JP2019117399A - Liquid crystal aligning agent, liquid crystal alignment film, method of manufacturing liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

To provide a liquid crystal aligning agent which allows for producing a liquid crystal display device with good afterimage and contrast characteristics.SOLUTION: A liquid crystal aligning agent contains a polymer having a main chain with a partial structure represented by a formula (1) below. In the formula (1), Rand Rindependently represent a hydrogen atom, halogen atom, cyano group, or monovalent organic group and Rrepresents a substituent, where at least either of Rand Rrepresents a halogen atom, cyano group, or monovalent organic group. Xrepresents an oxygen atom or -NR-, where Rrepresents a hydrogen atom, hydroxyl group, or monovalent organic group and may be bonded to another group to form a cyclic structure together with nitrogen atoms. Rmay be bonded to another group to form a cyclic structure. n represents an integer of 0 to 4. [*] represents a bonding hand.SELECTED DRAWING: None

Description

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

  Liquid crystal display devices are widely used in televisions, mobile devices, various monitors, and the like. Moreover, 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 of obtaining an organic film having liquid crystal alignment control power, 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, photosensitive organic There is known a method (light alignment method) of irradiating a film with light.

  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 moreover, since precise control of the liquid crystal alignment direction is also possible, various studies have been made in recent years. (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 its main chain, a polyimide or a polyamide.

International Publication No. 2013/161984

  In recent years, a liquid crystal television with a large screen and high definition is mainly used, and a small display terminal such as a smartphone and a tablet PC is widely used, and a demand for high definition of the liquid crystal panel is further increasing. Specifically, it is important for improving the display quality of the liquid crystal display element that the afterimage hardly occurs (afterimage characteristic) and the contrast is good (contrast characteristic), 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 capable of obtaining a liquid crystal display element having good afterimage characteristics and contrast characteristics.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the subject of the prior art as mentioned above, the present inventors discover that the said subject is solvable by containing the compound which has a specific structure in a liquid crystal aligning agent. We came to complete the invention. Specifically, the following liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment 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 its main chain.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent, provided that R ¹ and R ² are as well. at least one of a halogen atom, .X ¹ is a cyano group or a monovalent organic group is an oxygen atom or -NR ⁴ - (provided that, ^{R 4} is a hydrogen atom, a hydroxyl group or a monovalent organic group, ^{R 4} is R ³ may be bonded to another group to form a ring structure with a nitrogen atom) R ³ may be bonded to another group to form at least a part of a ring, n is 0 It is an integer of-4. When n is 2 or more, plural 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], a preferred 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 the formula (2-1), A ¹ represents a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² represents a single bond, 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) Group is a divalent organic group, and when A ² is a group represented by the following formula (1-2) or a single bond, it is a single bond or a divalent organic group: R ⁶ is a divalent group However, “* 1” in the following formulas (1-1) and (1-2) is bonded to R ⁶ )

(In formula (1-1) and 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-mentioned [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 which 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 represents a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ represents a single bond, the following formula (1 -1) or a group represented by the following formula (1-2): R ¹⁵ and R ¹⁷ each independently represent 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 following formulas (1-1) and (1-2) "* 1" binds to R ^16. )

(In formula (1-1) and 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 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-mentioned It is synonymous with Formula (1).)

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

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

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

  Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix | blended as needed are demonstrated.

（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 this indication contains the compound (Hereafter, it is also mentioned "compound (X)") which has a partial structure represented by following formula (1).

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent, provided that R ¹ and R ² are as well. at least one of a halogen atom, .X ¹ is a cyano group or a monovalent organic group is an oxygen atom or -NR ⁴ - (provided that, ^{R 4} is a hydrogen atom, a hydroxyl group or a monovalent organic group, ^{R 4} is R ³ may be bonded to another group to form a ring structure with a nitrogen atom) R ³ may be bonded to another group to form at least a part of a ring, n is 0 It is an integer of-4. When n is 2 or more, plural 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, and a fluoroalkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an epoxy group, an alkylsilyl group, an alkoxysilyl group and the like can be mentioned.
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 And heptyl group, octyl group, nonyl group, decyl group and the like. Moreover, as a C1-C20 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentoxy group etc. are mentioned, for example; As a C1-C20 fluoroalkyl group, a perfluoromethyl group, Per Fluoroethyl group, 2,2,2-trifluoroethyl group and the like; examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group and the like; and an aryl group having a carbon number of 6 to 20 As such, a phenyl group, a tolyl group, etc. can be mentioned; As a C6-C20 aralkyl group, a benzyl group etc. can be mentioned, respectively.
As a halogen atom of R < ¹ > and R < ² >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, 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 power of the liquid crystal by light irradiation. It is preferably an atom, a cyano group or a monovalent organic group. Specifically, among the above, 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 a hydrogen atom More preferable. 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 still more preferably a methyl group. Among them, a combination of R ¹ being a hydrogen atom and R ² being 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. As a protecting group, a carbamate type protecting group, an amide type protecting group, an imide type protecting group, a sulfonamide type protecting group etc. are mentioned, for example. Preferred is a carbamate 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 cyanoethyloxycarbonyl group, 9-fluorenylmethylcarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like. A t-butoxycarbonyl group is preferable in that it is easily deprotected by heat and is easy to discharge the released compound as a gas to the outside of the film.
Among 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 other groups to form a ring structure with a nitrogen atom. As such a ring structure, for example, piperidine, piperazine and the like can be mentioned. It is preferable that X ^{1 be} an oxygen atom.
As a substituent of R ³ , for example, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 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, an ester And the like. Examples of the ring formed by bonding R ³ to another group include an imide ring and the like. n is preferably 0 to 2, more preferably 0 or 1. “*” In the formula (1) may be bonded to a hydrogen atom, may be bonded to an organic group, or bonded to R ³ to form a ring structure (eg, an imide ring etc.) May be

The compound (X) may be a polymer component that can be a main component of the liquid crystal alignment film, or may be an additive component that is blended separately from the polymer component. Among them, it is preferable that at least a part of the polymer component is contained in the liquid crystal aligning agent, and the partial structure represented by the above formula (1) is preferable because the effect of expressing the anisotropy by the photoalignment method is high. It is particularly preferred to have in the main chain of the polymer.
Here, the "main chain" of the polymer in the present specification refers to the "stem" portion consisting of a chain of the longest atoms in the polymer. In addition, it is acceptable that this "stem" part includes a ring structure. Therefore, “having the partial structure represented by the above formula (1) in the main chain of the polymer” means that the partial structure constitutes a part of the main chain. However, it does not exclude that the partial structure represented by the said Formula (1) exists also in parts other than a principal chain, for example, side chains (parts branched from the "trunk" of a polymer). The "organic group" means a group containing a hydrocarbon group, and may contain a hetero atom in the structure.

The main skeleton in the case where the compound (X) is a polymer is not particularly limited. Main skeletons such as maleimide) derivatives and poly (meth) acrylates can be mentioned.
Among them, at least one selected from the group consisting of polyamic acids, polyimides, polyamic acid esters, polyamides, polyorganosiloxanes and poly (meth) acrylates from the viewpoints of heat resistance, mechanical strength, affinity with liquid crystals, etc. It is preferably a polymer (hereinafter also referred to as "polymer (A)"), and it is more preferably at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane. More preferably, it is at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester. In addition, the polymer used for preparation of a liquid crystal aligning agent may be only 1 type, and 2 or more types may be sufficient as it. (Meth) acrylate is meant to include acrylate and methacrylate.

[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 tetracarboxylic acid dianhydride with 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 / 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 above specific acid dihydrate and the above specified diamine The method of polymerizing a monomer, etc. are mentioned. Among these, it is preferable to use a specific diamine in that synthesis of the monomer is relatively easy, and specifically, the method of the above [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 preferred examples thereof include the following formula (5-1) And compounds represented by the following formula (5-2).

