupies the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it in 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. After the reaction is completed, it is preferable to wash the organic solvent layer separated from the reaction solution with water. After washing with water, the organic solvent layer is dried with a suitable desiccant, if necessary, and then the solvent is removed to obtain the polymer (S). The method for synthesizing the polyorganosiloxane is not limited to the above hydrolysis/condensation reaction, and for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol may be adopted.

（式（７）中、Ａ^１、Ａ^２、Ｒ^１１、Ｒ^１２、Ｒ^１３、ｓ及びｒは、それぞれ上記式（３）と同義である。Ｚ^１は２価の有機基である。「＊」は、珪素原子との結合手であることを示す。）
なお、Ｚ^１の２価の有機基については、上記式（２−１）のＲ^５〜Ｒ^７で例示した基などが挙げられる。 The polymer (S) obtained as described above preferably has a partial structure formed by the reaction of a polyorganosiloxane having an epoxy group and a carboxylic acid. Specifically, specifically, the following formula (7) It is preferable to have a partial structure represented by

(In the formula (7), A ¹ , A ² , R ¹¹ , R ¹² , R ¹³ , s, and r each have the same meaning as in the above formula (3). Z ¹ represents a divalent organic group. "*" indicates a bond with a silicon atom.)
The divalent organic group of Z ¹ includes the groups exemplified as R ^{5 to} R ⁷ in the above formula (2-1).

The polymer (S) contained in the liquid crystal aligning agent of the present disclosure preferably has a solution viscosity of 1 to 500 mPa·s when it is made into a solution having a concentration of 10% by weight, and preferably 3 to 200 mPa. More preferably, it has a solution viscosity of s. The polystyrene equivalent weight average molecular weight (Mw) of the polymer (S) measured by GPC is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and more preferably 3 More preferably, it is 2,000 to 20,000.

[Poly(meth)acrylate]
The poly(meth)acrylate as the compound (X) is, for example, a (meth)acrylic monomer (m-1) having an epoxy group, or the (meth)acrylic monomer (m-1) and other After polymerizing a mixture with the (meth)acrylic monomer in the presence of a polymerization initiator, the obtained polymer (hereinafter, also referred to as "epoxy group-containing poly(meth)acrylate"), It can be obtained by a method of reacting with a specific carboxylic acid.

Examples of the (meth)acrylic monomer (m-1) include unsaturated carboxylic acid esters having an epoxy group. Specific examples thereof include glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4-epoxybutyl acrylate (meth)acrylate. Α-ethyl acrylate 3,4-epoxybutyl, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 6,7-epoxyheptyl, α-ethyl acrylate 6,7-epoxyheptyl, Examples thereof include 4-hydroxybutyl glycidyl ether acrylate and (3-ethyloxetane-3-yl)methyl (meth)acrylate. The (meth)acrylic monomer (m-1) can be used alone or in combination of two or more of the above.

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, ( 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, methoxyethyl (meth)acrylate, -N,N-dimethylaminoethyl (meth)acrylate, (meth ) N-N,N-diethylaminoethyl acrylate, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and the like ( (Meth)acrylic acid ester: α-alkoxy acrylic acid ester such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate: unsaturated carboxylic acid ester such as crotonic acid ester such as methyl crotonate and ethyl crotonate;
And unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride. As the other (meth)acrylic monomers, one kind may be used alone, or two or more kinds may be used in combination.

In the synthesis of poly(meth)acrylate, the total amount (mol number) of epoxy groups per 1 g of epoxy group-containing poly(meth)acrylate is preferably 5.0×10 ⁻⁵ or more, and 1.0×10 5. ^{-4 to} 1.0 x 10 ^-2 mol/g is more preferable, and 5.0 x 10 ^{-4 to} 5.0 x 10 ^-3 mol/g is further preferable. Therefore, the usage ratio of the (meth)acrylic monomer (m-1) is adjusted so that the total number of moles of epoxy groups per 1 g of the epoxy group-containing poly(meth)acrylate falls within the above numerical range. It is preferable.
At the time of 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, and more preferably 20 mol% or less, based on the total amount of the monomers used for synthesizing the poly(meth)acrylate.

The polymerization reaction using the (meth)acrylic monomer is preferably carried out by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators usually used in radical polymerization, such as 2,2′-azobis(isobutyronitrile) and 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; and redox type initiators composed of these peroxides and a reducing agent. Among these, azo compounds are preferable, and 2,2′-azobis(isobutyronitrile) is more preferable. As the polymerization initiator, these may be used alone or in combination of two or more.
The proportion of the polymerization initiator used is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight, based on 100 parts by weight of all the monomers used in the reaction.

