TWI691526B - Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display element, polymer, diamine compound and carboxylic acid - Google Patents

Abstract

In the present invention, the liquid crystal alignment agent contains a compound (X) having a partial structure represented by the 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; wherein at least one of R ¹ and R ² is a halogen atom , Cyano group or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein, R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, R ⁴ can also be bonded to other groups and a nitrogen atom And form a ring structure). R ³ can also be bonded to other groups to form a ring structure; n is an integer from 0 to 4; "*" indicates a binding bond)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal alignment film manufacturing Method, liquid crystal display element, polymer, diamine compound and carboxylic acid

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

Liquid crystal display elements are widely used in televisions or mobile devices, various monitors, etc. In addition, in the liquid crystal display element, a liquid crystal alignment film is used for the alignment control of the liquid crystal molecules in the liquid crystal cell. As a method for obtaining an organic film having a specific liquid crystal alignment-limiting force, a method of rubbing an organic film, a method of obliquely vapor-depositing silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, and photosensitive A method of irradiating a light-emitting organic film (light alignment method) and the like.

The optical alignment method not only suppresses the generation of static electricity or dust, but also imparts uniform liquid crystal alignment to the photosensitive organic film, and can also precisely control the liquid crystal alignment direction. Therefore, various studies have been conducted in recent years (for example, refer to Patent Literature 1). Patent Document 1 discloses that a liquid crystal alignment agent is formed using a liquid crystal alignment agent containing a polyimide precursor having a cinnamamide group in the main chain, polyimide, or polyamide.

[Prior Art Literature]

[Patent Literature]

[Patent Literature 1] International Publication No. 2013/161984

[Problems to be Solved by the Invention] In recent years, large-screen and high-definition LCD TVs have become the main body. In addition, the popularization of small display terminals such as smartphones and tablet PCs has continued to increase the demand for high-definition LCD panels. improve. Specifically, in order to improve the display quality of the liquid crystal display element, it is important that afterimages (afterimage characteristics) are difficult to produce and the contrast is good (contrast characteristics), etc., and it is required to further improve these various characteristics.

The present invention was made in view of the above-mentioned problems, and one of the objects is to provide a liquid crystal alignment agent that can obtain a liquid crystal display element having good afterimage characteristics and contrast characteristics. [Means to solve the problem]

The inventors of the present invention conducted intensive research in order to achieve the above-mentioned problems of the prior art, and as a result, they found that by containing a compound having a specific structure in the liquid crystal alignment agent, the above problems can be solved, and the present invention has been completed. Specifically, the following liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element, polymer and compound are provided.

（式（1）中，R¹ 及R² 分別獨立地為氫原子、鹵素原子、氰基或一價有機基，R³ 為取代基；其中，R¹ 及R² 的至少一者為鹵素原子、氰基或一價有機基；X¹ 為氧原子或-NR⁴ -（其中，R⁴ 為氫原子、羥基或一價有機基，R⁴ 亦可鍵結於其他基團而與氮原子一併形成環結構）；R³ 亦可鍵結於其他基團而構成環的至少一部分；n為0～4的整數；於n為2以上的情況下，多個R³ 可相同，亦可不同；「*」表示結合鍵）。[1] A liquid crystal alignment agent containing a compound (X) having a partial structure represented by the following formula (1), [Chem. 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; wherein at least one of R ¹ and R ² is a halogen atom , Cyano group or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein, R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, R ⁴ can also be bonded to other groups and a nitrogen atom And form a ring structure); R ³ may also be bonded to other groups to form at least a part of the ring; n is an integer of 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different ; "*" indicates the combination key).

[2] A method for manufacturing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent of [1] on a substrate to form a coating film; and a step of irradiating the coating film with light. [3] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1]. [4] A liquid crystal display element comprising the liquid crystal alignment film according to [3]. [5] A polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyamidoamine, polyorganosiloxane and poly(meth)acrylate The polymer has a partial structure represented by the formula (1). [6] A diamine compound represented by the following formula (2-1) or formula (2-2),

（式（2-1）中，A¹ 為下述式（1-1）所表示的基團或下述式（1-2）所表示的基團，A² 為單鍵、下述式（1-1）所表示的基團或下述式（1-2）所表示的基團；於A¹ 為下述式（1-1）所表示的基團的情況下，R⁵ 為二價有機基，於A¹ 為下述式（1-2）所表示的基團的情況下，R⁵ 為單鍵或二價有機基；於A² 為下述式（1-1）所表示的基團的情況下，R⁷ 為二價有機基，於A² 為下述式（1-2）所表示的基團或單鍵的情況下，R⁷ 為單鍵或二價有機基；R⁶ 為二價有機基；其中，下述式（1-1）及式（1-2）中的「*1」鍵結於R⁶ ） [化3]

（式（2-2）中，A¹ 及A² 與所述式（2-1）為相同含義；於A¹ 為下述式（1-1）所表示的基團的情況下，R⁸ 為一價有機基，於A¹ 為下述式（1-2）所表示的基團的情況下，R⁸ 為氫原子或一價有機基；其中，於R⁸ 為氫原子的情況下，A¹ 具有二胺基苯基，於R⁸ 為一價有機基的情況下，R⁸ 具有二胺基苯基；於A² 為下述式（1-1）所表示的基團的情況下，R¹⁰ 為一價有機基，於A² 為下述式（1-2）所表示的基團或單鍵的情況下，R¹⁰ 為氫原子或一價有機基；R⁹ 為二價有機基；下述式（1-1）及式（1-2）中的「*1」鍵結於R⁹ ） [化4]

（式（1-1）及式（1-2）中，R¹ 及R² 分別獨立地為氫原子、鹵素原子、氰基或一價有機基，R³ 為取代基；其中，R¹ 及R² 的至少一者為鹵素原子、氰基或一價有機基；X¹ 為氧原子或-NR⁴ -（其中，R⁴ 為氫原子、羥基或一價有機基，R⁴ 亦可鍵結於其他基團而與氮原子一併形成環結構）；n為0～4的整數；於n為2以上的情況下，多個R³ 可相同，亦可不同；「*1」表示結合鍵）。[Chem 2]

(In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula ( 1-1) the group represented by or the group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is divalent Organic group, when A ¹ is a group represented by the following formula (1-2), R ⁵ is a single bond or a divalent organic group; and A ² is represented by the following formula (1-1) In the case of a group, R ⁷ is a divalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein, "*1" in the following formula (1-1) and formula (1-2) is bonded to R ⁶ ) [Chem. 3]

(In formula (2-2), A ¹ and A ² have the same meaning as the above formula (2-1); when A ¹ is a group represented by the following formula (1-1), R ⁸ Is a monovalent organic group, when A ¹ is a group represented by the following formula (1-2), R ⁸ is a hydrogen atom or a monovalent organic group; wherein, when R ⁸ is a hydrogen atom, A ¹ has a diaminophenyl group, and when R ⁸ is a monovalent organic group, R ⁸ has a diaminophenyl group; when A ² is a group represented by the following formula (1-1) , R ¹⁰ is a monovalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group Group; the "*1" in the following formula (1-1) and formula (1-2) is bonded to R ⁹ ) [Chem. 4]

(In formula (1-1) and formula (1-2), R ¹ and R ² are independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent; wherein, R ¹ and At least one of R ² is a halogen atom, a cyano group or a monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ may also be bonded In other groups, it forms a ring structure together with the nitrogen atom); n is an integer from 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different; "*1" represents a bond ).

（式（5-1）中，A³ 為所述式（1-1）所表示的基團或所述式（1-2）所表示的基團，A⁴ 為單鍵、所述式（1-1）所表示的基團或所述式（1-2）所表示的基團；R¹⁵ 及R¹⁷ 分別獨立地為芳香族環基、脂環式基或雜環基，R¹⁶ 為二價有機基，X³ 及X⁴ 分別獨立地為單鍵或二價連結基；其中，所述式（1-1）及式（1-2）中的「*1」鍵結於R¹⁶ ） [化6]

（式（5-2）中，R¹⁸ 為二價有機基，R¹⁹ 為芳香族環基、脂環式基或雜環基；R¹ 、R² 及X¹ 與所述式（5-1）為相同含義）。[7] An acid dianhydride, which is represented by the following formula (5-1) or formula (5-2), [化5]

(In formula (5-1), A ³ is a group represented by the formula (1-1) or a group represented by the formula (1-2), A ⁴ is a single bond, the formula ( 1-1) The group represented by or the group represented by the above formula (1-2); R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group, and R ¹⁶ is A divalent organic group, X ³ and X ⁴ are each independently a single bond or a divalent linking group; wherein, "*1" in the above formula (1-1) and formula (1-2) is bonded to R ¹⁶ ) [Chem 6]

(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} same as the above formula (5-1 ) Has the same meaning).

（式（3）中，A¹ 為所述式（1-1）所表示的基團或所述式（1-2）所表示的基團，A² 為單鍵、所述式（1-1）所表示的基團或所述式（1-2）所表示的基團；於A¹ 為所述式（1-1）所表示的基團的情況下，R¹¹ 為一價有機基，於A¹ 為所述式（1-2）所表示的基團的情況下，R¹¹ 為氫原子或一價有機基；R¹² 為二價有機基；於A² 為所述式（1-1）所表示的基團的情況下，R¹³ 為二價有機基，於A² 為所述式（1-2）所表示的基團的情況下，R¹³ 為單鍵或二價有機基；s及r分別獨立地為0或1；其中，式（3）中具有一個羧基；所述式（1-1）及式（1-2）中的「*1」鍵結於R¹² ）。 [發明的效果][8] A carboxylic acid represented by the following formula (3), [Chem. 7]

(In formula (3), A ¹ is a group represented by the formula (1-1) or a group represented by the formula (1-2), A ² is a single bond, the formula (1- 1) the group represented by or the group represented by the formula (1-2); when A ¹ is the group represented by the formula (1-1), R ¹¹ is a monovalent organic group , When A ¹ is a group represented by the formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the formula (1 -1) In the case of the group represented by R ¹³ is a divalent organic group, and when A ² is the group represented by the above formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are independently 0 or 1; wherein, formula (3) has a carboxyl group; "*1" in the formula (1-1) and formula (1-2) is bonded to R ¹² ). [Effect of invention]

By using the liquid crystal alignment agent containing the compound (X), it is possible to obtain a liquid crystal display element that is hard to produce afterimages (especially afterimages caused by an alternating voltage) and has good contrast.

Hereinafter, each component contained in the liquid crystal aligning agent of this disclosure, and other components arbitrarily mixed as needed are demonstrated.

（式（1）中，R¹ 及R² 分別獨立地為氫原子、鹵素原子、氰基或一價有機基，R³ 為取代基；其中，R¹ 及R² 的至少一者為鹵素原子、氰基或一價有機基；X¹ 為氧原子或-NR⁴ -（其中，R⁴ 為氫原子、羥基或一價有機基，R⁴ 亦可鍵結於其他基團而與氮原子一併形成環結構）；R³ 亦可鍵結於其他基團而構成環的至少一部分；n為0～4的整數；於n為2以上的情況下，多個R³ 可相同，亦可不同；「*」表示結合鍵）<Compound (X)> The liquid crystal alignment agent of the present disclosure contains a compound having a partial structure represented by the following formula (1) (hereinafter also referred to as "compound (X)"). [Chem 8]

(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; wherein at least one of R ¹ and R ² is a halogen atom , Cyano group or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein, R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, R ⁴ can also be bonded to other groups and a nitrogen atom And form a ring structure); R ³ may also be bonded to other groups to form at least a part of the ring; n is an integer of 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different ; "*" indicates the combination key)

In the formula (1), the monovalent organic groups of R ¹ and R ² may, for example, include a C 1-20 alkyl group, a C 1-20 alkoxy group, and a C 1-20 fluoroalkyl group. , Cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, aralkyl having 7 to 20 carbon atoms, epoxy group, alkyl silane group, alkoxy silane group, etc. Here, the alkyl group having 1 to 20 carbon atoms may be linear or branched, and specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups. , Octyl, nonyl, decyl, etc. In addition, examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples of the fluoroalkyl group having 1 to 20 carbon atoms include all: Fluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, etc.; cycloalkyl having 3 to 20 carbon atoms, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, etc.; carbon number 6 Examples of the aryl group of -20 include phenyl and tolyl, and examples of the aralkyl group of 6 to 20 carbon include benzyl. Examples of the halogen atom of R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

Regarding R ¹ and R ² , although at least one of these is a halogen atom, a cyano group, or a monovalent organic group, from the viewpoint of sufficiently exhibiting the alignment restrictive force of the liquid crystal by light irradiation, it is preferably at least R ² is a halogen atom, a cyano group or a monovalent organic group. Specifically, in the group, R ^{1 is} preferably a hydrogen atom, a fluorine atom or a C 1-10 alkyl group, more preferably a hydrogen atom, a fluorine atom or a methyl group, and particularly preferably a hydrogen atom. In addition, 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 particularly preferably a methyl group. Among them, particularly preferred is a combination in which R ¹ is a hydrogen atom and R ² is a methyl group.

R ⁴ in -NR ⁴ -is preferably a hydrogen atom, a hydroxyl group, a C 1-6 alkyl group, or a protective group. Examples of the protective group include carbamate-based protective groups, amide-based protective groups, amide-based protective groups, and sulfonamide-based protective groups. A carbamate-based protecting group is preferred, and specific examples thereof include, for example, a third butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1 , 1-Dimethyl-2-cyanoethyloxycarbonyl, 9-oxylmethylcarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, etc. The third butoxycarbonyl group is preferred in terms of being easily deprotected by heat, or in terms of easily discharging the released compound as a gas to the outside of the membrane. Among these groups, R ^{4 is} preferably a hydrogen atom, a methyl group, a hydroxyl group or a third butoxycarbonyl group, more preferably a hydrogen atom or a methyl group. R ⁴ may also bond with other groups to form a ring structure together with the nitrogen atom. Examples of the ring structure include piperidine and piperazine. X ^{1 is} preferably an oxygen atom. Examples of substituents for R ³ include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, carboxyl groups, amine groups, cyano groups, alkylsilyl groups, and alkoxysilanes. Group, ester group, etc. Examples of the ring formed by bonding R ³ to another group include an amide imine ring. n is preferably 0 to 2, more preferably 0 or 1. The "*" in formula (1) may be bonded to a hydrogen atom, an organic group, or R ³ to form a ring structure (such as an amide imide ring, etc.).