(In the formula (5-1), A ³ represents a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ represents a single bond, the following formula (1 -1) or a group represented by the following formula (1-2): R ¹⁵ and R ¹⁷ each independently represent 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 following formulas (1-1) and (1-2) "* 1" is bound to R ^16. )

(In formula (1-1) and 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 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-mentioned It is synonymous with Formula (1).)

In the above formula (5-1), R ¹⁵ and R ¹⁷ is an aromatic ring, a group was removed aliphatic ring or three hydrogen atoms from a ring portion of the heterocycle. It is preferably an aromatic ring group or an alicyclic group, more preferably a group obtained by removing three hydrogen atoms from the ring portion of a benzene ring, a naphthalene ring, a cyclopentane ring or a cyclohexane ring, and a benzene ring or a ring More preferably, it is a group in which three hydrogen atoms have been removed from the ring portion of a cyclohexane ring.
The divalent organic group R ^16, can be applied thereto in the description of ^R 5 to R ⁷ in the formula (2-1). In view of improving the afterimage characteristics and the contrast characteristics of the liquid crystal display device, a substituted or unsubstituted aromatic ring group or an alicyclic group is preferable, and more preferably a substituted or unsubstituted aromatic ring group It is.
Examples of the divalent linking group of X ³ and ^{X 4, -O -, - CO} -, - COO -, - CONR 4 - (. R 4 has the same meaning as the above formula (1)), the following equation (2 The bivalent organic group etc. which were illustrated by R < ⁵ > -R < ⁷ > of -1) are mentioned.
About R < ¹ >, R < ² >, R < ³ > and X < ¹ > in said Formula (1-1) and Formula (1-2), description of the said Formula (1) is applicable.
The compound represented by the above formula (5-1), from the viewpoint of synthesis easiness, it is preferred that A ³ is a compound represented by the above formula (1-2), further A ⁴ is a single bond It is more preferable that
In the said Formula (5-2), the illustration of the illustration of R < ⁵ > -R < ⁷ > of following formula (2-1) is applicable to the bivalent organic group of R < ¹⁸ >. As for R ¹⁹ , the illustrations of R ¹⁵ and R ^{17 in} the above formula (5-1) and the description of the preferred embodiments 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。） As a preferable specific example of a specific acid dianhydride, the compound etc. which are represented, for example with each of following formula (t-1)-a formula (t-31) are mentioned. In addition, specific acid dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  In the above 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. I will not. Specifically, in the case of 1 substitution, it may be 2-position, 3-position, 5-position or 6-position, and in the case of 2 substitution, 2,4- position or 3,5-position It is preferred that the R is preferably a methyl group.

The specific acid dianhydride can be synthesized by appropriately combining conventional organic chemistry methods. For example, a compound having “—C (R ¹ ) = C (R ² ) —CO—X ¹ —” is reacted with a phthalic acid derivative to obtain tetra-having tetrastructure represented by the above formula (1). It can be obtained by synthesizing a carboxylic acid and then performing acid anhydrideation of the resulting tetracarboxylic acid. However, the synthesis method of the specific acid dianhydride is not limited to the above.

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

（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. As specific examples of these, as aliphatic tetracarboxylic acid dianhydride, for example, butanetetracarboxylic acid dianhydride, the following formula (AN-2) or the formula (AN-3)

(In the formula (AN-2), X ¹³ and X ¹⁴ each independently represent a group obtained by removing one hydrogen atom from a methylene group or a nitrogen atom, and R ⁴¹ is a C 1-10 alkanediyl group In formula (AN-3), X ¹⁵ and X ¹⁶ each independently represent a group obtained by removing one hydrogen atom from a methylene group or a nitrogen atom, and B ¹ and B ² each independently represent a phenylene group And 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, plural R ^{42 's} are the same as or different from each other May)
Compounds and the like;
Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3) -Furanyl) -3 Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl norbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3, 5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetra Carboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride , Ethylene glycol bis (anhydrotri Melitate), 1,3-propylene glycol bis (anhydro trimellitate), the following formula (AN-4)

Compounds and the like;

（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 aromatic tetracarboxylic acid dianhydride, for example, pyromellitic acid dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, the following formula (AN-1)

(In the 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- (wherein, R ²¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. "*" Is a bond to R ^20. ) 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 having a nitrogen-containing heterocycle A group)
Or a compound represented by the following formula (AN-5-1) to a formula (AN-5-4)

The compound etc. which are represented by each of can be mentioned, respectively; Moreover, the tetracarboxylic acid dianhydride as described in Unexamined-Japanese-Patent No. 2010-97188 can be used.

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

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the formula (AN-1) in R ^20, for example a methylene group, an ethylene group, a propylene group, butanediyl group, pentanediyl group, hexanediyl group, Heputanjiiru Alkanediyl groups such as octanediyl group, nonanediyl group, decanediyl group and the like; divalent alicyclic hydrocarbon groups such as cyclohexylene group; divalent aromatic hydrocarbon groups such as phenylene group and biphenylene group; It can be mentioned. The number of oxygen atoms which may be introduced between carbon-carbon bonds of the hydrocarbon group may be one, or 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。 As specific examples of the compound represented by the above formula (AN-1), for example, a compound represented by each of the following formula (AN-1-1) to the formula (AN-1-27), the following formula (a-) The compound represented by 1), the compound represented by a following formula (a-3), etc. are mentioned.

In the synthesis of the polyamic acid, tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  From the viewpoint of electrical properties, the other acid dianhydrides preferably contain at least one selected from the group consisting of aliphatic tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides, specifically And 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 acid dianhydride, 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 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- It is preferable to include at least one compound selected from the group consisting of tetracarboxylic acid 2: 4: 6: 8-dianhydride and cyclohexanetetracarboxylic acid dianhydride. The amount of these preferred compounds used (the total amount of two or more, if used) is preferably 10 mol% or more based on the total amount of other acid dianhydrides used in the synthesis of the polyamic acid 20 mol% or more is more preferable, and 50 mol% or more is more preferable.

  The use ratio of the specific acid dianhydride in the above method [1] is the total amount of tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid from the viewpoint of sufficiently obtaining the improvement effect of the residual image characteristics and the contrast characteristics of the liquid crystal display element The amount is preferably 10 mol% or more, more preferably 20 mol% or more, and still more 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)
The specific diamine used in the synthesis of the polyamic acid is not particularly limited as long as it has the partial structure represented by the above formula (1), but it is represented, for example, by the following formula (2-1) Compounds, and compounds represented by the following formula (2-2).

(In the formula (2-1), A ¹ represents a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² represents a single bond, 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 some cases, it is a divalent organic group, and in the case of a group represented by the following formula (1-2) or a single bond, it is a single bond or a divalent organic group R ⁶ is a divalent organic group. )

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

(In Formula (1-1) and Formula (1-2), “* 1” represents a bond to be bonded to R ^9. R ¹ , R ² , R ³ , X ¹ and n are the above-mentioned Formula (1) It is synonymous with

In the above formula (2-1), examples of the divalent organic group of R ^{5 to} R ⁷ include, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a part of methylene groups that the hydrocarbon group has. 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, "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, "a chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed only of 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 including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has a chain-like structure in the part is also included. "Aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed of only an 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 are as chain hydrocarbon group such as methylene group, ethylene group, propane-diyl group, butanediyl group, pentanediyl group, 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 represents 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- (wherein , Ar ³ is phenylene group, biphenylene group or naphthylene ^{group, R 32} is also alkanediyl group having 1 to 3 carbon atoms . Cyclohexylene xylene group) and the like; may be mentioned, respectively.
As a bivalent heterocyclic group in R < ⁵ > -R < ⁷ >, the group etc. which remove | eliminated 2 hydrogen atoms from nitrogen-containing heterocyclic rings, such as a pyridine, a piperazine, a piperidine, etc. are mentioned, for example. The R ⁵ to R ⁷ are substituents which may have, for example, a halogen atom, an alkoxy group, a hydroxyl group, a carboxyl group, 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, a biphenylene group, a naphthylene group or a cyclohexylene group, and “* ³ ” represents a bond to a benzene ring. Is preferred. 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), examples of the monovalent organic group of R ⁸ and R ¹⁰ include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a part of the methylene group possessed by 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 of 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, cyclohexyl group, and phenyl Groups, tolyl groups, benzyl groups, biphenyl groups, naphthyl groups, pyridyl groups, piperidyl groups and the like.
The description of R ^{6 in} the above formula (2-1) can be applied to R ⁹ . In the diaminophenyl group which said Formula (2-2) has, it is preferable that two amino groups exist in a 2,4- or 3,5- position with respect to another group.
In addition, the description of the said Formula (1) can apply the description of R < ¹ >, R < ² >, R < ³ > and X < ¹ > in said Formula (1-1) and 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. The partial structure represented by the following formula (4) is preferable in that the reduction effect of the afterimage (AC afterimage) by the AC voltage can be enhanced in the liquid crystal display element.