The polymerization reaction of the (meth)acrylic monomer is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. 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 specific 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°C to 120°C, more preferably 60 to 110°C. The reaction time is preferably 1 to 36 hours, more preferably 2 to 24 hours. The amount (a) of the organic solvent used is such that the total amount (b) of the monomers used in the reaction is 0.1 to 50% by weight based on the total amount (a+b) of the reaction solution. Preferably.

The epoxy group-containing poly(meth)acrylate obtained by the above reaction is then reacted with a specific carboxylic acid. As specific examples of the specific carboxylic acid, the description of the polymer (S) can be applied. In the reaction, the specific carboxylic acid may be used alone, or other carboxylic acid 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 based on 1 mol of the total epoxy groups of the epoxy group-containing poly(meth)acrylate. preferable. The amount is more preferably 0.01 to 0.9 mol, and further preferably 0.05 to 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, examples of the catalyst used in the reaction include the compounds exemplified as the catalyst that can be used in the synthesis of the polymer (S). Of these, quaternary ammonium salts are 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 further preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing poly(meth)acrylate. Is.

As the organic solvent used in the reaction, the 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 proportion that the solid content concentration (the total weight of the components other than the solvent in the reaction solution occupies the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it in 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 poly(meth)acrylate as the compound (X) can be obtained. This reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be subjected to the preparation of the liquid crystal aligning agent after isolating the poly(meth)acrylate contained in the reaction solution, or the isolated poly(meth)acrylate may be used. The (meth)acrylate may be purified and then used for the preparation of the liquid crystal aligning agent. Isolation and purification of poly(meth)acrylate can be performed according to a known method.

The method for synthesizing the poly(meth)acrylate as the compound (X) is not limited to the above 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 is polymerized. It can also be obtained by a method of polymerizing in the presence of an initiator.

With respect to poly(meth)acrylate, the polystyrene-equivalent number average molecular weight (Mn) measured by GPC improves the liquid crystal alignment of the liquid crystal alignment film to be formed and secures the stability of the liquid crystal alignment over time. From this viewpoint, it is preferably 250 to 500,000, more preferably 500 to 100,000, and further preferably 1,000 to 50,000.

<Other ingredients>
The liquid crystal aligning agent according to the present invention contains the compound (X) as described above, but may contain other components as necessary. Examples of other components that may be added to the liquid crystal aligning agent include other polymers other than the compound (X), compounds having at least one epoxy group in the molecule (hereinafter, "epoxy group-containing compound"). , A functional silane compound, a compound having a photopolymerizable group (hereinafter, referred to as “photopolymerizable group-containing compound”), a photosensitizer, and the like.

[Other polymers]
The above-mentioned other polymers can be used for improving solution properties and electric properties. Such other polymer is a polymer having no partial structure represented by the above formula (1), and its main skeleton is not particularly limited. Specifically, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate and the like as the main skeleton Polymers can be mentioned. Among these, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly(meth)acrylate and polyamide is preferable.
When the other polymer is added to the liquid crystal aligning agent, the mixing ratio is preferably 90 parts by weight or less based on 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent, The amount is more preferably 80 parts by weight, further preferably 0.1 to 70 parts by weight.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesiveness of the liquid crystal alignment film to the surface of the substrate and the electrical characteristics. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N′,N′-tetraglycidyl-m-xylylenediene Amine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N , N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine and the like can be mentioned as preferable ones. In addition, as an example of the epoxy group-containing compound, the epoxy group-containing polyorganosiloxane described in WO 2009/096598 can be used.
When these epoxy compounds are added to the liquid crystal aligning agent, the compounding ratio thereof is preferably 40 parts by weight or less with respect to 100 parts by weight of the total amount of the polymer contained in the liquid crystal aligning agent, and is 0.1 to 30. It is more preferable to set it as a weight part.

[Functional silane compound]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane and N-(2-aminoethyl). )-3-Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl Methyl-3,6-diazananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane , 3-glycidoxypropyltrimethoxysilane and the like.
When these functional silane compounds are added to the liquid crystal aligning agent, the mixing ratio thereof is preferably 2 parts by weight or less based on 100 parts by weight of the total amount of the polymer contained in the liquid crystal aligning agent, and 0.02 It is more preferable that the amount is 0.2 parts by weight.

[Photopolymerizable group-containing compound]
The photopolymerizable group-containing compound should be used for the purpose of enhancing the alignment regulating force in the liquid crystal alignment film when imparting the liquid crystal alignment ability by irradiating the coating film formed using the liquid crystal alignment agent with light. You can Here, examples of the photopolymerizable group include a group having a polymerizable unsaturated bond, and specific examples thereof include (meth)acryloyloxy group, styryl group, (meth)acrylamide group, vinyl group, and vinylidene group. group, vinyloxy group _{(CH 2 = CH-O-)} , maleimide group.

