JP2015166844A - Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element, retardation film, method for manufacturing retardation film, polymer, and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent for obtaining a liquid crystal display element showing a good balance of various characteristics.SOLUTION: The liquid crystal aligning agent comprises a polymer (P) obtained by a reaction using at least one compound (C') selected from a group consisting of: a compound (C) having the following structure (a) and the following structure (c); and a compound (C1) having the structure (a) and the following structure (b1), in which a reactive group participating the polymerization is not bonded to an aromatic ring group in the structure (a). The structures are: (a) an aromatic amine structure having two or three aromatic ring groups bonded to the same nitrogen atom; (b) a linear structure such as a divalent linear hydrocarbon group having 6 or more carbon atoms; and (b1) a structure of a divalent linear hydrocarbon group having 1 to 5 carbon atoms, -O-, -S-, or the like.

Description

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

  Conventionally, as liquid crystal display elements, various drive systems having different electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, TN type, STN type, VA type, in-plane switching type ( Various liquid crystal display elements such as IPS type and FFS type are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid or polyimide is generally used from the viewpoints of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal.

  In recent years, with the increase in definition of liquid crystal display elements, there has been an increasing demand for reduction of afterimage phenomenon and suppression of contrast reduction, and various liquid crystal aligning agents have been proposed to satisfy such demand (for example, Patent Document 1). To 6). In those described in Patent Documents 1 to 6, by introducing a diphenylamine unit into a liquid crystal aligning agent, reduction of stored charge in a liquid crystal display element, suppression of a decrease in contrast, and the like are achieved.

  Specifically, Patent Document 1 discloses that a liquid crystal aligning agent contains polyamic acid or polyimide obtained by reacting a diamine containing 4,4′-diaminodiphenylamine with tetracarboxylic dianhydride. ing. Patent Document 2 discloses a polyimide obtained by reacting a diamine containing oligoaniline such as (4-aminophenyl) (4-((4-aminophenyl) amino) phenylamine) with tetracarboxylic dianhydride. Further, Patent Document 3 discloses that a compound having two or more diphenylamine units is added separately from a polymer such as polyamic acid or polyimide, or two or more compounds are included in Patent Document 3. It is disclosed that a polyamic acid obtained by reacting a diamine having a diphenylamine unit with tetracarboxylic dianhydride is contained in a liquid crystal aligning agent.

  Patent Document 4 discloses a diamine containing 1,3-bis-4- (N, N- (4-aminophenyl) aminophenyl) propane as a compound having two diphenylamine structures in the molecule and tetracarboxylic dianhydride. It is disclosed that a polyamic acid obtained by reacting a product with a liquid crystal is contained in a liquid crystal aligning agent. Patent Document 5 and Patent Document 6 disclose polyamics obtained by reacting a diamine containing N, N′-bis (4-aminophenyl) -N, N′-dimethylethylenediamine with tetracarboxylic dianhydride. It is disclosed that an acid is contained in a liquid crystal aligning agent.

  In addition, various optical materials are used for liquid crystal display elements. Above all, retardation films eliminate the object of viewing color dependency and the viewing angle dependency that the display color and contrast ratio change depending on the visual direction. It is used for the purpose. As such retardation films, those having a liquid crystal alignment film formed on the surface of a substrate such as a TAC film and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film are known. ing. In recent years, a liquid crystal alignment film in a retardation film has been produced by using a photo-alignment method that imparts liquid crystal alignment ability by irradiating a radiation-sensitive organic thin film formed on the substrate surface with polarized or non-polarized radiation. Various liquid crystal aligning agents for retardation films for producing a liquid crystal aligning film by such a method have been proposed (for example, see Patent Document 7).

Japanese Patent No. 4052307 JP 2000-44683 A Japanese Patent No. 4924832 JP 2011-207786 A JP 2012-155311 A Japanese Patent No. 5130907 JP 2012-37868 A

  However, when the liquid crystal aligning agent of Patent Document 1 is used, DC residual relaxation is insufficient in the liquid crystal display element, and the time until the afterimage disappears tends to be long. In addition, in the conventional liquid crystal aligning agent including a polymer using a diamine having a plurality of diphenylamine units as a monomer, although the DC residual relaxation performance is improved, the aromatic concentration increases, so the transmittance of the liquid crystal alignment film is increased. There were disadvantages such as low. In addition, AC afterimage performance, which is one of the characteristics affecting the contrast of the liquid crystal display element, is not sufficient, and various characteristics are not provided in a well-balanced manner. Further, with the recent diversification of liquid crystal display elements, the liquid crystal display elements are expected to be used in more severe conditions, and liquid crystal display elements that are excellent in heat resistance are required.