The compound (X) may be a polymer component capable of being a main component of the liquid crystal alignment film, or may be an additive component blended separately with the polymer component. Among these compounds, in terms of high anisotropic expression effect by the photo-alignment method, it is preferably contained in the liquid crystal alignment agent as at least a part of the polymer component, particularly preferably in the main polymer The chain has a partial structure represented by the formula (1). Here, the "main chain" of the polymer in this specification refers to the "dry" part of the polymer that contains the longest atomic chain. In addition, the "dry" part is allowed to contain a ring structure. Therefore, “having a 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. Among them, it is not excluded that the partial structure represented by the above formula (1) also exists in a portion other than the main chain, for example, a side chain (a portion that is “dried” from the polymer). The so-called "organic group" refers to a group containing a hydrocarbon group, and may also contain a heteroatom in the structure.

When the compound (X) is a polymer, the main skeleton is not particularly limited, and examples thereof include polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, and polyamidoamine. , Cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenyl maleimide) derivatives, poly (meth) acrylate and other main skeletons. Among these polymers, from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystal, etc., it is preferably selected from the group consisting of polyamic acid, polyimide, polyamidate, polyamidoamine, polyorganic At least one polymer (hereinafter also referred to as "polymer (A)") in the group consisting of siloxane and poly(meth)acrylate, more preferably selected from the group consisting of polyamic acid and polyimide , At least one polymer in the group consisting of polyamic acid ester and polyorganosiloxane, particularly preferably selected from the group consisting of polyamic acid, polyimide and polyamic acid ester Of at least one polymer. In addition, the polymer used in the preparation of the liquid crystal alignment agent may be only one kind, or two or more kinds. (Meth)acrylate refers to acrylate and methacrylate.

[Polyamic acid] The polyamic acid as the compound (X) is a polyamic acid having a partial structure represented by the formula (1), for example, by reacting a tetracarboxylic dianhydride with a diamine And get. Specifically, [1] a method of polymerizing a monomer including tetracarboxylic dianhydride (hereinafter also referred to as "specific acid dianhydride") having a partial structure represented by the formula (1); [2] A method of polymerizing a monomer containing a diamine having a partial structure represented by the formula (1) (hereinafter also referred to as "specific diamine"); [3] will contain the specific acid dianhydride And a method for polymerizing the monomer of the specific diamine. Among these methods, in terms of relatively easy synthesis of monomers, it is preferable to use a specific diamine, and specifically, the method of [2] above is preferable.

（式（5-1）中，A³ 為下述式（1-1）所表示的基團或下述式（1-2）所表示的基團，A⁴ 為單鍵、下述式（1-1）所表示的基團或下述式（1-2）所表示的基團；R¹⁵ 及R¹⁷ 分別獨立地為芳香族環基、脂環式基或雜環基，R¹⁶ 為二價有機基，X³ 及X⁴ 分別獨立地為單鍵或二價連結基；其中，下述式（1-1）及式（1-2）中的「*1」鍵結於R¹⁶ ） [化10]

（式（1-1）及式（1-2）中，R¹ 、R² 、R³ 、X¹ 及n與所述式（1）為相同含義；「*1」表示結合鍵） [化11]

（式（5-2）中，R¹⁸ 為二價有機基，R¹⁹ 為芳香族環基、脂環式基或雜環基；R¹ 、R² 及X¹ 與所述式（1）為相同含義）(Tetracarboxylic dianhydride) As long as the specific acid dianhydride used in the synthesis of the polyamic acid has a partial structure represented by the formula (1), the remaining structure is not particularly limited, and preferred specific examples include The compound represented by the following formula (5-1), the compound represented by the following formula (5-2), and the like. [化9]

(In formula (5-1), A ³ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ⁴ is a single bond, and the following formula ( 1-1) The group represented by or the group represented by the following formula (1-2); R ¹⁵ and R ¹⁷ are each independently an aromatic ring group, an alicyclic group or a heterocyclic group, and R ¹⁶ is A divalent organic group, X ³ and X ⁴ are each independently a single bond or a divalent linking group; wherein, "*1" in the following formula (1-1) and formula (1-2) is bonded to R ¹⁶ ) [Chem. 10]

(In formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the above formula (1); "*1" represents a bond) 11]

(In formula (5-2), R ¹⁸ is a divalent organic group, R ¹⁹ is an aromatic cyclic group, an alicyclic group or a heterocyclic group; R ¹ , R ² and X ¹ and the above formula (1) are Same meaning)

In the formula (5-1), R ¹⁵ and R ¹⁷ are groups obtained by removing three hydrogen atoms from the ring portion of an aromatic ring, an aliphatic ring or a heterocyclic ring. It is preferably an aromatic cyclic group or an alicyclic group, more preferably a group obtained by removing three hydrogen atoms from the ring portion of a benzene ring, naphthalene ring, cyclopentane ring or cyclohexane ring, particularly preferably A group formed by removing three hydrogen atoms from the benzene ring or cyclohexane ring. Regarding the divalent organic group of R ¹⁶ , the description exemplified by R ⁵ to R ⁷ in the following formula (2-1) can be applied. From the viewpoint of making the afterimage characteristics and contrast characteristics of the liquid crystal display element better, it is preferably a substituted or unsubstituted aromatic cyclic group or an alicyclic group, and more preferably a substituted or unsubstituted aromatic Ring group. Examples of the divalent linking groups of X ³ and X ⁴ include: -O-, -CO-, -COO-, and -CONR ^4- (R ⁴ has the same meaning as the above formula (1)), and the following formula (2- 1) Divalent organic groups exemplified in R ⁵ to R ⁷ . Regarding R ¹ , R ² , R ³ and X ^{1 in} the formula (1-1) and the formula (1-2), the description of the formula (1) can be applied. From the viewpoint of ease of synthesis, the compound represented by the formula (5-1) is preferably A ³ is a compound represented by the formula (1-2), and more preferably A ⁴ is a single bond. In the above formula (5-2), as for the divalent organic group of R ¹⁸ , the exemplified description of R ⁵ to R ⁷ in the following formula (2-1) can be applied. Regarding R ¹⁹ , the illustrations of R ¹⁵ and R ¹⁷ of the above formula (5-1) and descriptions of preferred specific examples can be applied. The compound represented by the formula (5-2), also by at least a portion of R ¹⁸ and R ¹⁹ bonded structure obtained by further forming a partial structure (1) represented by the formula.

[化13]

（式（t-1）～式（t-4）及式（t-11）～式（t-15）中，R為碳數1～5的烷基，k及j分別獨立地為0～2的整數）Preferable specific examples of the specific acid dianhydride include, for example, compounds represented by the following formula (t-1) to formula (t-31). In addition, the specific acid dianhydride may be used alone or in combination of two or more. [化12]

[Chem 13]

(In formula (t-1) to formula (t-4) and formula (t-11) to formula (t-15), R is a C 1-5 alkyl group, and k and j are independently 0 to An integer of 2)

[化14]

In addition, in the above formula (t-1) to formula (t-4) and formula (t-11) to formula (t-15), R bonded to the ring portion of 1,4-phenylene The location is not particularly limited. Specifically, in the case of substitution of 1, it can be set to the 2-position, 3-position, 5-position, or 6-position, and in the case of substitution of 2, it is preferably 2,4-position or 3,5- Bit. R is preferably methyl.

The specific acid dianhydride can be synthesized by appropriately combining ordinary methods of organic chemistry. For example, it can be obtained by reacting a compound having "-C(R ¹ )=C(R ² )-CO-X ¹ -" with a phthalic acid derivative to synthesize the formula ( 1) The partially structured tetracarboxylic acid represented, and then the obtained tetracarboxylic acid is acidified. 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 dianhydride used in the synthesis of the polyamic acid as the compound (X) may be only a specific acid dianhydride, or may not be used in combination. The tetracarboxylic dianhydride having a partial structure represented by the formula (1) (hereinafter also referred to as "other acid dianhydride"). In the method [2], when synthesizing the polyamic acid as the compound (X), another acid dianhydride is used as the tetracarboxylic dianhydride.

（式（AN-2）中，X¹³ 及X¹⁴ 分別獨立地為自亞甲基中去除一個氫原子而成的基團或氮原子，R⁴¹ 為碳數1～10的烷二基；式（AN-3）中，X¹⁵ 及X¹⁶ 分別獨立地為自亞甲基中去除一個氫原子而成的基團或氮原子，B¹ 及B² 分別獨立地為伸苯基或亞吡啶基，R⁴² 為碳數1～10的烷二基，m為1～3的整數；其中，於m為2或3的情況下，多個R⁴² 可相互相同，亦可不同） 所表示的化合物等； 脂環式四羧酸二酐例如可列舉：1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫呋喃-3-基)-8-甲基-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺環-3'-(四氫呋喃-2',5'-二酮)、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基甲基降冰片烷-2:3,5:6-二酐、雙環[3.3.0]辛烷-2,4,6,8-四羧酸-2:4,6:8-二酐、雙環[2.2.1]庚烷-2,3,5,6-四羧酸2:3,5:6-二酐、4,9-二氧雜三環[5.3.1.0^2,6 ]十一烷-3,5,8,10-四酮、1,2,4,5-環己烷四羧酸二酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、乙二胺四乙酸二酐、環戊烷四羧酸二酐、乙二醇雙(脫水偏苯三甲酸酯)、1,3-丙二醇雙(脫水偏苯三甲酸酯)、下述式（AN-4） [化16]

所表示的化合物等；Examples of other acid dianhydrides include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides include, for example, butane tetracarboxylic dianhydride, the following formula (AN-2) or formula (AN-3)

(In formula (AN-2), X ¹³ and X ¹⁴ are each independently a group or nitrogen atom obtained by removing one hydrogen atom from the methylene group, and R ⁴¹ is an alkanediyl group having 1 to 10 carbon atoms; In (AN-3), X ¹⁵ and X ¹⁶ are independently a group or nitrogen atom obtained by removing one hydrogen atom from methylene, and B ¹ and B ² are independently phenylene or pyridinylene , R ⁴² is an alkanediyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3; wherein, when m is 2 or 3, a plurality of R ⁴² may be the same as or different from each other) And the like; for example, alicyclic tetracarboxylic dianhydride includes: 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic 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'-diketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6 -Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid-2:4,6 :8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate), 1,3-propanediol bis (dehydrated) Trimellitate), the following formula (AN-4)

The compound represented, etc.;

（式（AN-1）中，X¹¹ 及X¹² 分別獨立地為單鍵、氧原子、硫原子、-CO-、*-COO-、*-OCO-、*-CO-NR²¹ -、*-NR²¹ -CO-（其中，R²¹ 為氫原子或者碳數1～6的一價烴基；「*」表示與R²⁰ 的結合鍵）；R²⁰ 為單鍵、碳數1～20的二價烴基、於該烴基的碳-碳鍵間包含-O-的二價基、或者具有含氮雜環的二價基） 所表示的化合物、下述式（AN-5-1）～式（AN-5-4） [化18]

分別所表示的化合物等；除此以外，還可使用日本專利特開2010-97188號公報中記載的四羧酸二酐。Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4′-(hexafluoroisopropylidene) diphthalic anhydride, and the following formula (AN-1)

(In formula (AN-1), X ¹¹ and X ¹² are independently a single bond, oxygen atom, 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; "*" represents a bonding bond with R ²⁰ ); R ²⁰ is a single bond and a carbon atom having 1 to 20 carbon atoms Valent hydrocarbon group, a divalent group containing -O- between carbon-carbon bonds of the hydrocarbon group, or a divalent group having a nitrogen-containing heterocyclic ring) The compound represented by the following formula (AN-5-1) to formula ( AN-5-4) [Chem. 18]

Compounds represented by each, etc.; in addition, tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can also be used.

[化20]

[化21]

[化22]

In the above formula (AN-2), R ⁴¹ and R ⁴² are C 1-10 alkanediyl groups, for example, methylene, ethylidene, propylidene, butanediyl, pentaneyl, hexyl Diyl, heptanediyl, octanediyl, nonanediyl, decanediyl, etc. These groups may be linear or branched. B ¹ and B ^{2 are} preferably 1,4-phenylene or 2,5-pyridylene. Specific examples of the compound represented by the formula (AN-2) include, for example, compounds represented by the following formula (a-2), etc. As specific examples of the compound represented by the formula (AN-3) Examples include compounds represented by the following formula (AN-3-1) to formula (AN-3-28). [Chem 19]

[化20]

[化21]

[化22]

Specific examples of the C 1-20 divalent hydrocarbon group of R ²⁰ in the formula (AN-1) include, for example, methylene, ethylidene, propylidene, butanediyl, and glutaryl , Hexanediyl, heptadiyl, octadiyl, nonanediyl, sebacyl and other alkyldiyl groups; divalent alicyclic hydrocarbon groups such as cyclohexyl; divalent aromatic hydrocarbon groups such as phenylene and biphenylene Wait. The number of oxygen atoms that can be introduced into the carbon-carbon bond of the hydrocarbon group may be one, or two or more. When R ²⁰ is a divalent group having a nitrogen-containing heterocyclic ring, examples of the nitrogen-containing heterocyclic ring include pyrrole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazine ring, piperidine ring, piperazine ring , Pyrrolidine ring, etc.

[化24]

[化25]

此外，合成聚醯胺酸時，四羧酸二酐可單獨使用一種或者將兩種以上組合使用。Specific examples of the compound represented by the formula (AN-1) include, for example, compounds represented by the following formulas (AN-1-1) to (AN-1-27), and the following formula ( The compound represented by a-1), the compound represented by the following formula (a-3), and the like. [化23]

[化24]

[化25]

In addition, when synthesizing polyamic acid, tetracarboxylic dianhydride may be used alone or in combination of two or more.

From the viewpoint of electrical characteristics, the other acid dianhydride preferably includes at least one selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, specifically, preferably Is selected from the compound represented by the formula (a-2), bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid-2:3,5:6-dianhydride, 1 ,2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxy ring Amylacetic 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 , Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid-2:4,6:8-dianhydride, and cyclohexane tetracarboxylic dianhydride at least the group consisting of A compound. Relative to the total amount of other acid dianhydrides used in the synthesis of polyamic acid, the preferred amount of these compounds (the total amount when two or more kinds are used) is preferably set to 10 Ear% or more, more preferably 20 mole% or more, particularly preferably 50 mole% or more.