As such a photopolymerizable group-containing compound, a (meth)acrylate compound can be preferably used because of its high photoreactivity, and specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl ( (Meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl Monofunctional (meth)acrylates such as (meth)acrylate; ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, polyether (meth)acrylate, ethoxylated Examples thereof include polyfunctional (meth)acrylates such as bisphenol A di(meth)acrylate.
When the photopolymerizable group-containing compound is added to the liquid crystal aligning agent, the mixing ratio is preferably 30 parts by weight or less based on 100 parts by weight of the total amount of the polymer contained in the liquid crystal aligning agent. More preferably, it is 20 parts by weight.

光増感剤を使用する場合、その配合割合は、液晶配向剤中に含まれる重合体１００重量部に対して、０．０１〜５０重量部とすることが好ましく、０．１〜２０重量部とすることがより好ましい。 [Photosensitizer]
As the photosensitizer, various compounds having a photosensitizing function can be used. Here, the term "photosensitization function" means that after a singlet excited state is generated by light irradiation, intersystem crossing may occur in some cases, and when it collides with another molecule, the partner changes to an excited state, and The function to return to the ground state. Specific examples of the photosensitizer include compounds represented by the following formulas (H-1) to (H-6).

When a photosensitizer is used, its blending ratio is preferably 0.01 to 50 parts by weight, and 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer contained in the liquid crystal aligning agent. Is more preferable.

As the other components, additives usually used for preparing a liquid crystal aligning agent can be used. Examples of the additives other than the above include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, dispersants and the like.

<Solvent>
The liquid crystal aligning agent according to the present invention is prepared as a liquid composition in which the above-mentioned specific compound and other components used as necessary are dispersed or dissolved in a suitable solvent.

Examples of the organic solvent 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 ethoxy propionate, 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 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 and the like. These may be used alone or in combination of two or more.

The liquid crystal aligning agent according to the present invention may contain only one kind of polymer as a polymer component, or may contain two or more kinds of polymers. In the case of containing two or more kinds of polymers, for example, the following [1] to [3] are exemplified.
[1] A polymer (hereinafter, also referred to as “specific polymer”) as the compound (X) and another polymer, and the specific polymer and the other polymer are polyamic acid, polyamic acid ester, An embodiment which is at least one selected from polyimide and polyamide.
[2] A mode in which a plurality of specific polymers are contained, and the plurality of specific polymers are at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide.
[3] A specific polymer and another polymer are contained, the specific polymer is a polyorganosiloxane, and the other polymer is at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide. Aspect.
In the aspect of [1], by using a specific polymer having a fluorine atom or a silicon atom, the specific polymer having a fluorine atom or a silicon atom does not have a fluorine atom and a silicon atom in the upper layer. It is presumed that the other polymer is unevenly distributed in the lower layer, and thus the polymer may be unevenly distributed in the liquid crystal alignment film.

The reason why the effect of improving the afterimage characteristic and the contrast characteristic of the liquid crystal display element is obtained when the liquid crystal aligning agent containing the compound (X) is used is not clear, but one hypothesis is as follows. .. That is, in the compound (X), in the partial structure represented by the above formula (1), a monovalent organic group is introduced into at least one of α carbon and β carbon of the carbonyl group, preferably α carbon of the carbonyl group. As a result, when light is irradiated, the photodimerization reaction is suppressed as compared with a compound having a partial structure (cinnamoyl group) in which R ¹ and R ² in the above formula (1) are hydrogen atoms. It is considered that the isomerization reaction proceeds predominantly. As a result, the liquid crystal alignment film formed by using the liquid crystal aligning agent containing the compound (X) has an improved liquid crystal alignment regulating force, and as a result, an effect of improving the afterimage characteristics and the contrast characteristics of the liquid crystal display device is obtained. Presumed to be.

The solid content concentration (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) in the liquid crystal aligning agent according to the present invention is appropriately selected in consideration of viscosity, volatility and the like. However, it is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent according to the present invention is applied to the surface of a substrate as described later and preferably heated to form a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. 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, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to deteriorate the coating property. There is a tendency.

The particularly preferable range of the solid content concentration depends 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 (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is in the range of 1.5 to 4.5% by weight. It is particularly preferable that When the printing method is used, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and 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 thus the solution viscosity is in the range of 3 to 15 mPa·s. The temperature for 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 alignment agent according to the present invention described above. Further, the liquid crystal display device according to the present invention includes a liquid crystal alignment film formed by using the above liquid crystal alignment agent. The operation mode of the liquid crystal display device according to the present invention is not particularly limited, and includes, for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type and the like. It can be applied to various operating modes.