(In the formula (4), Ar ¹ and Ar ² are independently a substituted or unsubstituted phenylene group or a cyclohexylene group, ^{X 2} represents a single bond, -COO- or ^-CONR 20 - ^{(R 20} is A hydrogen atom or a monovalent organic group) provided that Ar ¹ may constitute a 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 said Formula (4), as a monovalent organic group of R < ²⁰ >, a C1-C6 alkyl group, a protecting group, etc. are mentioned, for example. Specific examples of the protective group include, for example, t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 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, and more preferably a methyl group or a fluorine atom.
As preferable specific examples of the partial structure represented by the above formula (4), for example, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and the following formulas (4-1) to (4) And groups having a methyl group or a fluorine atom in the ring part of these groups, and the like.

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

  When an alignment regulating force is applied to a coating film formed using a liquid crystal alignment agent by a photoalignment method, the above formula (2) is used as the specific diamine in that the AC afterimage reduction effect and the contrast improvement effect of the liquid crystal display element are high. It is preferable to use the compound represented by -1). By using the compound represented by the said Formula (2-1) as a specific diamine, the polymer which has a partial structure represented by the said Formula (1) in a principal chain can be obtained.

As specific examples of the specific diamine, examples of the compound represented by the above formula (2-1) include the following formulas (b-1) to (b-17), and formulas (b-26) to (b-56) Compounds represented by the above-mentioned formula (2-2), for example, compounds represented by the following formulas (b-18) to (b-59), It can be mentioned.

  In addition, in the case of synthesis | combination of a polyamic acid, specific diamine can be used individually by 1 type or in combination of 2 or more types. Of the above formulas (b-1) to (b-59), the formulas (b-1), (b-3), (b-5) to (b-7), (b-11), the formula (b-1) b-18), the formula (b-20), the formulas (b-22) to (b-26), the formula (b-28), the formula (b-41) to the formula (b-45), and the formula (b-) 47), Formula (b-54), Formula (b-56) and Formula (b-57) correspond to a compound having a partial structure represented by the above Formula (4).

Specific diamines can be synthesized by combining conventional methods of organic chemistry as appropriate. As an example, a dinitro intermediate having a nitro group in place of the primary amino group of the compound represented by the above formula (2-1) or formula (2-2) is synthesized, and then the obtained dinitro intermediate is obtained. The method includes amination of 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 desired compound. Specifically, for example, a compound represented by "O ₂ N-R ^5- A ¹ -H" and a compound represented by "HO-R ⁶ -A ² -R ⁷ -NO ₂ " are preferable. 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, for example using a catalyst such as palladium on carbon, platinum oxide, zinc, iron, tin, nickel and the like. As an organic solvent used here, ethyl acetate, toluene, tetrahydrofuran, alcohol type etc. are mentioned, for example. However, the synthesis procedure of the specific diamine is not limited to the above method.

In the synthesis of the polyamic acid as the compound (X), a specific diamine may be used alone, or a diamine (other diamine) having no partial structure represented by the above formula (1) may be used in combination. May be
Such other diamines include, for example, aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes. As specific examples of these, as aliphatic diamines, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1 , 2-bis (2-aminoethoxy) ethane and the like;
As alicyclic diamines, for example, 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 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 each independently represent a single bond, -O-, * ⁴ -COO-or * ⁴ -OCO-(wherein "* ⁴ " is bonded to a benzene ring R ¹ is a C 1 -C 3 alkanediyl group, R ^II is a single bond or a C 1 -C 3 alkanediyl group, 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 can not be 0 simultaneously.)

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。 Or a compound represented by the following formula (da-1) or a formula (da-2)

Orientation 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) F) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropyl) Phenyl) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diamino Acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 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)

Compounds represented by each of
Examples of diaminoorganosiloxanes include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and besides, diamines described in JP-A-2010-97188 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 -, * -COO- or _{* -O-C 2 H 4 -O-} ( where bond marked with "*" is bonded to the diamino phenyl group.) is preferably. Examples of the group “—C _c H _{2c + 1} ” include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl and tetradecyl. Groups, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group etc. can be mentioned, and it is preferable that these are linear. The two amino groups in the diaminophenyl group are preferably in the 2,4- or 3,5-position relative to the other group.

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。 As a specific example of a compound represented by the said Formula (E-1), the compound etc. which are represented by following formula (E-1-1)-(E-1-4), for example can be mentioned.

In addition, as diamine used for the synthesis | combination of a polyamic acid, 1 type of these compounds can be used individually, or 2 or more types can be selected suitably, and can be used.

  When applied to a liquid crystal aligning agent for a liquid crystal display element of TN type, STN type or vertical alignment type, a functional group (liquid crystal alignment property capable of expressing liquid crystal alignment regulating force on the side chain of polyamic acid without 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, and a group having a steroid skeleton having 17 to 51 carbon atoms. The group which has ring structure (For example, group which has the partial structure represented by said Formula (4)) etc. are mentioned. The polyamic acid having a liquid crystal alignment group can be obtained, for example, by polymerization in which the above-mentioned alignment group-containing diamine is contained in the monomer composition. When using an orientation group-containing diamine, the blending ratio is preferably 3 mol% or more, and 5 to 70 mol%, with respect to all diamines used for synthesis, from the viewpoint of making the liquid crystal alignment good. It is more preferable to

When a polyamic acid is synthesized by the above method [2], the proportion of the specific diamine used is the total amount of diamine used in the synthesis of the polyamic acid from the viewpoint of sufficiently obtaining the improvement effect of the residual image characteristics and the contrast characteristics of the liquid crystal display element. On the other hand, it is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more.
Moreover, when synthesizing a polyamic acid 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 tetracarboxylic acid dianhydride and diamine used in the synthesis. It is preferable to set it as the above, It is more preferable to set it as 20 mol% or more, It is more preferable to set it as 30 mol% or more.

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

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

As a molecular weight modifier, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, the following formula (F-1) to formula (F-4)

Acid monoanhydrides such as compounds represented by each of the above, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenylisocyanate and naphthylisocyanate.
In addition, as a molecular weight modifier, a monofunctional compound having a partial structure represented by the above formula (1) may be used. As the said compound, a monoamine compound and an acid monoanhydride can be used preferably. 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), etc. Can be mentioned.

  The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic acid dianhydride and diamine used. In addition, a molecular weight modifier can be used individually by 1 type or in combination of 2 or more types.

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, and 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 for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group organic solvent It is preferable to use a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group organic solvents). In the latter case, the use ratio of the second group organic solvent is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.

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

  As described above, a reaction solution in which the polyamic acid is dissolved is obtained. The reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating polyamic acid contained in the reaction solution, or the isolated polyamic acid is purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be subjected to dehydration ring closure reaction as it is, or polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring closure reaction. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. The isolation and purification of the polyamic acid can be carried out according to known methods.

[Polyamic acid ester]
The polyamic acid ester as the compound (X) can be produced, for example, by a method of reacting a polyamic acid having a partial structure represented by [I] the above formula (1) with an esterification agent, [II] tetracarboxylic acid diester and the like It can be obtained by a method of reacting with a diamine, a method of reacting a [III] tetracarboxylic acid diester dihalide and a diamine, or the like.
In the present specification, the term "tetracarboxylic acid diester" means a compound in which two of four carboxyl groups possessed by a tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" means a compound in which two of four carboxyl groups possessed by the tetracarboxylic acid are esterified and the remaining two are halogenated.