From the viewpoint of sufficiently obtaining the effects of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element, the method [1] specifies the total amount of tetracarboxylic dianhydride used in the synthesis of polyamic acid. The use ratio of the acid dianhydride is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

（式（2-1）中，A¹ 為下述式（1-1）所表示的基團或下述式（1-2）所表示的基團，A² 為單鍵、下述式（1-1）所表示的基團或下述式（1-2）所表示的基團；於A¹ 為下述式（1-1）所表示的基團的情況下，R⁵ 為二價有機基，於下述式（1-2）所表示的基團的情況下，R⁵ 為單鍵或二價有機基；於A² 為下述式（1-1）所表示的基團的情況下，R⁷ 為二價有機基，於下述式（1-2）所表示的基團或單鍵的情況下，R⁷ 為單鍵或二價有機基；R⁶ 為二價有機基） [化27]

（式（2-2）中，A¹ 及A² 與所述式（2-1）為相同含義；於A¹ 為下述式（1-1）所表示的基團的情況下，R⁸ 為一價有機基，於下述式（1-2）所表示的基團的情況下，R⁸ 為氫原子或一價有機基；其中，於R⁸ 為氫原子的情況下，A¹ 具有二胺基苯基，於R⁸ 為一價有機基的情況下，R⁸ 具有二胺基苯基；於A² 為下述式（1-1）所表示的基團的情況下，R¹⁰ 為一價有機基，於下述式（1-2）所表示的基團或單鍵的情況下，R¹⁰ 為氫原子或一價有機基；R⁹ 為二價有機基） [化28]

（式（1-1）及式（1-2）中，「*1」表示鍵結於R⁹ 的結合鍵；R¹ 、R² 、R³ 、X¹ 及n與所述式（1）為相同含義）(Diamine) As long as the specific diamine used in the synthesis of the polyamic acid has a partial structure represented by the formula (1), the remaining structure is not particularly limited. For example, the following formula (2-1) may be mentioned. The compound represented, the compound represented by the following formula (2-2), etc. [化26]

(In formula (2-1), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula ( 1-1) the group represented by or the group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is divalent Organic group, in the case of the group represented by the following formula (1-2), R ⁵ is a single bond or a divalent organic group; in A ² is a group represented by the following formula (1-1) In the case, R ⁷ is a divalent organic group, and in the case of a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group ) [Chem. 27]

(In formula (2-2), A ¹ and A ² have the same meaning as the above formula (2-1); when A ¹ is a group represented by the following formula (1-1), R ⁸ Is a monovalent organic group, in the case of a group represented by the following formula (1-2), R ⁸ is a hydrogen atom or a monovalent organic group; wherein, when R ⁸ is a hydrogen atom, A ¹ has Diaminophenyl, when R ⁸ is a monovalent organic group, R ⁸ has a diaminophenyl; when A ² is a group represented by the following formula (1-1), R ¹⁰ Is a monovalent organic group, in the case of a group represented by the following formula (1-2) or a single bond, R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group) [Chem 28]

(In formula (1-1) and formula (1-2), "*1" represents a bonding bond to R ⁹ ; R ¹ , R ² , R ³ , X ¹ and n are in accordance with the above formula (1) For the same meaning)

In the above formula (2-1), examples of the divalent organic group of R ⁵ to R ⁷ include: a divalent hydrocarbon group having 1 to 20 carbon atoms; a part of the methylene group included in the hydrocarbon group is represented by -O-, -CO-, -COO- or -NR ^33- (R ³³ is a hydrogen atom or a C 1-6 alkyl group) substituted divalent group, divalent heterocyclic group, etc.; these groups may also have Substituents. Here, the "hydrocarbon group" in the present specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these groups, "chain hydrocarbon group" refers to a linear hydrocarbon group and a branched hydrocarbon group that are composed of only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. Among them, it is not necessary to be composed only of the structure of the alicyclic hydrocarbon, and those having a chain-like structure in a part thereof are also included. "Aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed only of an aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be included in a part thereof.

As specific examples of the C 1-20 divalent hydrocarbon group in R ⁵ to R ⁷ , the chain hydrocarbon group includes, for example, methylene, ethylidene, propanediyl, butanediyl, pentanediyl, and hexanediyl. Group, heptadiyl, octadiyl, nonanediyl, sebacyl, etc.; alicyclic hydrocarbon groups include, for example: cyclohexyl, -R ³⁰ -R ^31- (wherein R ³⁰ is cyclohexyl, R ³¹ (C1-C3 alkanediyl group) etc.; aromatic hydrocarbon groups include, for example, phenylene, alkyl-substituted phenylene, biphenylene, naphthyl, -Ar ³ -R ³² -( Among them, Ar ³ is phenylene, biphenylene, or naphthyl, and R ³² is a C1-C3 alkanediyl or cyclohexyl group). Examples of the divalent heterocyclic group in R ⁵ to R ⁷ include a group obtained by removing two hydrogen atoms from a nitrogen-containing heterocyclic ring such as pyridine, piperazine, and piperidine. Examples of the substituent that R ⁵ to R ⁷ may have include a halogen atom, an alkoxy group, etc., a hydroxyl group, a carboxyl group, and a cyano group. Among R ⁵ to R ⁷ , the divalent organic groups of R ⁵ and R ⁷ are preferably substituted or unsubstituted phenylene, biphenylene, naphthyl, cyclohexyl, Pyridinylene, or -Ar ⁴ -COO-* ³ (Ar ⁴ is substituted or unsubstituted phenylene, biphenylene, naphthylene, or cyclohexyl, "* ³ "represents the benzene ring Combining keys). R ^{6 is} preferably an alkanediyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, a biphenylene group or a naphthyl group.

In the formula (2-2), examples of the monovalent organic group of R ⁸ and R ¹⁰ include: a monovalent hydrocarbon group having 1 to 20 carbon atoms; a part of the methylene group included in the hydrocarbon group is represented by -O-, -CO-, -COO- or -NR ^33- (R ³³ is a hydrogen atom or a C 1-6 alkyl group) substituted monovalent group, monovalent heterocyclic group, etc.; these groups may also have Substituents. Specific examples of the monovalent organic group of R ⁸ and R ¹⁰ include, for example, C 1-20 alkyl groups, C 1-20 alkoxy groups, C 1-20 fluoroalkyl groups, and cyclohexyl groups. , Phenyl, tolyl, benzyl, biphenyl, naphthyl, pyridyl, piperidyl, etc. Regarding R ⁹ , the description of R ⁶ in the above formula (2-1) can be applied. In the diamino phenyl group of the formula (2-2), two amine groups are preferably located at the 2,4-position or the 3,5-position relative to other groups. In addition, the description of R ¹ , R ² , R ³ and X ¹ in the formula (1-1) and the formula (1-2) can be applied to the description of the formula (1).

（式（4）中，Ar¹ 及Ar² 分別獨立地為經取代或未經取代的伸苯基或伸環己基，X² 為單鍵、-COO-或-CONR²⁰ -（R²⁰ 為氫原子或一價有機基）；其中，Ar¹ 亦可構成所述式（1）中的苯環；t為1或2；t=2時，Ar² 、X² 分別獨立地具有所述定義；「*」表示結合鍵）The specific diamine is preferably a compound having a partial structure represented by the following formula (4) in the molecule. Having a partial structure represented by the following formula (4) is preferable in terms of improving the effect of reducing afterimages (alternating current (AC) afterimages) caused by AC voltage in the liquid crystal display element. [Chem 29]

(In formula (4), Ar ¹ and Ar ² are independently substituted or unsubstituted phenylene or cyclohexyl, X ² is a single bond, -COO- or -CONR ^20- (R ²⁰ is hydrogen Atom or monovalent organic group); wherein, Ar ¹ can also constitute the benzene ring in the formula (1); t is 1 or 2; when t=2, Ar ² and X ² independently have the above definition; "*" means a combination key)

（式中，「*」表示結合鍵）In the above formula (4), the monovalent organic group of R ²⁰ includes, for example, a C 1-6 alkyl group, a protective group, and the like. Specific examples of the protecting group include, for example, a third butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, and allyloxycarbonyl group. X ^{2 is} preferably a single bond or -COO-. The substituent of the ring portion of Ar ¹ and Ar ² is preferably a C 1-5 alkyl group or a halogen atom, more preferably a methyl group or a fluorine atom. Preferred specific examples of the partial structure represented by the formula (4) include, for example, 4,4′-biphenylene, 4,4′-biscyclohexyl, and the following formula (4-1 ) To groups represented by formula (4-4), groups having a methyl group or a fluorine atom in the ring portion of these groups, and the like. [化30]

(In the formula, "*" represents the bonding key)

In the case where a coating film formed using a liquid crystal alignment agent is given an alignment restricting force by an optical alignment method, in terms of reducing the AC afterimage of the liquid crystal display element and improving the contrast, it is preferably As the specific diamine, the compound represented by the formula (2-1) is used. By using the compound represented by the formula (2-1) as a specific diamine, a polymer having a partial structure represented by the formula (1) in the main chain can be obtained.

[化32]

[化33]

[化34]

As specific examples of the specific diamine, the compound represented by the formula (2-1) includes, for example, the following formula (b-1) to formula (b-17), formula (b-26) to formula (b- 56) Compounds represented by each, etc. The compounds represented by the above formula (2-2) include, for example, compounds represented by the following formulae (b-18) to (b-59), respectively. [化31]

[化32]

[化33]

[化34]

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

The specific diamine can be synthesized by appropriately combining common methods of organic chemistry. As an example, the following method can be cited: synthesis of a dinitro intermediate having a nitro group instead of the primary amine group of the compound represented by the formula (2-1) or formula (2-2), and then, using a suitable reduction system , The nitro group of the obtained dinitro intermediate is aminated. The method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. Specifically, for example, the compound represented by "O ₂ NR ⁵ -A ¹ -H" and the compound represented by "HO-R ⁶ -A ² -R ⁷ -NO ₂ "can preferably be The organic solvent is obtained by performing a reaction in the presence of a catalyst as needed. The reduction reaction of the dinitro intermediate is preferably carried out in an organic solvent, for example, using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel and the like. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis sequence of a specific diamine is not limited to the above method.

When synthesizing 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 formula (1) may be used in combination. Examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes. As specific examples of these diamines, aliphatic diamines include, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine. Amine, 1,3-bis(aminomethyl)cyclohexane, 1,2-bis(2-aminoethoxy)ethane, etc.; Examples of alicyclic diamines include 1,4-diamine Cyclohexane, 4,4'-methylenebis (cyclohexylamine), etc.;

（式（E-1）中，X^I 及X^II 分別獨立地為單鍵、-O-、*⁴ -COO-或*⁴ -OCO-（其中，「*⁴ 」為鍵結於苯環的結合鍵），R^I 為碳數1～3的烷二基，R^II 為單鍵或碳數1～3的烷二基，a為0或1，b為0～2的整數，c為1～20的整數，d為0或1；其中，a及b不會同時成為0）Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, and 18 Alkoxydiaminobenzene, cholesteryloxydiaminobenzene, cholestenyloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate Ester, lanolin alkyl diaminobenzoate, 3,6-bis(4-aminobenzyloxy)cholesterane, 3,6-bis(4-aminophenoxy)cholesterol Alkanes, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl) Phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4 -((Aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, N-(2,4-diaminophenyl)-4-(4-heptyl Cyclohexyl) benzamide, the following formula (E-1) [Chem 35]

(In formula (E-1), X ^I and X ^II are independently a single bond, -O-, * ⁴ -COO- or * ⁴ -OCO- (where "* ⁴ "is a bond to a benzene ring Bonding bond), R ^I is a C1-C3 alkanediyl group, R ^II is a single bond or a C1-C3 alkanediyl group, a is 0 or 1, b is an integer of 0-2, and c is 1 -20 integer, d is 0 or 1; where, a and b will not become 0 at the same time)

所表示的化合物等含配向性基的二胺： 對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基胺、4,4'-二胺基二苯基硫醚、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-二胺基偶氮苯、1,5-雙(4-胺基苯氧基)戊烷、1,7-雙(4-胺基苯氧基)庚烷、雙[2-(4-胺基苯基)乙基]己二酸、N,N-雙(4-胺基苯基)甲基胺、1,5-二胺基萘、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、9,9-雙(4-胺基苯基)茀、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4'-(對伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、2,6-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、N,N'-雙(4-胺基苯基)-聯苯胺、N,N'-雙(4-胺基苯基)-N,N'-二甲基聯苯胺、1,4-雙-(4-胺基苯基)-哌嗪、3,5-二胺基苯甲酸、下述式（da-3）～式（da-17） [化37]

分別所表示的化合物等； 二胺基有機矽氧烷例如可列舉：1,3-雙(3-胺基丙基)-四甲基二矽氧烷等；除此以外，還可使用日本專利特開2010-97188號公報中記載的二胺。The represented compound, the following formula (da-1) or formula (da-2) [Chem 36]

Represented compounds such as diamines containing alignment groups: p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-di Aminodiphenyl 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]adipic 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) stilbene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylene diisopropylidene) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) ) Biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6 -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) [Chem 37]

Compounds represented by each, etc.; Diaminoorganosiloxanes include, for example, 1,3-bis(3-aminopropyl)-tetramethyldisilaxane, etc.; in addition, Japanese patents can also be used The diamine described in Japanese Patent Laid-Open No. 2010-97188.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (E-1) is preferably: a C1-C3 alkanediyl group, *-O-, *-COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Examples of the group "-C _c H _2c+1 "include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and thirteen Alkyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, dodecyl, etc. These groups are preferably linear. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.

此外，聚醯胺酸的合成中使用的二胺可將該些化合物的一種單獨使用，或者適當選擇兩種以上來使用。Specific examples of the compound represented by the formula (E-1) include, for example, compounds represented by the following formulae (E-1-1) to (E-1-4), respectively. [化38]

In addition, the diamine used in the synthesis of the polyamic acid can be used alone, or two or more of them can be appropriately selected and used.