The liquid crystal display element according to the present invention can be manufactured, for example, by steps including the following steps (1-1) to (1-3). In the step (1-1), the substrate used differs depending on the desired operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[Step (1-1): Formation of coating film]
First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then the applied surface is heated to form a coating film on the substrate.
(1-1A) For example, when manufacturing a TN type, STN type or VA type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are made into a pair, and each transparent conductive film is formed. The liquid crystal aligning agent according to the present invention is applied onto each surface, preferably by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. As the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Co., USA), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ) and the like are used. Can be used. To obtain a patterned transparent conductive film, for example, a method of forming a pattern-free transparent conductive film and then forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming the transparent conductive film; You can In 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. You may perform the pre-processing which applies in advance.

After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing liquid dripping of the applied liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermal imidization of the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300°C, and more preferably 120 to 250°C. The post-baking 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.

(1-1B) When manufacturing an IPS-type or FFS-type liquid crystal display element, an electrode formation surface of a substrate provided with an electrode made of a comb-shaped patterned transparent conductive film or a metal film, and an electrode are provided. The liquid crystal aligning agent of the present invention is applied to one surface of the counter substrate which is not formed, and then the applied surface is heated to form a coating film. The materials of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferable film thickness of the coating film formed are as described above. It is the same as (1-1A). As the metal film, a film made of a metal such as chromium can be used.

In any of the above (1-1A) and (1-1B), after applying the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal aligning film or a coating film to be the liquid crystal aligning film. It At this time, by further heating after forming the coating film, the dehydration ring-closing reaction of the polyamic acid, polyamic acid ester and polyimide compounded in the liquid crystal aligning agent of the present invention may proceed to give a more imidized coating film.

[Step (1-2): Orientation Capability Treatment]
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display device, a treatment for imparting a liquid crystal aligning ability to the coating film formed in the step (1-1) is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the orientation ability imparting treatment, for example, a rubbing treatment of rubbing the coating film in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon and cotton, and photo-alignment of irradiating the coating film with polarized or unpolarized radiation Examples include processing. On the other hand, in the case of producing a VA type liquid crystal display device, the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment ability imparting treatment. May be.

Light irradiation in the photo-alignment treatment is performed by [1] irradiating the coating film after the post-baking step, [2] irradiating the coating film after the pre-baking step and before the post-baking step, [3] ] It can be performed by a method of irradiating the coating film while heating the coating film in at least one of the pre-baking step and the post-baking step. Among these, the method [2] is preferable because the effect of improving the afterimage characteristics and the contrast characteristics of the liquid crystal display element is high.

As the radiation for irradiating 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, the irradiation may be performed in a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the irradiation direction is an oblique direction.
As the 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 range can be obtained by means of using a light source in combination with a filter, a diffraction grating, or the like. The irradiation dose of radiation is preferably 100 to 50,000 J/m ² , and more preferably 300 to 20,000 J/m ² . Further, the light irradiation to the coating film may be performed while heating the coating film in order to increase the reactivity. The temperature at the time of heating is usually 30 to 250°C, preferably 40 to 200°C, and more preferably 50 to 150°C.

Note that the liquid crystal alignment film after the rubbing treatment is further irradiated with ultraviolet light on a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film, A resist film may be formed on each part and then a rubbing process may be performed in a different direction from the previous rubbing process, and then the resist film may be removed so that the liquid crystal alignment film has different liquid crystal alignment ability in each region. .. In this case, it is possible to improve the visual field characteristics of the obtained liquid crystal display element. The liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step (1-3): Construction of Liquid Crystal Cell]
(1-3A) A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates which are opposed to each other. For manufacturing the liquid crystal cell, for example, the following two methods can be mentioned. The first method is a conventionally known method. First, two substrates are arranged to face each other with 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 by using a sealant, and the substrate surface and the seal are sealed. 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 place on one of the two substrates having the liquid crystal alignment film formed thereon, and then liquid crystal is dripped at predetermined places on the surface of the liquid crystal alignment film. After that, the other substrate is bonded so that the liquid crystal alignment films face each other, 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. .. In either case, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature, so that the flow orientation at the time of filling the liquid crystal is improved. It is desirable to remove it.

As the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and 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 liquid crystal. A cyclohexane-based liquid crystal, a pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a cubane-based liquid crystal, or the like can be used. In addition, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate; chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate or the like may be added and used.