  As an esterifying agent used by method [I], a hydroxyl-containing compound, an acetal type compound, a halide, an epoxy-group containing compound etc. are mentioned, for example. Specific examples of these include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol, phenols such as phenol and cresol, etc .; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethylacetal and 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, chloromethyl isopropyl carbonate, chloromethyl pivalate, chloromethyl acetate, chloromethyl butyrate, chloromethyl methyl sulfide etc. as an epoxy group-containing compound, for example Such as propylene oxide, it 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 polyamic acid described above using an alcohol such as methanol or ethanol. As diamine to be used, the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned. The reaction of method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensing agents. -20-150 degreeC is preferable and, as for the reaction temperature at this time, 0-100 degreeC is more preferable. 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. As diamine to be used, the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned. The reaction of method [III] is preferably carried out in the presence of a suitable base in an organic solvent. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. As a base, for example, tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium hydroxide, potassium and the like can be preferably used. -20-150 degreeC is preferable and, as for the reaction temperature at this time, 0-100 degreeC is more preferable. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

  The polyamic acid ester to be contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated and then provided for preparation of a liquid crystal aligning agent. The purified or isolated polyamic acid ester may be purified and then subjected to the preparation of a liquid crystal aligning agent. Isolation and purification of the polyamic acid ester can be carried out according to known methods.

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

  The polyimide may be a completely imidized product obtained by dehydrating and ring closing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrating and ring closing, and the amic acid structure and the imide. It may be a partial imidate coexisting with a ring structure. The imidation ratio of the polyimide used for the reaction is preferably 20% or more, more preferably 30 to 99%, and still more preferably 40 to 99%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, part of the imide ring may be an isoimide ring.

  The dehydration ring closure of polyamic acid is preferably performed by a method of heating polyamic acid or a method of dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. . Among these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. As an organic solvent used for a dehydration ring-closing reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. 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.

  Thus, a reaction solution containing a polyimide is obtained. The reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring closure catalyst from the reaction solution. It may be subjected to the preparation of the alignment agent, or it may be subjected to the preparation of the liquid crystal alignment agent after purifying the isolated polyimide. These purification procedures can be performed according to known methods. Besides, 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。） When the compound represented by the above formula (5-1) is used among the above specific acid dianhydrides in the synthesis of the compound (X), 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 said Formula (5-2) is used among the said specific acid dianhydrides, it is represented by the partial structure represented by a following formula (6-3), and a following formula (6-4) A polymer having at least one partial structure selected from the group consisting of partial structures is obtained. Moreover, when the compound represented by the said Formula (2-1) is used among the said specific diamines, it is represented by the partial structure represented by a following formula (6-5), and a following formula (6-6) A polymer having at least one partial structure selected from the group consisting of: When the compound represented by the said Formula (2-2) is used among the said specific diamines, from the group which consists of a partial structure represented by each of following formula (6-7)-Formula (6-10) A polymer having at least one partial structure selected is obtained.

(In the formula (6-1) and the formula (6-2), A ³ , A ⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , X ³ and X ⁴ each have the same meaning as the above-mentioned formula (5-1) R ²⁰ and R ²¹ each independently represent 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 each have the same meaning as the above-mentioned formula (1), and R ¹⁸ and R ¹⁹ each have the above-mentioned formula (5- R ²⁰ and R ²¹ each independently represent a hydrogen atom or a monovalent organic group.)

(In the formula (6-5) and the formula (6-6), A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ each have the same meaning as that of 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 each have the same meaning as the above-mentioned formula (2-2). R ²⁰ and R ²¹ each represent 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 above formulas (6-1) to (6-8), examples of the monovalent organic group of R ²⁰ and R ²¹ include, for example, 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 R ²² and R ^23, chain hydrocarbon group, an alicyclic group, aromatic ring group, and heterocyclic groups. Preferably, an alicyclic group or an aromatic ring group, Specific examples thereof can be applied to the description of R ¹⁵ and R ¹⁷ in the formula (5-1).

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 is 10% by weight, and 15 to 500 mPa · s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above-mentioned polymer is a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone and the like). It is a value measured at 25 ° C. using an E-type rotational viscometer (the same applies to the following polymers).
The weight average molecular weight (Mw) in terms of polystyrene 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. By being in 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, for example, by a method of reacting dicarboxylic acid and diamine. Here, the dicarboxylic acid is preferably acid-chloridized with a suitable chlorinating agent such as thionyl chloride and then subjected to a reaction with a diamine.

The dicarboxylic acid to be used for the synthesis of the polyamide is not particularly limited. Aliphatic dicarboxylic acids such as 2-dimethyl glutaric acid, 3, 3-diethyl succinic acid, azelaic acid, sebacic acid, suberic acid, fumaric acid, muconic acid;
A dicarboxylic acid having an alicyclic structure such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid and the like;
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 dicarboxylic acids having an aromatic ring such as cyclobutane dicarboxylic acid. In addition, dicarboxylic acid can be used individually by 1 type or in combination of 2 or more types.

  The diamine used in synthesizing the polyamide as the compound (X) contains a specific diamine. In addition, other diamines may be used in combination as necessary. The proportion of the specific diamine used is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more based on the total amount of diamine used in the synthesis of the polyamide. preferable. In addition, diamine can be used individually by 1 type or in combination of 2 or more types.

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

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

  As described above, the reaction solution in which the polyamide is dissolved is obtained. The reaction solution may be used as it is for preparation of a liquid crystal alignment agent, or may be used for preparation of a liquid crystal alignment agent after isolating polyamide contained in the reaction solution, or after purifying the isolated polyamide. You may use for preparation of a liquid crystal aligning agent. The isolation and purification of the polyamide can be carried out according to known methods.

  The solution viscosity of the polyamide as the compound (X) is preferably one having a solution viscosity of 10 to 800 mPa · s when this is made into a solution having a concentration of 10% by weight, and a solution viscosity of 15 to 500 mPa · s. It is more preferable to have Moreover, about polyamide, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC is preferably 1,000 to 500,000, and 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] Hydrolytic condensation of the 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 Methods, etc. can be mentioned. Among these, the method of [1] is preferred in that it is simple and can increase the introduction rate of the partial structure represented by the above formula (1) in the polymer (S). In the method of [1], the reaction product of a polyorganosiloxane having an epoxy group and a carboxylic acid is used as a compound (X).

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

Other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like. Alkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane;
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3 -A nitrogen / sulfur atom-containing alkoxysilane such as cyclohexylamino) propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, etc .;
3- (Meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 6- (Meth) acryloyloxyhexyltrimethoxysilane, 3- (Meth) acryloxypropylmethyldimethoxysilane, 3- Unsaturated hydrocarbon-containing alkoxysilanes such as (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, and the like, as well as trimethoxysilylpropylsuccinic anhydride and the like Can be mentioned. The other silane compounds can be used alone or in combination of two or more.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent.
In the method of the above-mentioned [1], it is possible to introduce a sufficient amount of the partial structure represented by the above-mentioned formula (1) into the side chain of the polymer, and at the same time, 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, in synthesizing the epoxy group-containing polyorganosiloxane, it is preferable to adjust the use ratio of the silane compound (ms-1) so that the epoxy equivalent of the obtained polyorganosiloxane becomes the above range.
In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds and zirconium compounds. Among these catalysts, alkali metal compounds or organic bases are suitable as the catalyst in that they can suppress side reactions such as ring opening of epoxy groups, can accelerate the rate of hydrolysis and condensation, and are excellent in storage stability. In particular, tertiary or quaternary organic bases are preferred.
The amount of organic base used varies depending on the type of organic base, reaction conditions such as temperature, etc. and should be set appropriately, but it is preferably 0.01 to 3 times the molar amount to all silane compounds, More preferably, it is 0.05 to 1 mole.