In the case of liquid crystal aligning agent for liquid crystal display elements of twisted nematic (TN) type, super twisted nematic (STN) type or vertical alignment type, it can also be used in polyamic acid The side chain introduces a functional group (liquid crystal alignment group) that can exhibit liquid crystal alignment restrictive force regardless of whether or not light irradiation is performed. Examples of the liquid crystal alignment 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. Group, a group having a polycyclic structure (for example, a group having a partial structure represented by the formula (4)), and the like. The polyamic acid having a liquid crystal alignment group can be obtained, for example, by polymerizing the monomer group containing the alignment group-containing diamine. In the case of using an aligning group-containing diamine, from the viewpoint of making the liquid crystal alignment good, it is preferable to set the ratio of the aligning group-containing diamine to the total diamine used in the synthesis. It is 3 mol% or more, more preferably 5 mol% to 70 mol%.

In the case of synthesizing polyamic acid by the method [2], from the viewpoint of sufficiently obtaining the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element, it is used in the synthesis of polyamic acid. The total amount of diamines and the use ratio of specific diamines are preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. In addition, in the case of synthesizing polyamic acid by the above method [3], it is preferable to use a specific acid dianhydride and a specific diamine with respect to the total amount of tetracarboxylic dianhydride and diamine used in the synthesis. The total amount of is set to 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

(Synthesis of Polyamic Acid) Polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic dianhydride and diamine together with a molecular weight modifier if necessary. The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 equivalent to 2 equivalents It is more preferably a ratio of 0.3 to 1.2 equivalents.

分別所表示的化合物等酸單酐，苯胺、環己基胺、正丁基胺等單胺化合物，異氰酸苯基酯、異氰酸萘基酯等單異氰酸酯化合物等。 另外，分子量調整劑亦可使用具有所述式（1）所表示的部分結構的單官能性化合物。該化合物較佳為可使用單胺化合物及酸單酐。具體而言，例如可列舉下述式（ma-1）～式（ma-15）分別所表示的化合物、下述式（mt-1）～式（mt-10）分別所表示的化合物等。 [化40]

[化41]

Examples of the molecular weight modifier include maleic anhydride, phthalic anhydride, itaconic anhydride, and the following formula (F-1) to formula (F-4).

Acid monoanhydrides such as the compounds represented separately, monoamine compounds such as aniline, cyclohexylamine, n-butylamine, monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate, etc. In addition, as the molecular weight regulator, a monofunctional compound having a partial structure represented by the formula (1) may be used. The compound is preferably a monoamine compound and an acid monoanhydride. Specifically, for example, compounds represented by the following formula (ma-1) to formula (ma-15), compounds represented by the following formula (mt-1) to formula (mt-10), and the like can be exemplified. [化40]

[化41]

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride and diamine used. In addition, the molecular weight modifier may be used alone or in combination of two or more.

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

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

In this way, a reaction solution obtained by dissolving polyamide acid can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamic acid can be purified and then provided to Preparation of liquid crystal alignment agent. In the case of dehydration and ring closure of polyamic acid to form polyimide, the reaction solution may be directly supplied to the dehydration ring closure reaction, or the polyamic acid contained in the reaction solution may be separated and then provided. To the dehydration ring-closure reaction, or the separated polyamide can be purified and then supplied to the dehydration ring-closure reaction. The isolation and purification of polyamide can be performed according to a known method.

[Polyamide] The polyamide as the compound (X) can be obtained, for example, by the following method: [I] Polyamide having a partial structure represented by the formula (1), and Method of reacting esterification agent; [II] Method of reacting tetracarboxylic acid diester and diamine; [III] Method of reacting tetracarboxylic acid diester dihalide and diamine. In addition, the “tetracarboxylic acid diester” in this specification refers to a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" refers to a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include hydroxyl-containing compounds, acetal-based compounds, halides, and epoxy-containing compounds. As specific examples of these compounds, hydroxyl-containing compounds include, for example, alcohols such as methanol, ethanol, and propanol, and phenols such as phenol and cresol; and acetal-based compounds include, for example, N,N-dimethyl Formamide diethyl acetal, N,N-diethylformamide diethyl acetal, etc.; examples of halides include methyl bromide, ethyl bromide, octadecyl bromide, methyl chloride , Chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, chloromethyl methyl ether, 2-chloromethoxy-1,1,1-trifluoroethane, chloromethyl carbonate Isopropyl ester, chloromethyl trimethylacetate, chloromethyl acetate, chloromethyl butyrate, chloromethyl methyl sulfide, etc.; epoxy-containing compounds include, for example, propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by using an alcohol such as methanol or ethanol, and ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid. Examples of the diamine used include the diamines exemplified in the synthesis of polyamide. The reaction of method [II] is preferably carried out in an organic solvent in the presence of an appropriate dehydration catalyst. The organic solvent may be an organic solvent exemplified as a user in the synthesis of polyamide. Examples of dehydration catalysts include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensing agents Wait. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably from 0.1 hour to 24 hours, and more preferably from 0.5 hour 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 in the above manner with an appropriate chlorinating agent such as thionyl chloride. Examples of the diamine used include the diamines exemplified in the synthesis of polyamide. The reaction of method [III] is preferably carried out in an organic solvent in the presence of a suitable base. The organic solvent may be an organic solvent exemplified as a user in the synthesis of polyamide. As the base, for example, tertiary amines such as pyridine and triethylamine can be preferably used; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, and potassium. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably from 0.1 hour to 24 hours, and more preferably from 0.5 hour to 12 hours.

The polyamic acid ester contained in the liquid crystal alignment agent may have only the amide acid ester structure, or may be a partial esterified product in which the amide acid structure and the amide acid ester structure coexist. In addition, the reaction solution obtained by dissolving the polyamic acid ester can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or The separated polyamide can also be purified and then provided to the preparation of the liquid crystal alignment agent. The isolation and purification of the polyamic acid ester can be performed according to a known method.

[Polyimide] The polyimide as the compound (X) can be obtained by, for example, dehydrating and ring-closing the polyamic acid as the compound (X) synthesized in the above-described manner, and subjecting it to imidization.

The polyimide may be a complete imide compound obtained by dehydrating and ring-closing all the amidic acid structures of the polyamic acid as its precursor, or may be dehydrating and ring-closing only a part of the amidic acid structure. A part of the imidate compound that coexists with the imidate structure and the imidate ring structure. The polyimide used in the reaction preferably has an imidization ratio of 20% or more, more preferably 30% to 99%, and particularly preferably 40% to 99%. The imidate ratio is the sum of the number of amide acid structures of the polyimide and the number of amide imine ring structures, and expresses the ratio of the number of amide imine ring structures as a percentage. Here, a part of the amide imide ring may be an amide imide ring.

The dehydration and ring closure of the polyamic acid is preferably carried out by the following method: heating the polyamic acid; or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring-closing contact to the solution Media, the method of heating as needed. Among them, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, for example, an anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The use amount of the dehydrating agent is preferably 0.01 mol to 20 mol relative to 1 mol of the amic acid structure of the polyamic acid. For the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, tripicoline, lutidine, and triethylamine can be used. The use amount of the dehydration ring-closing catalyst is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as users in the synthesis of polyamide. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C, more preferably 10°C to 150°C. The reaction time is preferably 1.0 hour to 120 hours, and more preferably 2.0 hours to 30 hours.

In this way, a reaction solution containing polyimide can be obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, and can also be provided to the preparation of the liquid crystal alignment agent after the dehydrating agent and dehydration ring-closing catalyst are removed from the reaction solution, or the polyimide can be separated and then provided to the liquid crystal. The preparation of the alignment agent, or the separated polyimide can be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be carried out according to well-known methods. In addition to this, polyimide can also be obtained by the imidization of polyimide.

The polyamic acid, polyamic acid ester and polyimide obtained as the compound (X) obtainable in the above-mentioned manner preferably have respectively selected from the following formula (6-1) to formula (6-10) At least one of the groups composed of the represented partial structures.

（式（6-1）及式（6-2）中，A³ 、A⁴ 、R¹⁵ 、R¹⁶ 、R¹⁷ 、X³ 及X⁴ 分別與所述式（5-1）為相同含義；R²⁰ 及R²¹ 分別獨立地為氫原子或一價有機基） [化43]

（式（6-3）及式（6-4）中，R¹ 、R² 及X¹ 分別與所述式（1）為相同含義，R¹⁸ 及R¹⁹ 分別與所述式（5-2）為相同含義；R²⁰ 及R²¹ 分別獨立地為氫原子或一價有機基） [化44]

（式（6-5）及式（6-6）中，A¹ 、A² 、R⁵ 、R⁶ 及R⁷ 分別與所述式（2-1）為相同含義；R²⁰ 及R²¹ 分別獨立地為氫原子或一價有機基，R²² 及R²³ 分別獨立地為三價有機基） [化45]

（式（6-7）～式（6-10）中，A¹ 、A² 、R⁹ 及R¹⁰ 分別與所述式（2-2）為相同含義；R²⁰ 及R²¹ 分別獨立地為氫原子或一價有機基，R²² 及R²³ 分別獨立地為三價有機基）In addition, when synthesizing the compound (X), in the case of using the compound represented by the formula (5-1) in the specific acid dianhydride, a compound selected from the following formula (6-1) can be obtained The partial structure of the polymer and at least one partial structure polymer in the group consisting of the partial structure represented by the following formula (6-2). When the compound represented by the formula (5-2) in the specific acid dianhydride is used, a partial structure selected from the following formula (6-3) and the following formula (6) can be obtained -4) At least one partial structure polymer in the group consisting of the partial structure shown. In addition, in the case of using the compound represented by the formula (2-1) in the specific diamine, a partial structure selected from the following formula (6-5) and the following formula ( 6-6) At least one partial structure polymer in the group consisting of the partial structure represented. In the case where the compound represented by the formula (2-2) in the specific diamine is used, a part selected from the following formula (6-7) to formula (6-10) can be obtained At least one partially structured polymer in the group consisting of structures. [化42]

(In formula (6-1) and formula (6-2), A ³ , A ⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , X ³ and X ⁴ respectively have the same meaning as the above formula (5-1); R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group) [Chem. 43]

(In formula (6-3) and formula (6-4), R ¹ , R ² and X ¹ respectively have the same meaning as the above formula (1), and R ¹⁸ and R ¹⁹ are respectively the same as the above formula (5-2 ) Have the same meaning; R ²⁰ and R ²¹ are each independently a hydrogen atom or a monovalent organic group) [Chem 44]

(In formula (6-5) and formula (6-6), A ¹ , A ² , R ⁵ , R ⁶ and R ⁷ have the same meanings as the above formula (2-1); R ²⁰ and R ²¹ respectively Independently a hydrogen atom or a monovalent organic group, and R ²² and R ²³ are each independently a trivalent organic group) [化45]

(In formula (6-7) to formula (6-10), A ¹ , A ² , R ⁹ and R ¹⁰ have the same meaning as the above formula (2-2); R ²⁰ and R ²¹ are independently Hydrogen atom or monovalent organic group, R ²² and R ²³ are each independently trivalent organic group)

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

As the compound (X), polyamic acid, polyamic acid ester, and polyimide are preferably solutions having a concentration of 10 mPa·s to 800 mPa·s when they are made into a solution with a concentration of 10% by weight. The viscosity is more preferably a solution viscosity of 15 mPa·s to 500 mPa·s. In addition, the solution viscosity (mPa·s) of the polymer is 10% by weight for a good solvent using the polymer (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) % Polymer solution, the value measured at 25°C using an E-type rotary viscometer (the same applies to the following polymers). Polystyrene-converted weight average molecular weight (Mw) of polyacrylic acid, polyamic acid ester and polyimide determined by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. In addition, 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, and more preferably 10 or less. By being within the above-mentioned molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

[Polyamide] Polyamide as the compound (X) can be obtained, for example, by a method of reacting a dicarboxylic acid and a diamine. Here, the dicarboxylic acid is preferably chlorinated with an appropriate chlorinating agent such as thionyl chloride, and then supplied to the reaction with the diamine.

The dicarboxylic acid used in the synthesis of polyamide is not particularly limited, and examples thereof include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, and 2-methyl Adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, Aliphatic dicarboxylic acids such as fumaric acid and muconic acid; cyclobutane dicarboxylic acid, 1-cyclobutene dicarboxylic acid, cyclopentane dicarboxylic acid, cyclohexane dicarboxylic acid, etc. Dicarboxylic acid with alicyclic structure; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tributylbutyl isophthalic acid, 2,5-di Methyl terephthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4 ,4'-diphenyl ether dicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3'-[4,4'-(methylene Di-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(oxybis-p-phenylene)] dibutyric acid, 3,4-diphenyl-1,2-ring Dicarboxylic acids having aromatic rings such as butane dicarboxylic acid. In addition, one type of dicarboxylic acid may be used alone or two or more types may be used in combination.

The diamine used when synthesizing the polyamide as the compound (X) contains a specific diamine. In addition, other diamines can be used in combination as needed. The use ratio of the specific diamine is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 relative to the total amount of diamine used in the synthesis of the polyamide. More than %. In addition, the diamine may be used alone or in combination of two or more.

The use ratio of the dicarboxylic acid and the diamine provided for the synthesis reaction of the polyamine is preferably 1 equivalent to the amine group of the diamine, and the ratio of the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents, more preferably 0.3 The ratio of equivalent to 1.2 equivalent.

The reaction of the dicarboxylic acid (preferably dichlorinated 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, more preferably 10°C to 100°C. The reaction time is preferably 0.5 hour to 48 hours, and more preferably 1 hour to 36 hours. As the organic solvent used in the reaction, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrole can be preferably used. Pyridone etc. The amount of the organic solvent used is preferably 400 to 900 parts by weight, and more preferably 500 to 700 parts by weight with respect to 100 parts by weight of the total amount of dicarboxylic acid and diamine. As the base used in the reaction, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N,N-diisopropylamine can be preferably used. The use amount of the base is preferably 2 mol to 4 mol relative to 1 mol of diamine, and more preferably 2 mol to 3 mol.

In this manner, a reaction solution obtained by dissolving polyamide can be obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the polyamidide contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated polyamide can be purified and then provided to Preparation of liquid crystal alignment agent. The separation and purification of polyamide can be carried out according to a known method.