(1-3B) When manufacturing a PSA type liquid crystal display device, a liquid crystal cell is constructed in the same manner as in (1-3A) above except that a photopolymerizable compound is injected or dropped together with the liquid crystal. After that, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be a direct current or an alternating current of 5 to 50 V, for example. Further, as the light to be applied, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source of the 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, etc. can be used. The ultraviolet rays in the above preferable wavelength range 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.}

(1-3C) 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 in (1-3A) above. A method of manufacturing a liquid crystal display element may be adopted by performing a construction and then performing a step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates. According to this method, the merit of the PSA mode can be realized with a small light irradiation amount. The description in (1-3B) above can be applied to the applied voltage and the conditions of the light to be applied.

Then, a liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. As a polarizing plate to be attached to the outer surface of a liquid crystal cell, a polarizing film in which a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine and sandwiched between cellulose acetate protective films or the H film itself is used. A polarizing plate consisting of

The liquid crystal display device according to the present invention can be effectively applied to various devices, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones. , Various monitors, liquid crystal televisions, various display devices such as information displays.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw and the epoxy equivalent of the polymer were measured by the following methods. In the following, the compound represented by the formula A may be simply referred to as “compound A”.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene conversion value measured by GPC under the following conditions.
Column: Tosoh Corp., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40°C
Pressure: 68 kgf/cm ²
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

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

4-Nitrobenzaldehyde (9.6 g) and methylmalonic acid (15.0 g) were dissolved in pyridine (100 ml), and piperidine (12.5 ml) was added thereto, followed by stirring at 80° C. for 5 hours. The reaction solution was allowed to cool to room temperature, 100 ml of ethyl acetate was added, and then 100 ml of hydrochloric acid was added to separate this. After separating again with pure water, this was concentrated to obtain an intermediate (b-1-1) as a white solid (10.5 g, purity 99%).
10 g of the obtained intermediate (b-1-1) was added to 30 ml of thionyl chloride, N,N-dimethylformamide was added in a catalytic amount, and then the mixture was stirred at 80° C. for 1 hour. The reaction solution was concentrated, and the residue was dissolved in 100 ml of tetrahydrofuran. This solution was used as a reaction solution (A). 4-Hydroxy-4′-nitrobiphenyl (9.4 g) and triethylamine (8.9 g) were added to tetrahydrofuran (60 ml), which was cooled to 0° C. and stirred for 5 minutes. Then, the reaction solution (A) was slowly added dropwise. After completion of the dropping, the reaction was completed by stirring at room temperature for 4 hours. After adding 300 ml of ethyl acetate and 100 ml of THF and separating this solution with hydrochloric acid, an aqueous solution of sodium carbonate and pure water, this was concentrated, and the intermediate (b-1-2) was white solid 19.0 g, purity 99%. Got with.
Then, 18.0 g of the intermediate (b-1-2) and 14.5 g of zinc powder were added to 150 ml of tetrahydrofuran, and 5.4 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, 150 ml of ethyl acetate was added, the solution was separated with pure water, and then concentrated to obtain a compound (b-1) as a yellow solid (13.5 g) with a purity of 99%.

[Example 1-2: Synthesis of compound (b-2)]
Compound (b) was synthesized in the same manner as in Example 1-1, except that 4-hydroxy-4′-nitrobiphenyl was changed to 4-nitrophenol in the second step of Scheme 1 of Example 1-1. -2) was obtained.

[Example 1-3: Synthesis of compound (b-3)]
Synthesis was carried out in the same manner as in Example 1-1, except that 4-hydroxy-4′-nitrobiphenyl was changed to 4-amino-4′-nitrobiphenyl in the second step of Scheme 1 of Example 1-1. Then, the compound (b-3) was obtained.

[Example 1-4: Synthesis of compound (g-1)]
The same operation as in the first step of Scheme 1 was performed except that the 4-nitrobenzaldehyde was changed to 4-phenylbenzaldehyde in the first step of Scheme 1 of Example 1-1, and the compound (g-1) was obtained in one step. Got

[Example 1-5: Synthesis of compound (b-27)]
Synthesis was carried out in the same manner as in Example 1-1, except that 4-hydroxy-4′-nitrobiphenyl was changed to 2-methyl-4-nitroaniline in the second step of Scheme 1 of Example 1-1. , Compound (b-27) was obtained.

[Example 1-6: Synthesis of compound (t-5)]
Compound (t-5) was synthesized according to the following scheme 2.