  A liquid crystal display is manufactured by disposing a pair of substrates on which a liquid crystal alignment film is formed facing each other and disposing a liquid crystal between the pair of facing substrates. In that case, a pair of board | substrates are bonded together using sealing agents, such as an epoxy resin. Here, in touch panel type display panels represented by smartphones and tablet PCs, attempts have been made to reduce the frame size in order to make the movable area of the touch panel wider and to reduce the size of the liquid crystal panel (element). Yes. With such a narrowed frame of the liquid crystal panel, display unevenness may be visually recognized around the sealant, which is not fully satisfactory in terms of display quality. In order to increase the definition and life of the liquid crystal display, a liquid crystal display element is required in which display unevenness around such a sealant is hardly visible (high bezel unevenness resistance).

  The present invention has been made in view of the above-mentioned problems, has good permeability of the liquid crystal alignment film, has little display unevenness around the sealant, and has various properties such as afterimage characteristics, high contrast, and heat resistance in a well-balanced manner. One object is to provide a liquid crystal aligning agent for obtaining a liquid crystal display element.

  The present inventor has intensively studied to achieve the above-described problems of the prior art, and that the above problems can be solved by including a polymer having a specific structure as a polymer component in the liquid crystal aligning agent. The headline and the present invention were completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, retardation film, retardation film production method, polymer and compound.

In one aspect, the present invention includes a compound (C) having the following structure (a) and the following structure (b), and the following structure (a) and the following structure (b1). A polymer (P) obtained by using, in the reaction, at least one compound (C ′) selected from the group consisting of a compound (C1) in which a reactive group involved in polymerization is not bonded to an aromatic ring group therein The liquid crystal aligning agent containing is provided.
(A) An aromatic amine structure in which two or three aromatic ring groups are bonded to the same nitrogen atom.
(B) a divalent chain hydrocarbon group having 6 or more carbon atoms and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO. A chain structure selected from the group consisting of a divalent group substituted with —, —COO—, —COS—, or —Si (CH ₃ ) ₂ — (R represents a hydrogen atom or a monovalent organic group).
(B1) a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is represented by —O—, —S—, —CO—, —NR ³ —, — ^{NR 3 CO -, - COO -} , - COS- or -Si _{(CH 3) 2} - a divalent group obtained by replacing, -O -, - S -, - CO -, - NR 3 CO- (R 3 is A hydrogen atom or a monovalent organic group), a structure selected from the group consisting of —COO—, —COS—, and —Si (CH ₃ ) ₂ —.

  In another aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent. Moreover, a liquid crystal display element provided with the said liquid crystal aligning film and a phase difference film provided with the said liquid crystal aligning film are provided. Furthermore, in another aspect, the step of coating the liquid crystal aligning agent on a substrate to form a coating film, the step of irradiating the coating film with light, and the polymerization on the coating film after the light irradiation And a step of applying and curing a liquid crystal.

  In another aspect, the present invention provides a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). I will provide a. Further, at least one compound selected from the group consisting of a tetracarboxylic dianhydride, a tetracarboxylic acid diester compound and a tetracarboxylic acid diester dihalide, a compound represented by the following formula (1-1), and the following formula (1 -2) and a diamine containing at least one selected from the group consisting of the compound represented by the following formula (1-3), and a polyamic acid, a polyamic acid ester, and a polyimide obtained by using in the reaction A polymer selected from the group consisting of:

（式（１−１）中、Ａ^１及びＡ^３は、それぞれ独立に水素原子又は１価の有機基であり、Ａ^２及びＡ^４は、それぞれ独立に単結合又は２価の有機基である。Ｂ^１及びＢ^２は、それぞれ独立に単結合又は２価の有機基である。ただし、Ｂ^１が単結合である場合、Ａ^１及びＡ^２の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^１が２価の有機基である場合、Ａ^１、Ａ^２及びＢ^１のうち少なくとも２個は芳香環で窒素原子に結合している。Ｂ^２が単結合である場合、Ａ^３及びＡ^４の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^２が２価の有機基である場合、Ａ^３、Ａ^４及びＢ^２のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^１１は、炭素数６以上の２価の鎖状炭化水素基における少なくとも１個のメチレン基を−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＯ−、−ＣＯＳ−又は−Ｓｉ（ＣＨ_３）_２−（Ｒは水素原子又は１価の有機基である。）で置き換えてなる基を含む２価の基である。ただし、Ｌ^１１が炭素数１〜５のアルカンジイル基を有する場合、Ａ^１及びＡ^３の少なくともいずれかが水素原子であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