Examples of the organic solvent used in the hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers and alcohols. 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, cyclopentanone and the like; esters such as ethyl acetate , N-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate etc .; as ether, eg ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane etc .; as alcohol For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, eth Glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether and the like; may be mentioned, respectively. Among 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 hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of all silane compounds used in the reaction. .

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

  In the method of the above [1], the epoxy group-containing polyorganosiloxane obtained by the above reaction is then reacted with a specific carboxylic acid. Thus, 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。） As a specific example of a specific carboxylic acid, the compound etc. which are represented by following formula (3) are mentioned, for example.

(In Formula (3), A ¹ and A ² are respectively synonymous with the above Formula (2-1), provided that “* 1” in the above Formula (1-1) and Formula (1-2) is And a bond to be bonded to R ^12. R ¹¹ is a monovalent organic group when A ¹ is a group represented by the following formula (1-1), and A ¹ is a group represented by the following formula (1-2 ) ^{.R 12} is a hydrogen atom or a monovalent organic group when the group represented by is a divalent organic radical ^{.R 13} is a ^{group a 2} is represented by the following formula (1-1) When it is a divalent organic group, and when A ² is a group represented by the following formula (1-2), it is a single bond or a divalent organic group s and r are each independently It is 0 or 1. However, it has one carboxyl group in Formula (3).)

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

  The specific carboxylic acid preferably further has a partial structure represented by the above formula (4) in the molecule together with the partial structure represented by the above formula (1), from the viewpoint of enhancing the reduction effect of the AC residual image. In addition, the description in the case of specific diamine can apply the preferable specific example of the partial structure represented by said Formula (4). Further, the benzene ring in the above formula (1) may constitute a part of the structure represented by the above formula (4) as in 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。 As a specific example of a specific carboxylic acid, the compound etc. which are represented, for example with each of following formula (g-1)-a formula (g-13) can be mentioned.

In the synthesis of the polymer (S), the specific carboxylic acids can be used singly or in combination of two or more. Among the formulas (g-1) to (g-13), the formulas (g-1), (g-2), (g-4) to (g-8), and the formulas (g-11) to The formula (g-13) corresponds to a compound having a partial structure represented by the above 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%, and still more preferably 10 to 90 mol%. Therefore, when synthesizing the polymer (S), it is preferable to select the use ratio of the specific carboxylic acid so that the content ratio of the partial structure represented by the above formula (1) falls within the above range.

The specific carboxylic acid can be synthesized by appropriately combining conventional organic chemistry methods. As an example, for example, a compound represented by "R ¹¹ -A ¹ -H" and "HO-R ¹² -A ² -R ¹³ -COOM (wherein M is a protective group for a carboxyl group)" The compound can be obtained preferably by a reaction in an organic solvent, if necessary, in the presence of a catalyst, followed by deprotection. However, the synthesis procedure of 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 in the reaction with the epoxy group-containing polyorganosiloxane may be only the specific carboxylic acid, but other carboxylic acids other than the specific carboxylic acid may be used in combination .
The other carboxylic acids are not particularly limited as long as they do not have a partial structure represented by the above formula (1), and examples thereof include carboxylic acids having the above-mentioned liquid crystal aligning group. Specific examples of other carboxylic acids include, for example, fatty acids having 6 to 20 carbon atoms such as caproic acid, lauric acid, pentadecyl acid, palmitic acid, stearic acid, stearic acid, oleic acid, acetic acid, linoleic acid, linolenic acid, arachidic acid, etc. The compound etc. which are represented by each of a following formula (C-2-1)-a formula (C-2-10) can be mentioned.

(Wherein, j is an integer of 0 to 12 and h is an integer of 1 to 10)
Other carboxylic acids can be used singly or in combination of two or more selected from among these.

The proportion of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 moles, and preferably 0.01 to 1 mole, with respect to 1 mole in total of epoxy groups contained in the polyorganosiloxane. It is more preferable to set it to .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, preferably 50 mol% or less, with respect to the total amount of carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane. It is more preferable to make it% or less.

The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid can preferably be carried out in the presence of a catalyst and an organic solvent.
As a catalyst used in the reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid, for example, a known compound as a so-called curing accelerator which accelerates the reaction of an organic base or an epoxy compound can be used. Here, as the organic base, for example, primary to secondary organic amines such as ethylamine, piperazine and piperidine; tertiary organic amines such as triethylamine and pyridine; quaternary organic amines such as tetramethylammonium hydroxide; Can. Among these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines, imidazole compounds, organophosphorus compounds, quaternary phosphonium salts, organometallic compounds such as diazabicycloalkenes and tin octylate, quaternary ammonium salts, boron compounds, second chlorides And metal halogen compounds such as tin. Among these, quaternary ammonium salts are preferable, and specific examples thereof include tetraethyl ammonium bromide, tetra-n-butyl ammonium bromide, tetraethyl ammonium chloride, tetra-n-butyl ammonium chloride and the like.
The catalyst is used in a proportion of preferably not more than 100 parts by weight, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the epoxy group-containing polyorganosiloxane. Ru.

  Examples of the organic solvent used in the above reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Among them, ethers, esters and ketones are preferable from the viewpoint of solubility of raw materials and products, and ease of purification of the product, and as a specific example of particularly preferable solvents, 2-butanone, 2-hexanone, methyl Examples include isobutyl ketone and butyl acetate. The organic solvent is preferably used in a proportion such that the solid concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it in the ratio which will be 5 to 50 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. Further, after completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. After washing with water, the organic solvent layer is optionally dried with a suitable drying agent, and then the solvent is removed to obtain a polymer (S). The method for synthesizing polyorganosiloxane is not limited to the above-mentioned hydrolysis / condensation reaction, and for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol may be employed.

（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, the following formula (7): It is preferable to have a partial structure represented by

(In 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), and Z ¹ is a divalent organic group. * Indicates that it is a bond with a silicon atom.)
Note that the divalent organic group ^{Z 1,} such as the groups exemplified in ^R 5 to R ⁷ in the formula (2-1) can be mentioned.

  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 a solution having a concentration of 10% by weight, and 3 to 200 mPa More preferably, it has a solution viscosity of s. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC for the polymer (S) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, 3 It is more preferable that 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 others The resulting polymer (hereinafter, also referred to as "epoxy group-containing poly (meth) acrylate") is obtained by polymerizing a mixture with the (meth) acrylic monomer in the presence of a polymerization initiator. It can be obtained by a method of reacting with a specific carboxylic acid.

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

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

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

The polymerization reaction using a (meth) acrylic monomer is preferably performed by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include initiators commonly used in radical polymerization, and examples thereof include 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (2,4). -Azo compounds such as dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis ( Organic peroxides such as t-butylperoxy) cyclohexane; hydrogen peroxide; redox type initiators comprising these peroxides and a reducing agent, and the like. Among these, an azo compound is preferable, and 2,2′-azobis (isobutyronitrile) is more preferable. As a polymerization initiator, these can be used individually by 1 type or in combination of 2 or more types.
The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of all the monomers used for 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 alcohol and ether, and it is more preferable to use a partial ether of polyhydric alcohol. As a preferable specific example thereof, for example, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate and the like can be mentioned. 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., and more preferably 60 ° C. to 110 ° C. The reaction time is preferably 1 to 36 hours, and 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 for the reaction is 0.1 to 50% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable to do.

A specific carboxylic acid is then reacted with the epoxy group-containing poly (meth) acrylate obtained by the above reaction. The description of the polymer (S) can be applied as a specific example of the specific carboxylic acid. Further, in the reaction, the specific carboxylic acid may be used alone, or other carboxylic acids other than the specific carboxylic acid may be used in combination.
The use ratio of the carboxylic acid to be reacted with the epoxy group-containing poly (meth) acrylate may be 0.001 to 0.95 mol with respect to 1 mol in total of the epoxy groups contained in the epoxy group-containing poly (meth) acrylate. preferable. More preferably, it is 0.01 to 0.9 mol, and more preferably 0.05 to 0.8 mol.