5.0 g of piperazine and 12.3 g of triethylamine were dissolved in 100 ml of tetrahydrofuran, which was cooled to 0° C. and stirred for 5 minutes. A solution of 12.1 g of methacryloyl chloride in 100 ml of tetrahydrofuran was slowly added dropwise thereto. After completion of the dropping, the reaction was completed by stirring at room temperature for 4 hours. After adding 300 ml of ethyl acetate and separating this solution with hydrochloric acid, an aqueous solution of sodium carbonate and pure water, this was concentrated to obtain an intermediate (t-5-1) as a white solid (11.6 g) with a purity of 99%. It was
10 g of the obtained intermediate (t-5-1), 22.0 g of 4-bromophthalic acid, 1.0 g of palladium acetate, 2.7 g of tri(o-tolyl)phosphine, and 36.4 g of triethylamine were added to N,N-dimethyl. It was added to 120 ml of acetamide. Then, it stirred at 60 degreeC for 6 hours. The reaction solution was allowed to cool to room temperature, 300 ml of ethyl acetate was added, and this solution was separated with pure water. Hydrochloric acid was added to the obtained aqueous layer to make an acidic aqueous solution, and ethyl acetate was added to separate the layers. Finally, the organic layer was separated with pure water and then concentrated to obtain an intermediate (t-5-2) as a pale yellow solid (20.0 g, purity 99%).
Then, 18.0 g of the intermediate (t-5-2) was added to 100 ml of acetic anhydride. Then, it stirred at 60 degreeC for 12 hours. The reaction solution was allowed to cool to room temperature, the precipitated solid was filtered, washed with hexane and dried to obtain a compound (t-5) as a pale yellow solid (15.5 g, purity 99%).

<Synthesis of polymer>
[Example 2-1: Synthesis of polymer (A-1)]
100 parts by mole of the compound represented by the formula (a-1) as the tetracarboxylic dianhydride and 100 parts by mole of the compound (b-1) as the diamine were dissolved in N-methyl-2-pyrrolidone (NMP). The reaction was carried out at 60° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The weight average molecular weight Mw of the obtained polyamic acid (polymer (A-1)) was 45,000.

[Examples 2-2 to 2-9 and Synthesis Examples 1 to 3]
Polyamic acid (polymers (A-2) to (A-9)) was prepared in the same manner as in Example 2-1 except that the types and amounts of the tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below. And polymers (B-1) to (B-3)) were respectively synthesized.

In Table 1, the values in parentheses for tetracarboxylic dianhydride and diamine represent the usage ratio [mol part] with respect to 100 mol parts in total of the tetracarboxylic dianhydride used for polymer synthesis. The abbreviations in Table 1 have the following meanings.
<Tetracarboxylic acid dianhydride>
a-1: Compound represented by the above formula (a-1) a-2: Compound represented by the above formula (a-2) a-3:1,3-propylene glycol bis(anhydrotrimellitate) (Compound represented by the above formula (a-3))
a-4: 1,2,3,4-cyclobutanetetracarboxylic dianhydride a-5:4,4'-(hexafluoroisopropylidene)diphthalic anhydride a-6: pyromellitic dianhydride t- 5: Compound <diamine> represented by the above formula (t-5)
b-1: compound represented by the above formula (b-1) b-2: compound represented by the above formula (b-2) b-3: compound represented by the above formula (b-3) b- 27: Compound represented by the above formula (b-27) c-1: Compound represented by the following formula (c-1) c-2: Compound represented by the following formula (c-2) c-3: p-Phenylenediamine c-4:N,N-bis(4-aminophenyl)methylamine c-5:4,4′-diamino-2,2′-dimethylbiphenyl

[Synthesis Example 4: Synthesis of polymer (ES-1)]
100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of pure water was slowly dropped, and the mixture was stirred at 80° C. for 6 hours. Then, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then concentrated to give a polyorganosiloxane (ES-1) having an epoxy group. Obtained as a clear transparent liquid. The polyorganosiloxane (ES-1) having an epoxy group had an Mw of 2,200 and an epoxy equivalent of 186 g/mol.

[Synthesis Example 2-10: Synthesis of Polymer (S-1)]
9.3 g of the polyorganosiloxane (ES-1) having an epoxy group obtained in Synthesis Example 4 above, 26 g of methyl isobutyl ketone, 3 g of compound (g-1) obtained in Synthesis Example 1-4 above, and UCAT 18X (commodity). 0.10 g, which is a quaternary amine salt manufactured by San-Apro Co., Ltd.) was mixed and stirred at 80° C. for 12 hours. Then, the reaction mixture was poured into methanol, the generated precipitate was filtered, and this was dissolved in ethyl acetate to give a solution. The solution was separated with pure water and then concentrated to give compound (X). 6.3 g of the polyorganosiloxane (polymer (S-1)) was obtained as a white powder. The weight average molecular weight Mw of the polymer (S-1) was 4,000.