(In Formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. And when B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are bonded to the nitrogen atom through an aromatic ring, and when B ² is a single bond, When at least one of A ³ and A ⁴ is an aromatic ring bonded to a nitrogen atom, and B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings. .L ¹¹ attached to the nitrogen atom, at least one of the divalent chain hydrocarbon group having 6 or more carbon atoms Methylene -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group In the case where L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom. Or at least one of B ¹ and B ² is a divalent organic group.)

（式（１−２）中、Ｌ^１２は、炭素数６以上の２価の鎖状炭化水素基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は上記式（１−１）と同義である。ただし、Ｌ^１２が炭素数６〜１０のアルカンジイル基である場合、Ａ^１及びＡ^３の少なくともいずれかが１価の有機基であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² has the same meaning as the above formula (1-1), provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group. Or at least one of B ¹ and B ² is a divalent organic group.)

（式（１−３）中、Ａ^７は水素原子又は１価の有機基であり、Ａ^８及びＡ^９は、それぞれ独立に単結合又は２価の有機基である。ただし、Ａ^７、Ａ^８及びＡ^９のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^４は上記構造（ｂ１）であり、Ｌ^５は単結合又は２価の有機基である。）

(In Formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group. However, A ⁷ , A 9 ^At least two of ⁸ and A ⁹ are aromatic rings bonded to a nitrogen atom, L ⁴ is the structure (b1), and L ⁵ is a single bond or a divalent organic group.

  According to the liquid crystal aligning agent containing the polymer (P) as the polymer component, there is little display unevenness around the sealant, and a liquid crystal display element having various properties such as low afterimage, high contrast and heat resistance in a well-balanced manner. Can be obtained. In addition, a liquid crystal alignment film having good permeability can be obtained. Furthermore, the solubility with respect to the solvent of the said polymer (P) is favorable, and the storage stability of a liquid crystal aligning agent is also favorable.

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

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

<Polymer (P)>
The liquid crystal aligning agent of the present invention has, as a polymer component, a compound (C) having the structure (a) and the structure (b), and the structure (a) and the structure (b1). It is obtained by using at least one compound (C ′) selected from the group consisting of the compound (C1) in which the reactive group involved in polymerization is not bonded to the aromatic ring group in the structure (a), and the group consisting of A polymer (P) is included. Hereinafter, the structure (a) is also referred to as “aromatic amine structure (a)”, and the structure (b) is also referred to as “chain structure (b)”.

・ Compound (C)
(Aromatic amine structure (a))
The aromatic amine structure (a) of the compound (C) is a structure in which two or three aromatic ring groups are bonded to the same nitrogen atom. The aromatic ring group may be a group obtained by removing a hydrogen atom from the ring portion of the aromatic ring. Specifically, for example, an aromatic hydrocarbon ring such as a benzene ring, a toluene ring, a naphthalene ring, an anthracene ring; And a group obtained by removing a hydrogen atom from a ring portion in an aromatic ring such as a ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a triazine ring. Among these, a benzene ring is preferable from the viewpoint of good affinity with liquid crystal.
The number of aromatic amine structures (a) in the molecule of the compound (C) is 1 or 2 or more, and preferably 2 or more from the viewpoint of enhancing the residual DC relaxation performance. Further, from the viewpoint of the transmittance of the liquid crystal alignment film and the solubility of the polymer, the number is more preferably 2 to 4, and further preferably 2 or 3.

(Chain structure (b))
The chain structure (b) of the compound (C) is a divalent chain hydrocarbon group having 6 or more carbon atoms, or at least one of the divalent chain hydrocarbon groups having 6 or more carbon atoms. A methylene group of —O—, —S—, —CO—, —NR—, —NRCO—, —COO—, —COS— or —Si (CH ₃ ) ₂ — (where R is a hydrogen atom or a monovalent An organic group).