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

  As an organic solvent used for reaction, the illustration of the organic solvent which can be used in the case of superposition | polymerization of a (meth) acrylic-type monomer can be applied, Especially, it is preferable that it is ester. The organic solvent is preferably used in a proportion such that the solid concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it in the ratio which will be 5 to 50 weight%. The reaction temperature is preferably 0 to 200 ° C., and more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, and more preferably 0.5 to 20 hours.

  Thus, a solution containing poly (meth) acrylate as compound (X) can be obtained. This reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be subjected to the preparation of a liquid crystal aligning agent after the poly (meth) acrylate contained in the reaction solution is isolated. After purifying (meth) acrylate, it may be used for preparation of a liquid crystal aligning agent. The isolation and purification of poly (meth) acrylate can be carried out according to known methods.

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

  With respect to poly (meth) acrylate, the polystyrene equivalent number average molecular weight (Mn) measured by GPC makes the liquid crystal alignment of the liquid crystal alignment film to be formed good and secures the temporal stability of the liquid crystal alignment. From the viewpoint of the above, the value is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Other ingredients>
The liquid crystal aligning agent according to the present invention contains the compound (X) as described above, but may contain other components as necessary. As other components which may be added to the liquid crystal aligning agent, for example, other polymers other than the above compound (X), a compound having at least one epoxy group in the molecule (hereinafter, “epoxy group-containing compound”) And 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 other polymers can be used to improve solution properties and electrical properties. Such other polymers are polymers which do not have a partial structure represented by the above formula (1), and the main skeleton thereof 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, etc. 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 other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 90 parts by weight or less with respect to 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent, The amount is more preferably 80 parts by weight, and still more preferably 0.1 to 70 parts by weight.

[Epoxy group-containing compound]
An epoxy group containing compound can be used in order to improve the adhesiveness with the substrate surface in a liquid crystal aligning film, and an electrical property. Examples of such an epoxy group-containing compound 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, glycerine diglycidyl ether, trimethylolpropane triglycidyl ether, 2, 2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'- tetraglycidyl-m-xylylene di Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamide Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. In addition, as an example of an epoxy-group containing compound, the epoxy-group-containing polyorganosiloxane of WO2009 / 096598 can be used.
When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less with respect to 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent, and 0.1 to 30 It is more preferable to use parts by weight.

[Functional Silane Compound]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Such functional silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 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 -3, 6- Methyl azanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycide And xylpropyltrimethoxysilane and the like.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent, and 0.02 It is more preferable that the amount be about 0.2 parts by weight.

[Photopolymerizable Group-Containing Compound]
The photopolymerizable group-containing compound is used for the purpose of enhancing the alignment control force in the liquid crystal alignment film, when the liquid crystal alignment ability is imparted by irradiating the coating film formed with the liquid crystal alignment agent with light. Can. Here, examples of the photopolymerizable group include, for example, a group having a polymerizable unsaturated bond and the like. Specifically, for example, (meth) acryloyloxy group, styryl group, (meth) acrylamide group, vinyl group, vinylidene group, vinyloxy group _{(CH 2 = CH-O-)} , maleimide group.

As such a photopolymerizable group-containing compound, a (meth) acrylate compound can be preferably used from the viewpoint of high photoreactivity, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( Meta) 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) acrylates; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, polyether (meth) acrylate Over DOO, polyfunctional (meth) acrylates such as ethoxylated bisphenol A di (meth) acrylate; and the like.
When the photopolymerizable group-containing compound is added to the liquid crystal aligning agent, the blending ratio is preferably 30 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. 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, “photosensitizing function” means that, after being in a singlet excited state by irradiation of light, in some cases, an intersystem crossing occurs, and when it collides with another molecule, the partner is changed to an excited state, A function that returns to the ground state. As a specific example of a photosensitizer, the compound etc. which are represented, for example with each of following formula (H-1)-formula (H-6) can be mentioned.

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

  In addition, the additive normally used for preparation of a liquid crystal aligning agent can be used as another component. Examples of 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 which are optionally used are preferably dispersed or dissolved in a suitable solvent.

  As an organic solvent to be used, for example, 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 methoxy propionate, 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 Recall diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. be able to. These can be used alone or in combination of two or more.

The liquid crystal aligning agent which concerns on this invention may contain only 1 type of polymer as a polymer component, and may contain 2 or more types of polymers. As a preferable aspect in the case of containing 2 or more types of polymers, the following [1]-[3] etc. are mentioned, for example.
[1] A polymer (hereinafter also referred to as “specific polymer”) as the compound (X) and other polymers, and the specific polymer and the other polymers are polyamic acid, polyamic acid ester, The aspect which is at least 1 type chosen from a polyimide and a polyamide.
[2] An embodiment containing a plurality of specific polymers, and the plurality of specific polymers being at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide.
[3] A specific polymer and another polymer are contained, and 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 embodiment of [1], when the specific polymer is a 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 assumed that the other polymers are localized in the lower layer, and thus the distribution of the polymers can be biased in the liquid crystal alignment film.

In addition, when the liquid crystal aligning agent containing compound (X) is used, although the reason the improvement effect of the afterimage characteristic of a liquid crystal display element and contrast characteristic was acquired is not certain, the following thing is considered as one hypothesis . That is, in the partial structure represented by the above formula (1), the compound (X) is such that a monovalent organic group is introduced to at least one of α carbon and β carbon of a carbonyl group, preferably α carbon of a carbonyl group. In the presence of light, the photodimerization reaction is suppressed and light is emitted when light is irradiated, as compared to 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 conceivable that the isomerization reaction proceeds predominantly. Thereby, in the liquid crystal aligning film formed using the liquid crystal aligning agent containing a compound (X), the alignment control power of a liquid crystal is improved, As a result, the improvement effect of the afterimage characteristic and contrast characteristic of a liquid crystal display element was acquired It is guessed.

  The solid concentration in the liquid crystal aligning agent according to the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility and the like 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 substrate surface 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 and the coatability decreases. There is a tendency.

  The particularly preferred range of solid content concentration varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, in the case of using a spinner method, 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 Being particularly preferred. In the case of the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by weight and thereby to set the solution viscosity in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by weight and thereby to set the solution viscosity in the range of 3 to 15 mPa · s. The temperature at the time of 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 device>
A liquid crystal aligning film can be manufactured by using the liquid crystal aligning agent which concerns on this invention demonstrated above. Moreover, the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display device according to the present invention is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type It can be applied to various operation modes.

  The liquid crystal display element according to the present invention can be produced, for example, by the 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. The step (1-2) and the step (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 coated on a substrate, and then the coated 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, each transparent conductive film is formed by using two substrates provided with the patterned transparent conductive film as a pair. On the surface, the liquid crystal aligning agent according to the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. As the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of a substrate, a NESA film (registered trademark of US PPG) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. It can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo etching after forming a non-patterned transparent conductive film; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. At the time of application of 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 and a functional titanium compound are formed on the surface of the substrate surface on which the coating film is formed. It is possible to pre-treat etc. beforehand.

  After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebake temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and optionally thermally imidizing the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film 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 is provided on the electrode formation surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape. The liquid crystal aligning agent of the present invention is applied to one side of the opposite substrate which has not been treated, and then the coated surface is heated to form a coating film. The material 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 metal film, the pretreatment of the substrate, and the preferred thickness of the coating film formed It is the same as (1-1A). For example, a film made of a metal such as chromium can be used as the metal film.

  In any case of the above (1-1A) and (1-1B), after the liquid crystal aligning agent is applied on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film. Ru. At this time, by further heating after the formation of a coating, the dehydration ring closure reaction of the polyamic acid, polyamic acid ester and polyimide blended in the liquid crystal aligning agent of the present invention may be advanced to form a more imidized coating.