[Example 3-1]
1. Preparation of Liquid Crystal Aligning Agent NMP and butyl cellosolve (BC) were added to a solution containing the polymer (A-1) obtained in Example 2-1 as a polymer component, and the mixture was sufficiently stirred to give a solvent composition of NMP. :BC=70:30 (weight ratio) and 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 size of 0.45 μm.

2. Production of Optical FFS Type Liquid Crystal Display Element An FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a comb-shaped patterned top electrode 13 are formed in this order on a glass substrate 11a having an electrode pair on one side, and an electrode pair. The opposite glass substrate 11b not provided with is formed into a pair, and the surface of the glass substrate 11a having the transparent electrode and the one surface of the opposite glass substrate 11b are each subjected to the above 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 top electrode 13 used is shown in FIG. 2(a) is a top view of the top electrode 13, and FIG. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2(a). In this embodiment, the line width d1 of the electrodes is 4 μm, and the distance d2 between the electrodes is 6 μm. Further, as the top electrode 13, four-system drive electrodes of electrode A, electrode B, electrode C, and electrode D were used (FIG. 3). The bottom electrode 15 acts as a common electrode that acts on all four drive electrodes, and each of the four drive electrode regions serves as a pixel region.
After forming the coating film with the spinner, the coating film was pre-baked on a hot plate at 80° C. for 1 minute. Then, each surface of the coating film was irradiated with polarized ultraviolet rays of 5,000 J/m ² using a Hg-Xe lamp and a Glan-Taylor prism to obtain a pair of substrates having a liquid crystal alignment film. At this time, the irradiation direction of the polarized ultraviolet light is from the substrate normal direction, and the polarization plane direction is set so that the direction of the line segment projecting the polarized surface of the polarized ultraviolet light on the substrate is the direction of the double-headed arrow in FIG. 2B. After setting, light irradiation processing was performed. After irradiation with light, heating (post-baking) was performed at 230° C. for 1 hour in an oven whose interior 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 by screen printing to the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surfaces of the pair of substrates are applied. They were opposed to each other, and they were superposed and pressure-bonded so that the polarization planes of polarized ultraviolet rays were parallel to each other, and the adhesive was thermoset at 150° C. for 1 hour. Next, a liquid crystal "MLC-7028" manufactured by Merck & Co., Inc. was filled into the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow orientation at the time of liquid crystal injection, this was heated to 150° C. and then gradually cooled to room temperature.
Next, a FFS type liquid crystal display element was manufactured by bonding polarizing plates to both outer surfaces of the substrate. At this time, one of the polarizing plates was attached so that its polarization direction was parallel to the projection direction of the polarization plane of the polarized ultraviolet rays of the liquid crystal alignment film on the substrate surface, and the other one had the polarization direction first. It was attached so as to be orthogonal to the polarization direction of the polarizing plate.
In addition, by performing the above-described series of operations while changing the ultraviolet irradiation amount before post-baking in the range of 100 to 10,000 J/m ² , respectively, three or more liquid crystal display elements having different ultraviolet irradiation amounts can be obtained. Manufactured.

3. Evaluation of liquid crystal display device 2. The following evaluation (1) was performed using the liquid crystal display element manufactured in. In addition, except for the point that the polarizing plates were not stuck together, the above 2. A liquid crystal display element (a liquid crystal cell in which a polarizing plate is not attached) was manufactured by performing the same operation as in (1), and the following (2) was evaluated. As for the evaluation results, the best result was selected from three or more liquid crystal display elements having different ultraviolet irradiation doses and used for the evaluation of the liquid crystal display elements.

(1) Evaluation of AC afterimage characteristics 2. The FFS type liquid crystal display element manufactured in 1. was placed in an environment of 25° C. and 1 atm. The bottom electrode was used as a common electrode for all four drive electrodes, and the potential of the bottom electrode was set to 0 V potential (ground potential). While the electrodes B and D were short-circuited to the common electrode and 0 V was applied, a synthetic voltage composed of an AC voltage of 5 V was applied to the electrodes A and C for 100 hours. Immediately after 100 hours, a voltage of AC 1.5 V was applied to all of the electrodes A to D. Then, from the time when a voltage of AC 1.5 V is applied to all of the electrodes A to D, the driving stress application region (pixel regions of the electrodes A and C) and the driving stress non-application region (electrodes B and D). The time until it becomes impossible to visually confirm the difference in luminance from the pixel area) is defined as the afterimage erasing time Ts. It should be noted that the shorter this time, the less likely the afterimage will occur. When the afterimage erasing time Ts is less than 30 seconds, it is “good (◯)”, when it is 30 seconds or more and less than 120 seconds, it is “OK”, and when it is 120 seconds or more, it is “poor (×). )”, the liquid crystal display device of this example was evaluated as “good” in afterimage characteristics.