The divalent chain hydrocarbon group in the chain structure (b) means a hydrocarbon group composed only of a linear or branched chain structure without including a cyclic structure in the main chain. The divalent chain hydrocarbon group in the chain structure (b) may have 6 or more carbon atoms, and specific examples thereof include, for example, hexanezyl group, heptanediyl group, octanediyl group, nonanediyl group, decandiyl group, and dodecanedyl. A saturated hydrocarbon group having 6 to 30 carbon atoms such as a group, a tetradecandyl group, and an icosanediyl group; at least one carbon-carbon bond of the saturated hydrocarbon group having 6 to 30 carbon atoms is a double bond or a triple bond Examples thereof include unsaturated hydrocarbon groups having 6 to 30 carbon atoms. These may be linear or branched, but are preferably linear.
When the chain structure (b) is a divalent chain hydrocarbon group having 6 or more carbon atoms, the chain hydrocarbon group preferably has 6 to 30 carbon atoms, and preferably 6 to 20 carbon atoms. Is more preferable.

In the chain structure (b), at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms is represented by —O—, —S—, —CO—, —NR—, —NRCO—. , —COO—, —COS—, or —Si (CH ₃ ) ₂ — (wherein R is a hydrogen atom or a monovalent organic group), the number of substitution may be one or more. However, it can be set as appropriate according to the number of carbon atoms. The number of carbon atoms before replacing the methylene group with the functional group is preferably 6-30, and more preferably 7-20.
Examples of the monovalent organic group represented by R include a chain hydrocarbon group having 1 to 5 carbon atoms such as an alkyl group and an alkenyl group, and a carbon-carbon bond of a chain hydrocarbon group having 1 to 5 carbon atoms. And groups having —O—, —CO—, and the like, and protecting groups for amino groups. Specific examples of the protecting group for amino group include, for example, t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1-dimethyl-2-cyanoethyloxycarbonyl group, A 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a 2- (trimethylsilyl) ethoxycarbonyl group and the like can be mentioned, and a t-butoxycarbonyl group is preferable.

The number of the chain structures (b) in the molecule of the compound (C) may be one or two or more. Preferably it is 1-5, More preferably, it is 1-3. The compound (C) has an aromatic amine structure (a) and a chain structure (b) as the main chain of the compound (C), specifically, the longest carbon chain (having a functional group among the compounds). Is preferably in the longest carbon chain containing it.
The molecular weight of the compound (C) is preferably 1,200 or less from the viewpoint of reducing the surface irregularity of the liquid crystal alignment film. Therefore, it is preferable to set the number of the aromatic amine structure (a) and the chain length of the chain structure (b) so that the molecular weight of the compound (C) falls within the above range. More preferably, the molecular weight is 1,000 or less, and still more preferably 800 or less.

Compound (C1)
The compound (C1) has the aromatic amine structure (a) and the structure (b1). However, in the compound (C1), a reactive group involved in polymerization is not bonded to the aromatic ring group in the aromatic amine structure (a). The reactive group differs depending on the main skeleton of the polymer (P). For example, when the main skeleton of the polymer (P) is polyamic acid or polyimide, the reactive group is an acid anhydride group or a primary amino group. In the case of polyester, the reactive group is a hydroxyl group or a carboxyl group, and in the case of polyamide, the reactive group is a carboxyl group or a primary amino group.
The description of the compound (C) can be applied to the description of the aromatic ring of the aromatic amine structure (a) that the compound (C1) has. The number of aromatic amine structures (a) in one molecule of compound (C1) is preferably one.

The structure (b1) of the compound (C1) has a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is represented by —O—, —S—, — A divalent group substituted by CO—, —NR ³ —, —NR ³ CO—, —COO—, —COS— or —Si (CH ₃ ) ₂ —, —O—, —S—, —CO—, It is a structure selected from the group consisting of —NR ³ CO—, —COO—, —COS—, and —Si (CH ₃ ) ₂ — (R ³ is a hydrogen atom or a monovalent organic group). In addition, the compound (C1) may have only 1 type in these in a molecule | numerator, and may have 2 or more types in a molecule | numerator.
Specific examples of the divalent chain hydrocarbon group having 1 to 5 carbon atoms in the structure (b1) include, for example, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a vinylene group, a propenediyl group, and a butenediyl group. Group, pentenediyl group and the like. These may be linear or branched, but are preferably linear.

In the structure (b1), at least one methylene group in the divalent chain hydrocarbon group having 1 to 5 carbon atoms is represented by —O—, —S—, —CO—, —NR ³ —, —NR ³ CO In the case of a divalent group substituted with —, —COO—, —COS— or —Si (CH ₃ ) ₂ —, the number of substitutions may be one or more, and is appropriately set according to the number of carbon atoms. be able to. The description of R of the compound (C) can be applied to the description of the monovalent organic group of R ³ .
The number of the structure (b1) in the molecule of the compound (C1) may be one or two or more. The number is preferably 2 or more, and particularly preferably 2. The description of the compound (C) can be applied to the molecular weight of the compound (C1).