[Step (1-2): Processing for Providing Orientation Ability]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process which provides liquid crystal aligning ability to the coating film formed at the said process (1-1) is implemented. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. For example, rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc., and light alignment in which polarized or non-polarized radiation is irradiated to the coating film. Processing etc. are mentioned. On the other hand, in the case of producing a VA-type liquid crystal display element, the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film. May be

  [1] A method of irradiating the coating film after the [1] post-baking process, [2] a method of irradiating the coating film after the [2] pre-baking process and before the post-baking process, [3] The coating film can be irradiated during the heating of the coating film in at least one of the pre-baking step and the post-baking step, or the like. Among these, the method of [2] is preferable in that the improvement effect of the afterimage characteristic and the contrast characteristic of the liquid crystal display element is high.

As a radiation which irradiates a coating film, the ultraviolet-ray and visible light which contain the light of a wavelength of 150-800 nm, for example can be used. If the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from the direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of irradiation is oblique.
As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. Ultraviolet light in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating or the like. The dose of radiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . In addition, light irradiation of the coating may be performed while heating the coating in order to enhance the reactivity. The temperature upon heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, and more preferably 50 to 150 ° C.

  The liquid crystal alignment film after rubbing treatment is further irradiated with ultraviolet light to a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film, or The resist film may be formed on the portion, and the rubbing treatment may be performed in a direction different from the rubbing treatment described above, and then the resist film may be removed to make the liquid crystal alignment film have different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. The liquid crystal alignment film suitable for a VA type liquid crystal display element can be suitably used also for a liquid crystal display element of PSA (Polymer sustained alignment) type.

[Step (1-3): Construction of Liquid Crystal Cell]
(1-3A) A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed as described above, and disposing a liquid crystal between two substrates disposed opposite to each other. For example, the following two methods may be mentioned to manufacture a liquid crystal cell. The first method is a conventionally known method. First, two substrates are disposed opposite to each other with a gap (cell gap) in such a manner that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent. The liquid crystal is injected and filled in the cell gap partitioned by the agent, and then the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and then liquid crystal is dropped on a predetermined number of places on the liquid crystal alignment film. After that, the other substrate is pasted together so that the liquid crystal alignment film faces each other, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent. . Regardless of which method is used, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, thereby achieving flow alignment at the time of liquid crystal filling. It is desirable to remove.

As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.
Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl A cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cubane type liquid crystal, or the like can be used. In addition, cholesteric liquid crystals such as colestil chloride, cholesteryl nonaate, cholesteryl carbonate, and the like; and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). And ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

(1-3B) When manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as (1-3A) except that a photopolymerizable compound is injected or dropped together with liquid crystal. After that, light is irradiated to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Further, as the light to be irradiated, for example, ultraviolet light including visible light having a wavelength of 150 to 800 nm and visible light may be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, 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, for example. In addition, the ultraviolet-ray of said preferable wavelength area can be obtained by the means etc. which use a light source together with a filter diffraction grating etc., for example. 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 formed in the same manner as the above (1-3A). Alternatively, a method of manufacturing a liquid crystal display element may be adopted by passing through a process of irradiating a liquid crystal cell in a state where a voltage is applied between conductive films of a pair of substrates. According to this method, the merits of the PSA mode can be reduced and the light irradiation amount can be realized. The description of the above (1-3B) can be applied to the voltage to be applied and the conditions of light to be applied.

  Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, whereby the liquid crystal display element of the present invention can be obtained. As a polarizing plate to be bonded to the outer surface of a liquid crystal cell, the polarizing plate or H film itself is a polarizing film called “H film” which absorbs iodine while drawing and orienting polyvinyl alcohol, sandwiched by a cellulose acetate protective film The polarizing plate which consists of can be mentioned.

  The liquid crystal display device according to the present invention can be effectively applied to various devices. For example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone And various displays such as various monitors, liquid crystal televisions, and information displays.

  Hereinafter, the present invention will be more specifically described 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. TSKgel GRC XLII
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)
The compound (b-1) was synthesized according to the following scheme 1.

9.6 g of 4-nitrobenzaldehyde and 15.0 g of methyl malonic acid were dissolved in 100 ml of pyridine, to which 12.5 ml of piperidine was added, 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 it. The reaction solution was separated again with pure water, and concentrated to obtain an intermediate (b-1-1) as white solid 10.5 g, purity 99%.
10 g of the obtained intermediate (b-1-1) was added to 30 ml of thionyl chloride, a catalytic amount of N, N-dimethylformamide was added, 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). 9.4 g of 4-hydroxy-4'-nitrobiphenyl and 8.9 g of triethylamine were added to 60 ml of tetrahydrofuran, and this was cooled to 0 ° C and stirred for 5 minutes. Then, the reaction solution (A) was slowly dropped. After completion of the dropwise addition, the reaction was stirred at room temperature for 4 hours to complete the reaction. Add 300 ml of ethyl acetate and 100 ml of THF, separate this solution with hydrochloric acid, an aqueous solution of sodium carbonate and pure water, concentrate it, and intermediate (b-1-2) as a white solid 19.0 g, purity 99% I got it.
Subsequently, 18.0 g of 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, and the mixture was partitioned with pure water, and concentrated to obtain a compound (b-1) as a yellow solid 13.5 g, purity 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 in the same manner as in Example 1-1 except that 4-hydroxy-4'-nitrobiphenyl is changed to 4-amino-4'-nitrobiphenyl in the second step of Scheme 1 of Example 1-1 The compound (b-3) was obtained.

Example 1-4 Synthesis of Compound (g-1)
In the first step of Scheme 1 of Example 1-1, the same operation as in the first step of Scheme 1 is carried out except that 4-nitrobenzaldehyde is changed to 4-phenylbenzaldehyde, and a compound (g-1) is obtained in one step. I got

Example 1-5 Synthesis of Compound (b-27)
In the second step of Scheme 1 of Example 1-1, the 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. , The compound (b-27) was obtained.

Example 1-6 Synthesis of Compound (t-5)
The 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, this was cooled to 0 ° C. and stirred for 5 minutes. A solution prepared by adding 12.1 g of methacryloyl chloride to 100 ml of tetrahydrofuran was slowly dropped there. After completion of the dropwise addition, the reaction was stirred at room temperature for 4 hours to complete the reaction. After 300 ml of ethyl acetate was added, this solution was partitioned with hydrochloric acid, aqueous sodium carbonate solution and pure water, and then concentrated to give an intermediate (t-5-1) as a white solid 11.6 g, purity 99%. The
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 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 the solution was partitioned with pure water. Hydrochloric acid was added to the obtained aqueous layer to make an acidic aqueous solution, and then 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) at 20.0 g of a pale yellow solid with a purity of 99%.
Then, 18.0 g of intermediate (t-5-2) was added to 100 ml of acetic anhydride. Then, it stirred at 60 degreeC for 12 hours. The reaction mixture was allowed to cool to room temperature, and the precipitated solid was filtered, washed with hexane and dried to give compound (t-5) as a pale yellow solid 15.5 g with a purity of 99%.

<Synthesis of polymer>
Example 2-1 Synthesis of Polymer (A-1)
100 mol parts of the compound represented by the above formula (a-1) as tetracarboxylic acid dianhydride and 100 mol parts of the compound (b-1) as diamine are 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 acids (polymers (A-2) to (A-9) were prepared in the same manner as in Example 2-1 except that the type and amount of tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 1 below. And polymers (B-1) to (B-3)) were synthesized respectively.

In Table 1, the numerical value in the parenthesis of tetracarboxylic acid dianhydride and diamine represents the use ratio [mol part] with respect to a total of 100 mol parts of tetracarboxylic acid dianhydride used for the synthesis of the polymer. 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 acid dianhydride a-5: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride a-6: pyromellitic acid dianhydride t- 5: Compound represented by the above formula (t-5) <diamine>
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. Subsequently, 100 g of pure water was slowly dropped, and the mixture was stirred at 80 ° C. for 6 hours. Thereafter, the organic layer is taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing becomes neutral, and then concentrated to obtain an epoxy group-containing polyorganosiloxane (ES-1). Obtained as a clear liquid. Mw of the polyorganosiloxane (ES-1) which has this epoxy group was 2,200, and the epoxy equivalent was 186 g / mol.