(2) Evaluation of contrast after driving stress The liquid crystal display device manufactured in 1. was driven for 30 hours at an alternating voltage of 10 V, and then a device in which a polarizer and an analyzer were arranged between a light source and a light quantity detector was used to calculate the minimum relative distance represented by the following formula (1). The transmittance (%) was measured.
Minimum relative transmittance (%)=(β−B ⁰ )/(B ¹⁰⁰ −B ⁰ )×100 (1)
(In Formula (1), B ⁰ is the amount of transmission of light under a blank and crossed Nicols. B ¹⁰⁰ is the amount of transmission of light under a blank and under para Nicol. β is a polarizer under crossed Nicols. The liquid crystal display element is sandwiched between the analyzers, which 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. Those with a minimum relative transmittance of less than 0.5% are considered “good (○)”, those with a minimum relative transmittance of 0.5% or more and less than 1.0% are evaluated as “OK”, and those with a minimum relative transmittance of 1.0% or more are evaluated. It was defined as “poor (x)”. As a result, the contrast evaluation of this liquid crystal display element was judged to be “good”.

[Examples 3-2 to 3-7, 3-9, 3-10, Reference Example 3-8 and Comparative Example 1]
Liquid crystal aligning agents were prepared with 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. Further, a liquid crystal display element was manufactured in the same manner as in Example 3-1 using each liquid crystal aligning agent, and various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below.

In the liquid crystal display element manufactured using the liquid crystal aligning agent containing the compound (X), the evaluation of the AC afterimage characteristic and the contrast characteristic was “good” or “good” in each of the examples. (Example 3-1 to Example 3-7, Reference Example 3-8, Example 3-9, Example 3-10). Particularly, in Example 3-1 to Example 3-7 and Example 3-9 to Example 3-10 having the partial structure represented by the above formula (1) in the main chain of the polymer, the partial structure Good results were obtained as compared with Examples 3-8 having a polysiloxane skeleton on the side chain. It was also found that the use of a diamine having a polycyclic structure such as a biphenyl structure enhances the effect of improving the AC afterimage characteristics.
On the other hand, in the liquid crystal aligning agent of the comparative example not containing the compound (X), the AC afterimage characteristics and the contrast characteristics were inferior to those of the example.

Claims (9)

Containing a polymer having a partial structure represented by the following formula (1) in the main chain ,
The liquid crystal aligning agent , wherein the partial structure is derived from diamine or tetracarboxylic dianhydride .

(In the formula (1), R ¹ is a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, R ² is a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and R ³ is a substituent. X ¹ is an oxygen atom or —NR ⁴ — (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ is bonded to another group to form a ring structure together with a nitrogen atom. R ³ may be bonded to another group to form at least a part of the ring, n is an integer of 0 to 4, and when n is 2 or more, A plurality of R ³ 's may be the same or different. “*” represents a bond.) The polymer having a partial structure represented by the formula (1) in the main chain is at least one polymer (A) selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, and polyamide. The liquid crystal aligning agent described in. The polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and a moiety derived from a diamine having a partial structure represented by the above formula (1). The liquid crystal aligning agent according to claim 2, having a structure. The liquid crystal aligning agent according to claim 3, wherein the diamine has a partial structure represented by the following formula (4) in the molecule.

(In the formula (4), Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenylene group or a substituted or unsubstituted cyclohexylene group, and X ² is a single bond, —COO— or —CONR. ²⁰ − (R ²⁰ is a hydrogen atom or a monovalent organic group), provided that Ar ¹ may form the benzene ring in the above formula (1), and t is 1 or 2. When t=2, Ar ² and X ² each independently have the above definition. “*” represents a bond.) The polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and has tetracarboxylic dianhydride having a partial structure represented by the above formula (1). The liquid crystal aligning agent according to claim 2, which has a partial structure derived from a product. The liquid crystal aligning agent according to claim 1, wherein R ² is an alkyl group having 1 to 3 carbon atoms. A method for producing a liquid crystal alignment film, comprising the steps of applying the liquid crystal alignment agent according to claim 1 on a substrate to form a coating film, and irradiating the coating film with light. A liquid crystal alignment film formed using the liquid crystal alignment agent according to claim 1. A liquid crystal display device comprising the liquid crystal alignment film according to claim 8.

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