The solution viscosity of the polyamide as the compound (X) is preferably a solution having a solution viscosity of 10 mPa·s to 800 mPa·s when it is made into a solution with a concentration of 10% by weight, more preferably 15 mPa · Those with a solution viscosity of s to 500 mPa·s. In addition, regarding polyamide, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

[Polyorganosiloxane] The polyorganosiloxane (hereinafter also referred to as "polymer (S)") as the compound (X) can be obtained by, for example, hydrolyzing and condensing a hydrolyzable silane compound. Specifically, the following [1] or [2] may be mentioned: [1] The hydrolyzable silane compound (ms-1) having an epoxy group, or the silane compound (ms-1) and other silane compounds The mixture is hydrolyzed and condensed to synthesize an epoxy-containing polyorganosiloxane, and then the obtained epoxy-containing polyorganosiloxane and a carboxylic acid having a partial structure represented by the formula (1) ( Hereinafter also referred to as "specific carboxylic acid") a method for carrying out the reaction; [2] a hydrolyzable silane compound (ms-2) having the partial structure represented by the formula (1) or the silane compound (ms- 2) The method of hydrolyzing and condensing the mixture with other silane compounds. Among these methods, the method of [1] is simple and is preferable in terms of increasing the introduction rate of the partial structure represented by the formula (1) in the polymer (S). In the method of [1], the reaction product of an epoxy group-containing polyorganosiloxane and a carboxylic acid is used as the compound (X).

Specific examples of the hydrolyzable silane compound (ms-1) having an epoxy group include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidol Oxyethylethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycidoxyethyldimethylethoxysilane, 4-glycidoxy Butyltrimethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane , 4-glycidoxybutyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, etc. As the silane compound (ms-1), one kind of these compounds may be used alone or two or more kinds may be used in combination.

Other silane compounds are not particularly limited as long as they exhibit hydrolyzable silane compounds, and examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Alkoxy silanes such as phenyl trimethoxy silane, phenyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane; 3-mercaptopropyl trimethoxy silane, 3- Mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , N-(3-cyclohexylamino)propyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and other alkoxysilanes containing nitrogen and sulfur atoms ; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 6-(meth)acryloyloxyhexyl Trimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxy Unsaturated hydrocarbon-containing alkoxysilanes such as silane, vinyltriethoxysilane, p-styryltrimethoxysilane, and the like; in addition, trimethoxysilylpropyl succinic anhydride and the like can also be mentioned. The other silane compounds may be used alone or in combination of two or more.

The hydrolysis and condensation reaction of the silane compound can be carried out by reacting one or two or more of the silane compounds described above with water, preferably in the presence of an appropriate catalyst and an organic solvent. In the method of [1], not only can a sufficient amount of the partial structure represented by the formula (1) be introduced into the side chain of the polymer, but also the side reaction caused by the excessive amount of epoxy groups can be suppressed From a viewpoint, the epoxy equivalent of the polyorganosiloxane containing epoxy groups is preferably 100 g/mol to 10,000 g/mol, and more preferably 150 g/mol to 1,000 g/mol. Therefore, when synthesizing the epoxy group-containing polyorganosiloxane, it is preferable to adjust the use ratio of the silane compound (ms-1) such that the epoxy equivalent of the obtained polyorganosiloxane is within the above range. In the hydrolysis/condensation reaction, the use ratio of water is preferably 0.5 mol to 100 mol, and more preferably 1 mol to 30 mol, relative to 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. The catalyst is preferably an alkali metal compound or the like in terms of being capable of suppressing side reactions such as ring-opening of epoxy groups, being able to accelerate the rate of hydrolysis and condensation, and being excellent in storage stability. The organic base is particularly preferably a third or fourth grade organic base. The amount of the organic base used varies depending on the type of organic base, reaction conditions such as temperature, etc., and can be appropriately set. It is preferably 0.01 times to 3 times the molar ratio, and more preferably 0.05 times the molar ratio with respect to all the silane compounds. ~ 1 times mole.

Examples of the organic solvent used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Specific examples of these organic solvents include hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and diethyl ketone. Cyclohexanone, cyclopentanone, etc.; esters include, for example, ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate Examples of ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of alcohols include 1-hexanol, 4-methyl-2-pentanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. Among these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents may be used alone or in combination of two or more. The use ratio of the organic solvent in the hydrolysis condensation reaction is preferably 10 parts by weight to 10,000 parts by weight, and more preferably 50 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of all silane compounds used in the reaction.

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

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

（式（3）中，A¹ 及A² 分別與所述式（2-1）為相同含義；其中，所述式（1-1）及式（1-2）中的「*1」表示鍵結於R¹² 的結合鍵；於A¹ 為下述式（1-1）所表示的基團的情況下，R¹¹ 為一價有機基，於A¹ 為下述式（1-2）所表示的基團的情況下，R¹¹ 為氫原子或一價有機基；R¹² 為二價有機基；於A² 為下述式（1-1）所表示的基團的情況下，R¹³ 為二價有機基，於A² 為下述式（1-2）所表示的基團的情況下，R¹³ 為單鍵或二價有機基；s及r分別獨立地為0或1；其中，式（3）中具有一個羧基）Specific examples of the specific carboxylic acid include, for example, compounds represented by the following formula (3). [化46]

(In formula (3), A ¹ and A ² have the same meaning as the above formula (2-1); wherein, “*1” in the formula (1-1) and formula (1-2) means Bonding bond to R ¹² ; where A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group, and A ¹ is the following formula (1-2) In the case of the group represented, R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; in the case where A ² is a group represented by the following formula (1-1), R ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group; s and r are independently 0 or 1; Among them, formula (3) has a carboxyl group)

In the formula (3), for the illustration of the monovalent organic group of R ¹¹ , the description of R ⁸ and R ¹⁰ in the formula (2-2) can be applied. In addition, as an example of the divalent organic group of R ¹² and R ¹³ , the description of R ⁵ to R ⁷ in the above formula (2-1) can be applied. The 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).

From the viewpoint of improving the reduction effect of the AC residual image, the specific carboxylic acid preferably has not only a partial structure represented by the formula (1) but also a partial structure represented by the formula (4) in the molecule. . In addition, the description of the case where a specific diamine can be applied as a preferable specific example of the partial structure represented by said formula (4). In addition, a part of the structure represented by the formula (4) may be constituted by the benzene ring in the formula (1), which is the same as the specific diamine.

此外，於合成聚合物（S）時，特定羧酸可單獨使用一種或者將兩種以上組合使用。所述式（g-1）～式（g-13）中，式（g-1）、式（g-2）、式（g-4）～式（g-8）、及式（g-11）～式（g-13）相當於具有所述式（4）所表示的部分結構的化合物。Specific examples of the specific carboxylic acid include, for example, compounds represented by the following formula (g-1) to formula (g-13). [化47]

In addition, when synthesizing the polymer (S), the specific carboxylic acid may be used alone or in combination of two or more. In the above formula (g-1) to formula (g-13), formula (g-1), formula (g-2), formula (g-4) to formula (g-8), and formula (g- 11) to formula (g-13) correspond to a compound having a partial structure represented by the formula (4).

From the viewpoint of improving the sensitivity to light, the content ratio of the partial structure represented by the formula (1) in one molecule of the polymer (S) is preferably relative to the silicon contained in the polymer (S) Atoms are set to 3 mol% to 100 mol%, more preferably 5 mol% to 95 mol%, and particularly preferably 10 mol% 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 formula (1) becomes the above range.

In addition, a specific carboxylic acid can be synthesized by appropriately combining ordinary methods of organic chemistry. As an example, it can be obtained by, for example, the following method: a compound represented by "R ¹¹ -A ¹ -H" and "HO-R ¹² -A ² -R ¹³ -COOM (where M is a carboxyl group The compound represented by "protecting group" is preferably reacted in the presence of a catalyst in an organic solvent, if necessary, and then deprotected. However, the synthesis order of a specific carboxylic acid is not limited to the above method.

（式中，j為0～12的整數，h為1～10的整數） 此外，其他羧酸可單獨使用選自該些羧酸中的一種或者將兩種以上組合使用。When synthesizing the polymer (S), the carboxylic acid used in the reaction with the epoxy group-containing polyorganosiloxane may be only a specific carboxylic acid, or other carboxylic acids other than the specific carboxylic acid may be used in combination. The other carboxylic acid is not particularly limited as long as it does not have a partial structure represented by the formula (1), and examples thereof include a carboxylic acid having the liquid crystal alignment group. Specific examples of other carboxylic acids include, for example, caproic acid, lauric acid, pentadecyl acid, palmitic acid, stearic acid, oleic acid, 11-octadecenoic acid (vaccenic acid), linolenic acid, Fatty acids having 6 to 20 carbon atoms such as linolenic acid and arachidic acid, compounds represented by the following formula (C-2-1) to formula (C-2-10), etc., respectively. [Chemical 48]

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

The use ratio of the carboxylic acid which reacts with the epoxy group-containing polyorganosiloxane is preferably 0.001 mol to 1.5 mol relative to 1 mol of the total epoxy group of the polyorganosiloxane It is more preferably set to 0.01 mol to 1.0 mol. From the viewpoint of sufficiently obtaining the effects of the present invention, the use ratio of other carboxylic acids is preferably 80 mol% or less relative to the total amount of carboxylic acids reacted with the epoxy group-containing polyorganosiloxane. It is more preferably set to 50 mol% or less.

The reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst used in the reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid, for example, a compound known as a so-called hardening accelerator that promotes the reaction of an organic base and an epoxy compound can be used. Here, the organic base includes, for example, primary organic amines to secondary organic amines such as ethylamine, piperazine, and piperidine; tertiary organic amines such as triethylamine and pyridine; and tetramethylammonium hydroxide. Grade organic amines, etc. Among these compounds, the organic base is preferably a tertiary organic amine or a tertiary organic amine. Examples of the hardening accelerator include: tertiary amines, imidazole compounds, organophosphorus compounds, quaternary phosphonium salts, diazabicycloolefins, organic metal compounds such as tin octoate, quaternary ammonium salts, boron compounds, tin chloride Such as metal halogen compounds. Among these compounds, quaternary ammonium salts are preferred, and specific examples include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butyl chloride. Ammonium, etc. The catalyst is preferably 100 parts by weight or less relative to 100 parts by weight of epoxy group-containing polyorganosiloxane, more preferably 0.01 parts by weight to 100 parts by weight, particularly preferably 0.1 parts by weight to 20 parts by weight To use.

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

The reaction temperature in the reaction is preferably 0°C to 200°C, more preferably 50°C to 150°C. The reaction time is preferably from 0.1 hour to 50 hours, and more preferably from 0.5 hour to 20 hours. In addition, after the reaction is completed, the organic solvent layer separated from the reaction solution is preferably washed with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as needed, and then the solvent is removed, thereby obtaining a polymer (S). In addition, the synthesis method of polyorganosiloxane is not limited to the above-mentioned hydrolysis and condensation reaction, and for example, a method of allowing a hydrolyzable silane compound to react in the presence of oxalic acid and alcohol may be used.

（式（7）中，A¹ 、A² 、R¹¹ 、R¹² 、R¹³ 、s及r分別與所述式（3）為相同含義；Z¹ 為二價有機基；「*」表示與矽原子的結合鍵） 此外，關於Z¹ 的二價有機基，可列舉所述式（2-1）的R⁵ ～R⁷ 所例示的基團等。The polymer (S) obtained in the above-described manner preferably includes a partial structure formed by the reaction of a polyorganosiloxane having an epoxy group and a carboxylic acid, and specifically, preferably includes the following formula ( 7) Part of the structure shown. [Chem 49]

(In formula (7), A ¹ , A ² , R ¹¹ , R ¹² , R ¹³ , s and r have the same meanings as the above formula (3); Z ¹ is a divalent organic group; “*” means Bonding bond of silicon atom) In addition, regarding the divalent organic group of Z ¹ , the groups exemplified in R ⁵ to R ⁷ of the above formula (2-1) can be cited.

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

[Poly(meth)acrylate] The poly(meth)acrylate as the compound (X) can be obtained by, for example, a method of using a (meth)acrylic monomer having an epoxy group (m-1) ), or a mixture of the (meth)acrylic monomer (m-1) and other (meth)acrylic monomers, after polymerization in the presence of a polymerization initiator, the resulting polymerization Substances (hereinafter also referred to as "epoxy group-containing poly(meth)acrylates"), reacting with specific carboxylic acids.

Examples of the (meth)acrylic monomer (m-1) include unsaturated carboxylic acid esters having an epoxy group. Specific examples thereof include, for example, glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (methyl ) 3,4-epoxybutyl acrylate, 3,4-epoxybutyl α-ethylacrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, (meth)acrylic acid 6 ,7-epoxyheptyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, 4-hydroxybutyl glycidyl acrylate, (meth)acrylic acid (3-ethyloxetane- 3-yl) methyl ester, etc. In addition, the (meth)acrylic unitary body (m-1) may be used alone or in combination of two or more kinds.

Examples of other (meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid ω-carboxypolycaprolactone, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, Unsaturated carboxylic acids such as α-n-butyl acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid; methyl (meth)acrylate, ( Ethyl meth)acrylate, propyl (meth)acrylate, allyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, methoxyethyl (meth)acrylate, (meth)acrylic acid -N,N-dimethylaminoethyl, (meth)acrylic acid-N,N-diethylaminoethyl, (meth)acrylic acid methoxypolyethylene glycol, (meth)acrylic acid octyl (Meth)acrylates such as oxypolyethylene glycol, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; α-methoxymethyl acrylate, α-ethoxy Α-alkoxy acrylates such as methyl acrylate; unsaturated carboxylic acid esters such as methyl crotonate, ethyl crotonate and other crotonates; maleic anhydride, itaconic anhydride, citraconic anhydride, cis Formula -1,2,3,4-tetrahydrophthalic anhydride and other unsaturated polycarboxylic acid anhydride and so on. In addition, the other (meth)acrylic unitary substance may be used alone or in combination of two or more.

When synthesizing poly(meth)acrylate, the total amount (moles) of epoxy groups per 1 g of epoxy group-containing poly(meth)acrylate is preferably 5.0×10 ^-5 moles/g or more , more preferably 1.0 × 10 ^-4 mole /g~1.0×10 ^-2 mole / g, particularly preferably 5.0 × 10 ^-4 mole /g~5.0×10 ^-3 mole / g. Therefore, with regard to the use ratio of (meth)acrylic unit mass (m-1), it is preferable that the total number of moles per 1 g of epoxy groups of the epoxy group-containing poly(meth)acrylate be Adjust the range of values. In addition, other monomers other than (meth)acrylic monomers may be used during polymerization. Examples of other monomers include: conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; aromatics such as styrene, methylstyrene and divinylbenzene Vinyl compounds, etc. The use ratio of other monomers is preferably 30 mol% or less, and more preferably 20 mol% or less with respect to the total amount of monomers used in the synthesis of poly(meth)acrylate.