Synthesis Example 2-10 Synthesis of Polymer (S-1)
9.3 g of epoxy-containing polyorganosiloxane (ES-1) obtained in the above Synthesis Example 4, 26 g of methyl isobutyl ketone, 3 g of the compound (g-1) obtained in the above Synthesis Example 1-4, and UCAT 18X Name, a quaternary amine salt manufactured by San-Apro Co., Ltd.) 0.10 g was mixed and stirred at 80 ° C. for 12 hours. Thereafter, the reaction mixture is poured into methanol, and the formed precipitate is filtered and dissolved in ethyl acetate to form a solution, and the solution is separated with pure water and concentrated to give compound (X) 6.3g of 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 Alignment 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, and the solvent composition was NMP. : It was set as the solution of BC = 70: 30 (weight ratio) and 3.0 weight% of solid content concentration. The solution was filtered using a filter with a pore size of 0.45 μm to prepare a liquid crystal aligning agent.

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 glass substrate 11a having an electrode pair on one side of which is formed a bottom electrode 15 not having a pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape in this order And the opposite glass substrate 11b not provided with a pair, the surface of the glass substrate 11a having the transparent electrode and the one surface of the opposite glass substrate 11b are respectively the above-mentioned 1. The liquid crystal aligning agent prepared in the above 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. Also, as the top electrode 13, drive electrodes of four systems of the electrode A, the electrode B, the electrode C, and the electrode D were used (FIG. 3). The bottom electrode 15 functions as a common electrode acting on all of the four drive electrodes, and each of the four drive electrode regions is a pixel region.
After the formation of the coating film by a spinner, the coating film was prebaked on a hot plate at 80 ° C. for 1 minute. Subsequently, each surface of the coated film was irradiated with polarized ultraviolet light 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 polarized ultraviolet light is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment of the polarization plane of polarized ultraviolet light projected onto the substrate is the direction of the double-headed arrow in FIG. The light irradiation process was performed after setting. After light irradiation, the inside of the chamber was heated (post-baked) at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having an average film thickness of 0.1 μm.

Subsequently, 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 having the liquid crystal alignment film of one of the above substrates, and then the liquid crystal alignment film surfaces of the pair of substrates are It was made to face each other, superimposed so that the direction of polarization plane of polarized ultraviolet light projected onto the substrate was parallel, and pressed, and the adhesive was thermally cured at 150 ° C. for 1 hour. Then, after filling liquid crystal "MLC-7028" manufactured by Merck into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, this was heated to 150 ° C. and then gradually cooled to room temperature in order to remove the flow alignment at the time of liquid crystal injection.
Next, polarizing plates were attached to both outer sides of the substrate to manufacture an FFS liquid crystal display element. At this time, one of the polarizing plates is attached so that the polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other has its polarization direction first. It stuck so as to be orthogonal to the polarization direction of the polarizing plate.
Further, by performing the above-described series of operations while changing the ultraviolet irradiation dose 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 doses can be obtained. Manufactured.

3. Evaluation of Liquid Crystal Display Element Above 2. The following (1) was evaluated using the liquid crystal display element manufactured by above. In addition, except that the polarizing plates were not attached, the above 2. The liquid crystal display element (liquid crystal cell which is not bonded to the polarizing plate) was manufactured by performing the same operation as in the above, and the following (2) was evaluated. In addition, about the evaluation result, the best result was chosen out of 3 or more liquid crystal display elements from which an ultraviolet irradiation amount differs, and it used for evaluation of a liquid crystal display element.

(1) Evaluation of AC afterimage characteristics described above 2. The FFS type liquid crystal display device manufactured in the above was placed under an environment of 25 ° C. and 1 atm. The potential of the bottom electrode was set to a 0 V potential (ground potential), with the bottom electrode as a common electrode for all the four drive electrodes. The electrode B and the electrode D were short-circuited with the common electrode to apply 0 V, and a combined voltage of 5 V AC was applied to the electrodes A and C for 100 hours. After 100 hours, a voltage of AC 1.5 V was immediately 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 drive stress application region (pixel region of the electrodes A and C) and the drive stress non-application region (electrode B and electrode D) The time until the difference in luminance with the pixel region of (1) could not be confirmed visually was measured, and this was taken as the residual image erasing time Ts. Note that as this time is shorter, afterimage is less likely to occur. If the residual image erasing time Ts is less than 30 seconds is "good (○)", if it is 30 seconds or more and less than 120 seconds is "good ())", if it is 120 seconds or more "defect (×) The liquid crystal display element of this example was evaluated as having "good" afterimage characteristics.

(2) Evaluation of contrast after driving stress Using a device in which a polarizer and an analyzer are disposed between the light source and the light quantity detector after driving the liquid crystal display element manufactured in step 30 for 30 hours with an AC voltage of 10 V, the minimum relative The transmittance (%) was measured.
Minimum relative transmittance (%) = (β-B ⁰ ) / (B ¹⁰⁰ -B ⁰ ) × 100 (1)
(In the formula (1), B ⁰ is a blank and transmission of light under crossed nicols. B ¹⁰⁰ is a blank and transmission of light under paranicole. Β is a polarizer and crossed polarizers under crossed nicols. The liquid crystal display element is sandwiched between the analyzers, and the light transmission amount is minimized.)
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 regarded as “good (○)” and those with a minimum relative transmittance of 0.5% or more and less than 1.0% are regarded as “good (Δ)”. "Defective (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]
A liquid crystal aligning agent was prepared with the same solvent ratio and solid content concentration as in Example 3-1 except that the type of the polymer used was changed as shown in Table 2 below. Moreover, while manufacturing a liquid crystal display element similarly to Example 3-1 using each liquid crystal aligning agent, various evaluation was 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 a compound (X), evaluation of AC afterimage characteristic and contrast characteristic was "good" or "OK" in any Example. (Examples 3-1 to 3-7, Reference 3-8, Examples 3-9, and Examples 3-10). In particular, 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 to Examples 3-8 having the side chain of the polysiloxane skeleton. Moreover, it turned out that the improvement effect of AC afterimage characteristic becomes high by using the diamine which has a polycyclic structure like a biphenyl structure.
On the other hand, in the liquid crystal aligning agent of the comparative example which does not contain a compound (X), AC afterimage characteristic and contrast characteristic were inferior to the thing of an Example.

Claims (9)

The liquid crystal aligning agent containing the polymer which has a partial structure represented by following formula (1) in a principal chain.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent, provided that R ¹ and R ² are as well. at least one of a halogen atom, .X ¹ is a cyano group or a monovalent organic group is an oxygen atom or -NR ⁴ - (provided that, ^{R 4} is a hydrogen atom, a hydroxyl group or a monovalent organic group, ^{R 4} is R ³ may be bonded to another group to form a ring structure with a nitrogen atom) R ³ may be bonded to another group to form at least a part of a ring, n is 0 It is an integer of-4. When n is 2 or more, plural R ^{3 s} may be the same or different. "*" Represents a bond.)   The polymer having a partial structure represented by the above 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 as described in.   The polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and is a part derived from a diamine having a partial structure represented by the above formula (1) The liquid crystal aligning agent of Claim 2 which has 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 a molecule.

(In formula (4), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted phenylene group or a substituted or unsubstituted cyclohexylene group, and X ² represents a single bond, -COO- or -CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group) provided that Ar ¹ may constitute a benzene ring in the above formula (1) t is 1 or 2 Ar ² and X ² each independently have the above definition when t = 2. "*" 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 is tetracarboxylic acid dianhydride having a partial structure represented by the above formula (1) The liquid crystal aligning agent as described in any one of Claims 2-4 which has the partial structure derived from a thing. The liquid crystal aligning agent as described in any one of Claims 1-5 whose said R < ² > is a C1-C10 alkyl group.   The manufacturing method of the liquid crystal aligning film including the process of apply | coating the liquid crystal aligning agent as described in any one of Claims 1-6 on a board | substrate, and forming a coating film, and the process of light-irradiating to the said coating film.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-6.   The liquid crystal display element which comprises the liquid crystal aligning film of Claim 8.

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