The polymerization reaction using a (meth)acrylic monomer is preferably carried out by radical polymerization. Examples of the polymerization initiator used in the polymerization reaction include those generally used in radical polymerization, and examples thereof include 2,2′-azobis(isobutyronitrile) and 2,2′-azobis( 2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, laurel peroxide Organic peroxides such as acetyl, tributyl peroxytrimethylacetate, 1,1'-bis (third butyl peroxy) cyclohexane; hydrogen peroxide; those containing these peroxides and reducing agents Redox type initiators, etc. Among these compounds, azo compounds are preferred, and 2,2'-azobis (isobutyronitrile) is more preferred. The polymerization initiator may be used alone or in combination of two or more of these compounds. The use ratio of the polymerization initiator is preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of all monomers used in the reaction.

The polymerization reaction of the (meth)acrylic monomer is preferably carried out in an organic solvent. Examples of the organic solvent used in this reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Among these compounds, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. As preferred specific examples thereof, for example, diethylene glycol methyl ether, propylene glycol monomethyl ether acetate, etc. may be mentioned. In addition, the organic solvent may use these compounds alone or in combination of two or more.

In the polymerization reaction of (meth)acrylic monomers, the reaction temperature is preferably 30°C to 120°C, more preferably 60°C to 110°C. The reaction time is preferably 1 hour to 36 hours, and more preferably 2 hours to 24 hours. In addition, the amount of use of the organic solvent (a) is preferably an amount relative to the total amount of the reaction solution (a+b), and the total amount of monomers used in the reaction (b) becomes 0.1% to 50% by weight .

The epoxy group-containing poly(meth)acrylate obtained by the reaction is then reacted with a specific carboxylic acid. For the specific examples of the specific carboxylic acid, the description of the polymer (S) can be applied. In this reaction, a specific carboxylic acid may be used alone, or a carboxylic acid other than the specific carboxylic acid may be used in combination. The use ratio of the carboxylic acid which reacts with the epoxy group-containing poly(meth)acrylate to 1 mole of the total epoxy group of the epoxy group-containing poly(meth)acrylate is preferably It is set to 0.001 mol to 0.95 mol. More preferably, it is 0.01 mol to 0.9 mol, and particularly preferably 0.05 mol to 0.8 mol.

The reaction of the epoxy group-containing poly(meth)acrylate and carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. Here, the catalyst used in the reaction may, for example, be a compound exemplified as a catalyst usable in the synthesis of the polymer (S). Among these compounds, quaternary ammonium salts are preferred. The amount of catalyst used is preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight or less, and particularly preferably 0.1 parts by weight relative to 100 parts by weight of epoxy group-containing poly(meth)acrylate. 20 parts by weight.

The organic solvent used for the reaction can be exemplified by an organic solvent that can be used when polymerizing a (meth)acrylic monomer, and among them, an ester is preferred. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) becomes 0.1% by weight or more, and more preferably 5% by weight % To 50% by weight. The reaction temperature is preferably 0°C to 200°C, and more preferably 50°C to 150°C. The reaction time is preferably 0.1 hour to 50 hours, and more preferably 0.5 hour to 20 hours.

In this way, a solution containing poly(meth)acrylate as compound (X) was obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the poly(meth)acrylate contained in the reaction solution can be separated and then provided to the preparation of the liquid crystal alignment agent, or the separated poly(methyl) ) Preparation of liquid crystal alignment agent after purification of acrylate. The separation and purification of poly(meth)acrylate can be performed according to a known method.

In addition, the method of synthesizing the poly(meth)acrylate as the compound (X) is not limited to the above method. For example, it can also be obtained by a method such as a (meth)acrylic unitary body having a partial structure represented by the formula (1), or the (meth)acrylic unitary body and other (meth ) A mixture of acrylic monomers is polymerized in the presence of a polymerization initiator.

In terms of not only improving the liquid crystal alignment of the formed liquid crystal alignment film but also ensuring the stability of the liquid crystal alignment over time, the poly(meth)acrylate is converted to polystyrene measured by GPC The number average molecular weight (Mn) is preferably 250 to 500,000, more preferably 500 to 100,000, and particularly preferably 1,000 to 50,000.

<Other components> The liquid crystal aligning agent of this invention contains the compound (X) mentioned above, and may contain other components as needed. Other components that can be added to the liquid crystal alignment agent include, for example, polymers other than the compound (X) and compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound") , Functional silane compounds, compounds with photopolymerizable groups (hereinafter referred to as "photopolymerizable group-containing compounds"), photosensitizers, etc.

[Other Polymers] The other polymers can be used to improve solution properties or electrical properties. The other polymer is a polymer that does not have the partial structure represented by the formula (1), and its main skeleton is not particularly limited. Specifically, for example, a derivative of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene can be cited Polymers, such as poly(styrene-phenyl maleimide) derivatives, poly(meth)acrylates, etc. as the main skeleton. Among these polymers, it is preferably selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly(meth)acrylate, and polyamide Of at least one polymer. When other polymers are added to the liquid crystal aligning agent, the mixing ratio of the other polymers is preferably 90 parts by weight or less with respect to the total of 100 parts by weight of the polymers contained in the liquid crystal aligning agent. More preferably, it is 0.1 to 80 parts by weight, and particularly preferably 0.1 to 70 parts by weight.

[Epoxy group-containing compound] The epoxy group-containing compound can be used to improve the adhesion or electrical characteristics of the liquid crystal alignment film to the substrate surface. Examples of the epoxy group-containing compound described above include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether Ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N, N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethyl Cyclohexane, N,N-diglycidyl-cyclohexylamine, etc. are preferable. In addition, as an example of the epoxy group-containing compound, the epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used. When adding these epoxy compounds to a liquid crystal aligning agent, it is preferable to set the said epoxy compound formulation ratio to 40 weight part with respect to the total of 100 weight parts of polymers contained in a liquid crystal aligning agent. Hereinafter, it is more preferably 0.1 to 30 parts by weight.

[Functional Silane Compound] The functional silane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of the functional silane compound described above include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-amino Propyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethyl Oxysilylpropyltriethylidenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. In the case where these functional silane compounds are added to the liquid crystal alignment agent, it is preferable to set the ratio of the functional silane compound to 2 with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal alignment agent It is preferably 0.02 to 0.2 parts by weight or less.

[Photopolymerizable group-containing compound] When a coating film formed using a liquid crystal alignment agent is irradiated with light to give liquid crystal alignment ability, the photopolymerizable group-containing compound may be used to improve the alignment of the liquid crystal alignment film Used for limiting purposes. Here, the photopolymerizable group may, for example, be a group having a polymerizable unsaturated bond, and specifically, for example, (meth)acryloyloxy, styryl, (meth)acryloylamide. Group, vinyl, vinylidene, vinyloxy (CH ₂ =CH-O-), maleimide, etc.

In terms of high photoreactivity, as the photopolymerizable group-containing compound, a (meth)acrylate compound can be preferably used, and specific examples include methyl (meth)acrylate and (meth) Group) ethyl acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (methyl ) Monofunctional (meth)acrylates such as acrylate, methoxytriethylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; ethylene glycol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, polyether (meth)acrylate, ethoxylated bisphenol A di( Multifunctional (meth)acrylates such as meth)acrylates. When a compound containing a photopolymerizable group is added to a liquid crystal alignment agent, the compounding ratio of the compound containing a photopolymerizable group is preferably 100 parts by weight of the total amount of polymers contained in the liquid crystal alignment agent It is 30 parts by weight or less, and more preferably 1 part by weight to 20 parts by weight.

於使用光增感劑的情況下，相對於液晶配向劑中所含的聚合物100重量份，所述光增感劑的調配比例較佳為設為0.01重量份～50重量份，更佳為設為0.1重量份～20重量份。[Photosensitizer] As the photosensitizer, various compounds having a photosensitizer function can be used. Here, the so-called "light sensitization function" means that after being irradiated with light, it becomes a single excited state, and then intersects intersects depending on the situation. If it collides with other molecules, it will change the other party to the excited state, and itself The function of returning to the basal state. Specific examples of the photosensitizer include compounds represented by the following formula (H-1) to formula (H-6), respectively. [化50]

In the case of using a light sensitizer, the formulation ratio of the light sensitizer is preferably 0.01 to 50 parts by weight relative to 100 parts by weight of the polymer contained in the liquid crystal alignment agent, and more preferably It is set to 0.1 to 20 parts by weight.

In addition, as other components, additives commonly used in the preparation of liquid crystal alignment agents can be used. Examples of additives other than the above include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, and dispersants.

<Solvent> The liquid crystal alignment agent of the present invention is prepared in the form of a liquid composition in which the specific compound and other components used as needed are preferably dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethyl Ethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate Ester, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyl ether Glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethyl ether Glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, etc. These organic solvents may be used alone or in combination of two or more.

The liquid crystal alignment agent of the present invention may contain only one polymer as a polymer component, or may contain two or more polymers. Preferred forms when two or more polymers are included include, for example, the following [1] to [3]. [1] It contains a polymer (hereinafter also referred to as "specific polymer") and other polymers as the compound (X), and the specific polymer and other polymers are selected from polyamic acid, polyamic acid ester, The form of at least one of polyimide and polyimide. [2] A plurality of specific polymers are contained, and the plurality of specific polymers are in a form of at least one selected from polyamic acid, polyamic acid ester, polyimide, and polyamidoamine. [3] Contains a specific polymer and other polymers, and the specific polymer is polyorganosiloxane, and the other polymer is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamidoamine At least one form. In addition, in the aspect of [1], it is presumed that by setting the specific polymer as a polymer having fluorine atoms or silicon atoms, the specific polymer having fluorine atoms or silicon atoms is located in the upper layer, and does not have fluorine atoms and Other polymers of silicon atoms are localized in the lower layer, so that the distribution of the polymer can be varied in the liquid crystal alignment film.

In addition, when the liquid crystal alignment agent containing the compound (X) is used, the reason for obtaining the effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element is not certain. As one of the assumptions, the following is considered. That is, it is considered that in the partial structure represented by the formula (1), the compound (X) introduces a monovalent organic group onto at least one of the α carbon and β carbon of the carbonyl group, preferably the α carbon of the carbonyl group, Then, when irradiated with light, the photodimerization reaction is suppressed and the photoisomerization reaction takes precedence over the compound having a partial structure (cinnamyl group) in which R ¹ and R ² are hydrogen atoms in the formula (1) get on. Thereby, the alignment restricting force of the liquid crystal in the liquid crystal alignment film formed using the liquid crystal alignment agent containing the compound (X) is improved, and it is presumed that the result is an effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc. It is preferably in the range of 1% by weight to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate by the method described below, and is preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that 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, making it 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, and it is difficult to obtain a good liquid crystal alignment film. In addition, there is an increase in the viscosity of the liquid crystal alignment agent and a decrease in coatability. tendency.

The range of particularly good solid content concentration differs depending on the method used when applying the liquid crystal alignment agent to the substrate. For example, when the spinner method is used, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is in the range of 1.5% by weight to 4.5% by weight . In the case of using the printing method, it is particularly preferable to set the solid content concentration in the range of 3% by weight to 9% by weight, thereby setting the solution viscosity in the range of 12 mPa·s to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to the range of 1% by weight to 5% by weight, and thereby to set the solution viscosity to the range of 3 mPa·s to 15 mPa·s. The temperature when preparing the liquid crystal alignment agent of the present invention is preferably 10°C to 50°C, more preferably 20°C to 30°C.

<Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment film can be manufactured by using the liquid crystal alignment agent of the present invention described above. In addition, the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display device of the present invention is not particularly limited, for example, it can be applied to TN type, STN type, vertical alignment (Vertical Alignment, VA) type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), In-Plane Switching (IPS) type, Fringe Field Switching , FFS) type, Optically Compensatory Bend (Optically Compensatory Bend, OCB) type and other action modes.

The liquid crystal display element of the present invention can be manufactured by including the following steps (1-1) to (1-3), for example. Step (1-1) uses different substrates according to the required operation mode. Step (1-2) and step (1-3) are common to each operation mode.

[Step (1-1): Formation of coating film] First, the liquid crystal alignment agent of the present invention is coated on a substrate, and then the coating surface is heated to form a coating film on the substrate. (1-1A) In the case of manufacturing a liquid crystal display element such as TN type, STN type, or VA type, first, two substrates provided with a patterned transparent conductive film are used as a pair, and each of the substrates On the transparent conductive film forming surface, it is preferable to apply the liquid crystal alignment agent of the present invention separately by a lithography method, a spin coating method, a roll coater method, or an inkjet printing method. For the substrate, for example, glass such as float glass and soda glass; including plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether ash, polycarbonate, poly(alicyclic olefin), etc. Transparent substrate. The transparent conductive film provided on one side of the substrate can be used: a NESA film containing tin oxide (SnO ₂ ) (registered trademark of US PPG company), or containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium Tin Oxide (ITO) film, etc. In order to obtain a patterned transparent conductive film, for example, the following method can be used: a method of forming a pattern by light and etching after forming an unpatterned transparent conductive film; using a mask with a desired pattern when forming the transparent conductive film Methods, etc. When applying the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound or a functional titanium compound in advance Etc.

After the liquid crystal alignment agent is applied, for the purpose of preventing sagging of the applied liquid crystal alignment agent, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30°C to 200°C, more preferably 40°C to 150°C, and particularly preferably 40 to 100°C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, the solvent is completely removed, and if necessary, a calcination (post-baking) step is performed for the purpose of thermally amidating the amide acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80°C to 300°C, more preferably 120°C to 250°C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this way is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, the liquid crystal of the present invention is applied to the electrode formation surface of the substrate provided with the following electrode and the surface of the counter substrate not provided with the electrode The alignment agent, in turn, heats each coated surface to form a coating film, and the electrode includes a transparent conductive film or metal film patterned into a comb-teeth shape. 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 the metal film, the pretreatment of the substrate, and the preferred coating film formed The film thickness is the same as in (1-1A) above. For the metal film, for example, a film containing metal such as chromium can be used.

In any of the above (1-1A) and (1-1B), the liquid crystal alignment film or the coating film that becomes the liquid crystal alignment film is formed by applying the liquid crystal alignment agent on the substrate and then removing the organic solvent. In this case, the polyamic acid, the polyamic acid ester and the polyimide prepared in the liquid crystal alignment agent of the present invention may be subjected to dehydration ring-closure reaction by further heating after the coating film is formed to form a further Amidified coating.

[Step (1-2): Alignment ability-imparting process] In the case of manufacturing a TN type, STN type, IPS type or FFS type liquid crystal display element, the application to the coating film formed in the step (1-1) is carried out Handling of liquid crystal alignment capabilities. With this, the alignment ability of the liquid crystal molecules is given to the coating film to become a liquid crystal alignment film. Examples of the treatment for aligning ability are: rubbing treatment in which the coating film is wiped in a certain direction by using a roll wound with a cloth containing fibers such as nylon, rayon, and cotton; and optical alignment in which polarized or unpolarized radiation is irradiated to the coating film Processing etc. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (1-1) may be used directly as a liquid crystal alignment film, or the coating film may be subjected to an alignment ability-imparting treatment.

The light irradiation in the photo-alignment process can be obtained by the following methods: [1] a method of irradiating the coating film after the post-baking step; [2] a coating film after the pre-baking step and before the post-baking step Irradiation method; [3] In at least any one of the pre-baking step and the post-baking step, a method of irradiating the coating film during heating of the coating film, etc. Among these methods, the method of [2] is preferably used in terms of a high effect of improving the afterimage characteristics and contrast characteristics of the liquid crystal display element.

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

In addition, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment to make the liquid crystal alignment film have different liquid crystal alignment capabilities in each region: a part of the liquid crystal alignment film is irradiated by irradiating a part of the liquid crystal alignment film with ultraviolet rays The pre-tilt angle change process; or after forming a resist film on a part of the surface of the liquid crystal alignment film, after performing a rubbing process in a direction different from the previous rubbing process, the process of removing the resist film. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. The liquid crystal alignment film suitable for the VA type liquid crystal display element can also be suitably used for the polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell] (1-3A) The liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed in the above-mentioned manner, arranging liquid crystal between the two substrates facing each other . In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a previously known method. First, the two substrates are opposed to each other via a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealant to the cells divided by the substrate surface and the sealant After filling and filling the liquid crystal into the gap, the injection hole is sealed, thereby manufacturing a liquid crystal cell. The second method is a method called liquid crystal drop infusion (One Drop Fill, ODF) method. On one of the two substrates on which the liquid crystal alignment film is formed, apply a UV-curable sealant to a predetermined portion of the substrate, and then drop liquid crystal on a predetermined number of positions on the surface of the liquid crystal alignment film. The liquid crystal alignment film is attached to another substrate in a facing manner, and the liquid crystal is spread on the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using either method, it is desirable that the liquid crystal cell manufactured in the above manner is further heated to a temperature at which the used liquid crystal obtains an isotropic phase, and then slowly cooled to room temperature, thereby removing the liquid crystal filling Flow alignment.

For the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers can be used. Liquid crystals include nematic liquid crystals and discotic liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, and phenyl rings can be used. Hexane liquid crystal, ester liquid crystal, triphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, etc. In addition, these liquid crystals can also be used by adding the following substances: for example, cholesterol-type liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate, etc.; under the trade name " Chiral agents sold by "C-15" and "CB-15" (manufactured by Merck); iron such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate Electric LCD, etc.

(1-3B) In the case of manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in (1-3A) except that the photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here may be, for example, 5 V to 50 V DC or AC. In addition, as the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, and preferably ultraviolet rays including light having a wavelength of 300 nm to 400 nm. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the preferred wavelength region can be obtained by a method of using a light source with a filter, a diffraction grating, and the like. The irradiation amount of light is preferably 1,000 J/m ² or more and less than 200,000 J/m ² , and more preferably 1,000 J/m ² to 100,000 J/m ² .

(1-3C) When a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group is used to form a coating film on a substrate, the following method may also be used: ) The liquid crystal cell is constructed in the same manner, and then a liquid crystal display element is manufactured by the step of irradiating the liquid crystal cell with a voltage applied between the conductive films of a pair of substrates. According to this method, the advantages of the PSA mode can be realized with a small amount of light irradiation. The description of (1-3B) can be applied to the applied voltage or the conditions of the irradiated light.

Next, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate sandwiching a polarizing film called "H film" with a cellulose acetate protective film, or a polarizing plate including the H film itself. It is made by absorbing iodine while extending the alignment of polyvinyl alcohol.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as: watches, portable game consoles, word processors, notebook personal computers, car navigation, camcorders, and personal digital assistants (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, LCD TV, information display and other display devices. [Example]

Hereinafter, the present invention will be further 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 epoxy equivalent of the polymer were measured by the following method. In addition, in the following, the compound represented by Formula A may only be represented as "Compound A". [Weight average molecular weight of polymer Mw] Mw is a polystyrene conversion value measured by GPC under the following conditions. Column: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40°C Pressure: 68 k gf/cm ² [Epoxy Equivalent] The epoxy equivalent is based on hydrochloric acid-methyl ethyl as described in JIS C 2105 Ketone method to determine.

<Synthesis of Compound> [Example 1-1: Synthesis of Compound (b-1)] The compound (b-1) was synthesized according to the following scheme 1. [化51]

9.6 g of 4-nitrobenzaldehyde and 15.0 g of methylmalonic acid were dissolved in 100 ml of pyridine, 12.5 ml of piperidine was added thereto, and then stirred at 80°C for 5 hours. After the reaction solution was left to cool to room temperature, 100 ml of ethyl acetate was added, followed by 100 ml of hydrochloric acid, and the solution was separated. After the pure water was separated again, it was concentrated to obtain 10.5 g of an intermediate (b-1-1) as a white solid with a purity of 99%. 10 g of the obtained intermediate (b-1-1) was added to 30 ml of sulfenyl chloride, a catalyst amount of N,N-dimethylformamide was added, and then 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, which was cooled to 0°C and stirred for 5 minutes. Then, the reaction solution (A) was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 4 hours to complete the reaction. After adding 300 ml of ethyl acetate and 100 ml of tetrahydrofuran (THF), the solution was separated with hydrochloric acid, aqueous sodium carbonate, and pure water, and then concentrated to obtain 19.0 g of white solid with a purity of 99%. Intermediate (b-1-2). Then, 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 was stirred at 60°C for 5 hours. After the reaction liquid was left to cool to room temperature, 150 ml of ethyl acetate was added, and after liquid separation with pure water, it was concentrated to obtain 13.5 g of compound (b-1) as a yellow solid with a purity of 99%.

[Example 1-2: Synthesis of Compound (b-2)] Except for the second step of Scheme 1 of Example 1-1, 4-hydroxy-4'-nitrobiphenyl was changed to 4-nitrophenol Other than that, it was synthesized by the same method as in Example 1-1 to obtain compound (b-2).

[Example 1-3: Synthesis of Compound (b-3)] Except for the second step of Scheme 1 of Example 1-1, 4-hydroxy-4'-nitrobiphenyl was changed to 4-amino- Except for 4'-nitrobiphenyl, it was synthesized by the same method as in Example 1-1 to obtain compound (b-3).

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

[Example 1-5: Synthesis of compound (b-27)] Except for the second step of Scheme 1 of Example 1-1, 4-hydroxy-4'-nitrobiphenyl was changed to 2-methyl- Except for 4-nitroaniline, it was synthesized by the same method as in Example 1-1 to obtain compound (b-27).

[Example 1-6: Synthesis of compound (t-5)] The compound (t-5) was synthesized according to the following scheme 2. [化52]

5.0 g of piperazine and 12.3 g of triethylamine were dissolved in 100 ml of tetrahydrofuran, cooled to 0°C, and stirred for 5 minutes. To this, a solution prepared by adding 12.1 g of methacryloyl chloride in 100 ml of tetrahydrofuran was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 4 hours to complete the reaction. After adding 300 ml of ethyl acetate, the solution was separated with hydrochloric acid, aqueous sodium carbonate, and pure water, and then concentrated to obtain 11.6 g of an intermediate as a white solid (t-5-1) with a purity of 99%. . 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 tris Ethylamine was added to 120 ml of N,N-dimethylacetamide. Then, it was stirred at 60°C for 6 hours. After the reaction solution was left to cool to room temperature, 300 ml of ethyl acetate was added, and the solution was separated with pure water. After adding hydrochloric acid to the obtained water layer to form an acidic aqueous solution, ethyl acetate was added to perform liquid separation. Finally, after separating the organic layer with pure water, it was concentrated to obtain 20.0 g of an intermediate (t-5-2) as a pale yellow solid with a purity of 99%. Then, 18.0 g of the intermediate (t-5-2) was added to 100 ml of acetic anhydride. Then, it was stirred at 60°C for 12 hours. After the reaction liquid was left to cool to room temperature, the precipitated solid was filtered, washed with hexane, and dried to obtain 15.5 g of a compound (t-5) as a pale yellow solid with a purity of 99%.

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

[Example 2-2 to Example 2-9 and Synthesis Example 1 to Synthesis Example 3] In addition to changing the type and amount of the tetracarboxylic dianhydride and diamine used as described in Table 1 below, the Polyamide (polymer (A-2) to polymer (A-9) and polymer (B-1) to polymer (B-3)) were synthesized in the same manner as in Example 2-1.

[Table 1]

In Table 1, the numerical value in parentheses of tetracarboxylic dianhydride and diamine shows the usage ratio [mol parts] with respect to the total of 100 mol parts of tetracarboxylic dianhydride used for synthesizing a polymer. The abbreviations in Table 1 have the following meanings. <Tetracarboxylic dianhydride> a-1: Compound represented by the formula (a-1) a-2: Compound represented by the formula (a-2) a-3: 1,3-propanediol bis( Dehydrated trimellitate) (the compound represented by the formula (a-3)) a-4: 1,2,3,4-cyclobutane tetracarboxylic dianhydride a-5: 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride a-6: pyromellitic dianhydride t-5: the compound represented by the formula (t-5) <diamine> b-1: the Compound b-2 represented by formula (b-1): Compound b-3 represented by formula (b-2): Compound b-27 represented by formula (b-3): Formula (b-3) b-27) Compound c-1 represented by: Compound c-2 represented by the following formula (c-1): Compound c-3 represented by the following formula (c-2): p-phenylenediamine c- 4: N, N-bis (4-aminophenyl) methylamine c-5: 4,4'-diamino-2,2'-dimethylbiphenyl [Chem. 53]

[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 was mixed at room temperature. Then, after 100 g of pure water was slowly added dropwise, it was stirred at 80° C. for 6 hours. Then, the organic layer was taken out, washed with 0.2% by weight aqueous ammonium nitrate solution until the washed water became neutral, and then concentrated to obtain a polyorganosiloxane having an epoxy group as a viscous transparent liquid (ES-1). The epoxy group-containing polyorganosiloxane (ES-1) has an Mw of 2,200 and an epoxy equivalent of 186 g/mole.

[Example 2-10: Synthesis of polymer (S-1)] 9.3 g of the polyorganosiloxane (ES-1) having epoxy group obtained in the above Synthesis Example 4 and 26 g of methyl group Isobutyl ketone, 3 g of the compound (g-1) obtained in Examples 1-4, and 0.10 g of UCAT 18X (trade name, quaternary amine manufactured by San-Apro) Salt), and stirred at 80°C for 12 hours. Then, the precipitate produced by throwing the reaction mixture into methanol was filtered, dissolved in ethyl acetate to form a solution, and the solution was separated with pure water and then concentrated to obtain a white powder. In the form, 6.3 g of polyorganosiloxane (polymer (S-1)) as compound (X) was obtained. The weight average molecular weight Mw of the polymer (S-1) was 4,000.

[Example 3-1] 1. Preparation of liquid crystal alignment agent In a solution containing the polymer (A-1) obtained in Example 2-1 as a polymer component, NMP and butyl cellosolve (BC) were added , Fully stirred to form a solution with a solvent composition of NMP:BC=70:30 (weight ratio) and a solid content concentration of 3.0% by weight. The solution was filtered using a filter with a pore size of 0.45 μm, thereby preparing a liquid crystal alignment agent.

2. Manufacturing of optical FFS type liquid crystal display element The FFS type liquid crystal display element 10 shown in FIG. 1 is produced. First, the glass substrate 11a having the following electrode pairs on one side and the opposing glass substrate 11b not provided with electrodes are used as a pair. The glass substrate 11a has a transparent electrode surface and the opposing glass substrate 11b side is used. The rotator separately coats the liquid crystal alignment agent prepared in 1. to form a coating film, and the electrode pair is formed with a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and patterned in this order是的齿状顶顶13。 The comb-shaped top electrode 13. A schematic plan view of the top electrode 13 used is shown in FIGS. 2(a) and 2(b), where E represents an electrode and F represents a pixel edge portion. In addition, FIG. 2( a) is a plan view of the top electrode 13, and FIG. 2( b) is an enlarged view of the portion C1 surrounded by the dotted line in FIG. 2( a ). In this embodiment, the line width d1 of the electrodes is set to 4 μm, and the distance d2 between the electrodes is set to 6 μm. In addition, the top electrode 13 is a four-system drive electrode using the electrode A, the electrode B, the electrode C, and the electrode D (FIG. 3 ). In addition, the bottom electrode 15 functions as a common electrode that functions for all of the four-system drive electrodes, and the areas of the four-system drive electrodes each become a pixel area. After forming the coating film with a spinner, the coating film was prebaked for 1 minute under a hot plate at 80°C. Then, on each surface of the coating film, Hg-Xe lamp and Glan-Taylor prism were used to irradiate polarized ultraviolet light of 5,000 J/m ² to obtain a pair of substrates having a liquid crystal alignment film. At this time, the irradiation direction of the polarized ultraviolet rays is set from the normal direction of the substrate, and the polarizing plane direction is set so that the direction of the line segment projected on the substrate by the polarized surface of the polarized ultraviolet rays becomes the direction of the bidirectional arrow in FIG. 2(b). Perform light irradiation treatment. After light irradiation, it was heated (post-baked) at 230° C. for 1 hour in an oven in which nitrogen was replaced in the chamber, to form a coating film having an average film thickness of 0.1 μm.

Then, on one of the substrates, the outer periphery of the surface of the substrate with the liquid crystal alignment film was coated with an epoxy resin adhesive containing an alumina ball with a diameter of 3.5 μm by screen printing, and a The liquid crystal alignment films of the substrate faced each other, and were pressure-bonded so as to parallelize the direction in which the polarized surface of the polarized ultraviolet light was projected onto the substrate, and the adhesive was thermally cured at 150°C for 1 hour. Then, the liquid crystal "MLC-7028" manufactured by Merck was filled into the substrate gap from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated to 150°C and then slowly cooled to room temperature. Then, the FFS-type liquid crystal display element was manufactured by bonding polarizing plates on both outer sides of the substrate. At this time, one of the polarizing plates is attached in such a way that its polarization direction becomes parallel to the projection direction of the polarized ultraviolet of the liquid crystal alignment film on the substrate surface, and the other is based on the polarization direction of the polarizing plate just now The polarized light direction is perpendicular to the attachment. In addition, by changing the ultraviolet irradiation amount before post-baking within the range of 100 J/m ² to 10,000 J/m ² to carry out the series of operations described above, three or more liquid crystal displays with different ultraviolet irradiation amounts are manufactured element.

3. Evaluation of liquid crystal display element The following (1) evaluation was performed using the liquid crystal display element manufactured in 2. above. In addition, except that the polarizing plate was not bonded, the same operation as in the above 2. was performed to thereby manufacture a liquid crystal display element (liquid crystal cell to which the polarizing plate was not bonded), and the following evaluation (2) was performed. In addition, regarding the evaluation result, an optimal result was selected from three or more liquid crystal display elements having different ultraviolet irradiation amounts, and provided to the evaluation of the liquid crystal display element.

(1) Evaluation of AC afterimage characteristics The FFS-type liquid crystal display element manufactured in 2. above was placed in an environment of 25°C and 1 atmosphere. The bottom electrode was set as the common electrode of all the driving electrodes of the four systems, and the potential of the bottom electrode was set to 0 V potential (ground potential). The electrode B and the electrode D were short-circuited to a common electrode to be in a 0 V application state, and a combined voltage including an AC voltage of 5 V was applied to the electrode A and the electrode C for 100 hours. Immediately after 100 hours, a voltage of 1.5 V AC was applied to all of electrodes A to D. Next, from the time when the application of a voltage of 1.5 V AC to all of the electrodes A to D is started, the driving stress application area (the pixel area of the electrode A and the electrode C) and the driving stress unapplied area can no longer be confirmed visually. The time until the difference in brightness of the (pixel area of electrode B and electrode D) is taken as the afterimage erasing time Ts. In addition, the shorter the time, the more difficult it is to produce afterimages. A case where the afterimage erasing time Ts is less than 30 seconds is evaluated as "good (○)", a case of 30 seconds or more and less than 120 seconds is evaluated as "OK (△)", and a case of 120 seconds or more is evaluated as "bad ( ×)”. As a result, the liquid crystal display element of this example was evaluated as having “afterimage characteristics” of “good”.

(2) Evaluation of contrast after driving stress After driving the liquid crystal display element manufactured in 2. above at an AC voltage of 10 V for 30 hours, a device in which a polarizer and an analyzer are arranged between a light source and a light amount detector is used Measure the minimum relative transmittance (%) expressed by the following mathematical formula (1). Minimum relative transmittance (%) = (β-B ⁰ )/(B ¹⁰⁰ -B ⁰ )×100… (1) (In the formula (1), B ⁰ is the blank sample under the crossed Nicols The amount of light transmission; B ¹⁰⁰ is the amount of light transmission under parallel Nicols in the blank sample; β is the liquid crystal display element sandwiched between the polarizer and the analyzer under crossed Nicols to become the smallest Transmittance) The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. The smaller the black level in the dark state, the better the contrast; the minimum relative transmittance of less than 0.5% is regarded as "good (○)" , Those with 0.5% or more and less than 1.0% are regarded as "possible (△)", and those with 1.0% or more are regarded as "defective (×)". As a result, the contrast evaluation of the liquid crystal display element was judged to be "good".

[Example 3-2 to Example 3-10 and Comparative Example 1] The solvent ratio was the same as in Example 3-1 except that the type of polymer used was changed as shown in Table 2 below. The liquid crystal alignment agent is prepared separately by the solid content concentration. In addition, using each liquid crystal alignment agent, a liquid crystal display element was manufactured in the same manner as in Example 3-1, and various evaluations were performed using the obtained liquid crystal display element. The results are shown in Table 2 below.

[Table 2]

In the liquid crystal display element manufactured using the liquid crystal aligning agent containing a compound (X), the evaluation of AC afterimage characteristics and contrast characteristics was "good" or "possible" in any Example. (Example 3-1 to Example 3-10). Especially in Examples 3-1 to 3-7 and Examples 3-9 to 3-10, which have a partial structure represented by the above formula (1) in the main chain of the polymer, and Good results were obtained in comparison with Examples 3-8 in which the side chain of the polysiloxane skeleton had this partial structure. In addition, it can be seen that by using a diamine having a polycyclic structure such as a biphenyl structure, the effect of improving the AC afterimage characteristics is improved. In contrast, in the liquid crystal alignment agent of the comparative example that does not include the compound (X), the AC afterimage characteristics and contrast characteristics are worse than those of the liquid crystal alignment agent of the example.

10‧‧‧FFS type liquid crystal display element 11a‧‧‧glass substrate 11b‧‧‧‧ facing glass substrate 13‧‧‧top electrode 14‧‧‧insulation layer 15‧‧‧ bottom electrode d1‧‧‧line width of electrode d2 ‧‧‧Distance between electrodes C1‧‧‧Parts A, B, C, D, E surrounded by dotted lines

FIG. 1 is a schematic configuration diagram of a fringe field switching (FFS) type liquid crystal display element. 2(a) and 2(b) are schematic plan views of top electrodes for manufacturing liquid crystal display elements by optical alignment processing. FIG. 2(a) is a top view of the top electrode, and FIG. 2(b) is a partially enlarged view of the top electrode. FIG. 3 is a diagram showing four-system drive electrodes.

10: FFS type liquid crystal display element

11a: glass substrate

11b: Opposite glass substrate

13: Top electrode

14: Insulation

15: bottom electrode

Claims (14)

A liquid crystal alignment agent containing a compound (X) having a partial structure represented by the following formula (1) in the main chain of a polymer,

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; wherein at least one of R ¹ and R ² is a halogen atom, Cyano group or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein, R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, R ⁴ can also be bonded to other groups together with the nitrogen atom Forming a ring structure); R ³ may also be bonded to other groups to form at least a part of the ring; n is an integer of 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different; "*" indicates a combination key. The liquid crystal alignment agent as described in item 1 of the patent application scope, which comprises at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane (A) as the compound (X). The liquid crystal alignment agent according to item 2 of the patent application scope, wherein the polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide And has a partial structure derived from a specific diamine consisting of a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2) At least one of the groups, H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ⁷ -NH ₂ (2-1) Formula (2-1), A ¹ is the following formula (1-1) The group represented by or the group represented by the following formula (1-2), A ² is a single bond, the group represented by the following formula (1-1) or the group represented by the following formula (1-2) Group; when A ¹ is a group represented by the following formula (1-1), R ⁵ is a divalent organic group, and A ¹ is a group represented by the following formula (1-2) In the case of R ⁵ is a single bond or a divalent organic group; in the case where A ² is a group represented by the following formula (1-1), R ⁷ is a divalent organic group and in A ² is the following In the case of a group or a single bond represented by formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein, the following formula (1-1) and formula ( The "*1" in 1-2) is bonded to R ⁶ ; R ⁸ -A ¹ -R ⁹ -A ² -R ¹⁰ (2-2) In formula (2-2), A ¹ and A ² are The formula (2-1) has the same meaning; in the case where A ¹ is a group represented by the following formula (1-1), R ⁸ is a monovalent organic group, and in A ¹ is the following formula (1- 2) In the case of the group represented, R ⁸ is a hydrogen atom or a monovalent organic group; where R ⁸ is a hydrogen atom, A ¹ has a diaminophenyl group, and R ⁸ is a monovalent organic group In the case of a group, R ⁸ has a diaminophenyl group; when A ² is a group represented by the following formula (1-1), R ¹⁰ is a monovalent organic group, and in A ² is the following formula In the case of the group or single bond represented by (1-2), R ¹⁰ is a hydrogen atom or a monovalent organic group; R ⁹ is a divalent organic group; the following formula (1-1) and formula (1-2 ) "*1" is bonded to R ⁹ ;

In formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the above formula (1); "*1" represents a bond. The liquid crystal alignment agent as described in Item 3 of the patent application range, wherein the specific diamine has a partial structure represented by the following formula (4) in the molecule,

In formula (4), Ar ¹ and Ar ² are independently substituted or unsubstituted phenylene, or substituted or unsubstituted cyclohexyl, X ² is a single bond, -COO- or -CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group); wherein, Ar ¹ can also constitute the benzene ring in the formula (1); t is 1 or 2; when t=2, Ar ² and X ² are respectively Have the definition independently; "*" indicates a bond. The liquid crystal alignment agent according to item 2 of the patent application scope, wherein the polymer (A) is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide It has a partial structure derived from a specific acid dianhydride that is at least one selected from the group consisting of compounds represented by the following formula (5-2),

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 same as the above formula (1) meaning. The liquid crystal alignment agent according to item 2 of the patent application range, wherein the polymer (A) contains a partial structure formed by the reaction of a polyorganosiloxane having an epoxy group and a carboxylic acid, and the carboxyl group The acid includes a compound represented by the following formula (3),

In formula (3), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1-1 ) Or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group, When A ¹ is a group represented by the following formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the following formula (1- 1) In the group represented by R ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are independently 0 or 1; wherein, there is a carboxyl group in formula (3); "*1" in the following formula (1-1) and formula (1-2) is bonded to R ¹² ;

In formula (1-1) and formula (1-2), R ¹ , R ² , R ³ , X ¹ and n have the same meaning as the above formula (1); "*1" represents a bond. The liquid crystal alignment agent according to item 6 of the patent application scope, wherein the compound represented by the formula (3) has a partial structure represented by the following formula (4) in the molecule,

In formula (4), Ar ¹ and Ar ² are independently substituted or unsubstituted phenylene, or substituted or unsubstituted cyclohexyl, X ² is a single bond, -COO- or -CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group); wherein, Ar ¹ can also constitute the benzene ring in the formula (1); t is 1 or 2; when t=2, Ar ² and X ² are respectively Have the definition independently; "*" indicates a bond. The liquid crystal aligning agent according to any one of items 1 to 7 of the patent application range, wherein the R ² is an alkyl group having 1 to 10 carbon atoms. A method for manufacturing a liquid crystal alignment film, comprising: the step of applying a liquid crystal alignment agent as described in any one of patent application items 1 to 8 to a substrate to form a coating film; and coating the coating The film is irradiated with light. A liquid crystal alignment film is formed using the liquid crystal alignment agent as described in any one of claims 1 to 8. A liquid crystal display element including the liquid crystal alignment film as described in item 10 of the patent application. A polymer, which is a polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, and polyorganosiloxane, and has a main chain of the polymer The partial structure represented by the 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 monovalent organic group; wherein at least one of R ¹ and R ² is halogen Atom, cyano group or monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein, R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, R ⁴ may also be bonded to other groups to form a nitrogen atom Together form a ring structure); R ³ may also be bonded to other groups to form at least part of the ring; n is an integer from 0 to 4; when n is 2 or more, multiple R ³ may be the same or Different; "*" indicates a bond. A diamine compound represented by the following formula (2-1), H ₂ NR ⁵ -A ¹ -R ⁶ -A ² -R ⁷ -NH ₂ (2-1) in formula (2-1) , A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, a group represented by the following formula (1-1) Group or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ⁵ is a divalent organic group, and A ¹ is below In the case of the group represented by the formula (1-2), R ⁵ is a single bond or a divalent organic group; in the case where A ² is a group represented by the following formula (1-1), R ⁷ Is a divalent organic group, and when A ² is a group or a single bond represented by the following formula (1-2), R ⁷ is a single bond or a divalent organic group; R ⁶ is a divalent organic group; wherein , “*1” in the following formula (1-1) and formula (1-2) is bonded to R ⁶ ;

In formula (1-1) and formula (1-2), R ¹ and R ² are independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent; wherein, R ¹ and R At least one of ² is a halogen atom, a cyano group or a monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ may also be bonded to Other groups form a ring structure together with the nitrogen atom); n is an integer from 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different; "*1" represents a bonding bond. A carboxylic acid, which is represented by the following formula (3) and has a partial structure represented by the following formula (4) in the molecule,

In formula (3), A ¹ is a group represented by the following formula (1-1) or a group represented by the following formula (1-2), A ² is a single bond, and the following formula (1-1 ) Or a group represented by the following formula (1-2); when A ¹ is a group represented by the following formula (1-1), R ¹¹ is a monovalent organic group, When A ¹ is a group represented by the following formula (1-2), R ¹¹ is a hydrogen atom or a monovalent organic group; R ¹² is a divalent organic group; and A ² is the following formula (1- 1) In the group represented by R ¹³ is a divalent organic group, and when A ² is a group represented by the following formula (1-2), R ¹³ is a single bond or a divalent organic group S and r are independently 0 or 1; wherein, there is a carboxyl group in formula (3); "*1" in the following formula (1-1) and formula (1-2) is bonded to R ¹² ;

In formula (1-1) and formula (1-2), R ¹ and R ² are independently a hydrogen atom, a halogen atom, a cyano group or a monovalent organic group, and R ³ is a substituent; wherein, R ¹ and R At least one of ² is a halogen atom, a cyano group or a monovalent organic group; X ¹ is an oxygen atom or -NR ^4- (wherein R ⁴ is a hydrogen atom, a hydroxyl group or a monovalent organic group, and R ⁴ may also be bonded to Other groups form a ring structure together with the nitrogen atom); n is an integer from 0 to 4; when n is 2 or more, a plurality of R ³ may be the same or different; "*1" represents a bonding bond,

In formula (4), Ar ¹ and Ar ² are independently substituted or unsubstituted phenylene, or substituted or unsubstituted cyclohexyl, X ² is a single bond, -COO- or -CONR ^20- (R ²⁰ is a hydrogen atom or a monovalent organic group); wherein, Ar ¹ may also constitute the benzene ring in the formula (1-1) or the formula (1-2); t is 1 or 2; When t=2, Ar ² and X ² each independently have the above definition; "*" indicates a bonding bond.

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