Examples of the main skeleton of the polymer (P) include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, and poly (styrene-phenylmaleimide) derivative. And skeletons composed of poly (meth) acrylate derivatives and the like. As the polymer (P), one or more polymers selected from these can be appropriately selected according to the use of the liquid crystal aligning agent and the like. In addition, (meth) acrylate means containing an acrylate and a methacrylate. The polymer (P) may have the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in either the main chain or the side chain of the polymer. It is preferable to have it in the main chain of the coalescence.
The main skeleton of the polymer (P) is preferably at least one selected from the group consisting of a polyamic acid, a polyimide and a polyamic acid ester. The aromatic amine structure (a) and the chain structure (b) are preferred. Or it is more preferable that it is at least 1 type chosen from the group which consists of a polyamic acid which has a structure (b1) in a principal chain, a polyimide, and a polyamic acid ester. The polymer (P) is preferably a polymer obtained by using the compound (C ′) as a monomer.

  Here, the “main chain” of the polymer in the present invention refers to a “trunk” portion composed of the longest chain of atoms in the polymer. It is allowed that the “trunk” portion includes a ring structure. Therefore, “having the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in the main chain of the polymer” means that these structures constitute a part of the main chain. Say. However, in the polymer (P), the aromatic amine structure (a), the chain structure (b), and the structure (b1) are branched from a portion other than the main chain, such as a side chain (the “trunk” of the polymer). It does not exclude the presence of (part).

[Polyamic acid (P)]
When the polymer (P) is a polyamic acid (hereinafter also referred to as “polyamic acid (P)”), it can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid Product, 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-di Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2 ] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1 , 3-Propylene glycol bis (am Hydrotrimellitate) etc .;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, as tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid, these 1 type can be used individually or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride in that the liquid crystal orientation and the solubility in a solvent can be improved. 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2, -C] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -C] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5 -(2,5-dioxote Lahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8- Selected from the group consisting of tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic dianhydride, 1,3-propylene glycol bis (anhydrotrimellitate) and pyromellitic dianhydride It preferably contains at least one compound (hereinafter also referred to as “specific tetracarboxylic dianhydride”). The amount of the specific tetracarboxylic dianhydride used is preferably 5 mol% or more, preferably 10 mol% or more, based on the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid. More preferably, it is particularly preferably 20 mol% or more.

(Diamine)
The diamine used for the synthesis of the polyamic acid (P) is a diamine having the aromatic amine structure (a) and the chain structure (b) (hereinafter also referred to as “diamine (C)”), and It is preferable to include at least one compound (C ′) selected from the group consisting of the compound (C1) having the structure (a1) and the structure (b1) and the group (C1).

（式（１）中、Ａ^１及びＡ^３は、それぞれ独立に水素原子又は１価の有機基であり、Ａ^２及びＡ^４は、それぞれ独立に単結合又は２価の有機基である。Ｂ^１及びＢ^２は、それぞれ独立に単結合又は２価の有機基である。ただし、Ｂ^１が単結合である場合、Ａ^１及びＡ^２の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^１が２価の有機基である場合、Ａ^１、Ａ^２及びＢ^１のうち少なくとも２個は芳香環で窒素原子に結合している。Ｂ^２が単結合である場合、Ａ^３及びＡ^４の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^２が２価の有機基である場合、Ａ^３、Ａ^４及びＢ^２のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^１は、前記構造（ｂ）を含む２価の基である。） ・ Diamine (C)
The diamine (C) preferably has a structure capable of introducing the aromatic amine structure (a) and the chain structure (b) into the main chain of the polymer (P). Specifically, It is preferable that it is a compound represented by following formula (1).

(In Formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. In the case where B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings bonded to a nitrogen atom, and when B ² is a single bond, A ³ And A ⁴ is an aromatic ring bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and a nitrogen atom L ¹ is a divalent group containing the structure (b).

In the above formula (1), examples of the monovalent organic group in A ¹ and A ³ include, for example, —O—, —COO— between a carbon-carbon bond in a monovalent hydrocarbon group and a monovalent hydrocarbon group, Examples thereof include monovalent groups in which functional groups such as —CO—, —NHCO—, —S—, and —NH— are introduced, and protecting groups for amino groups. In A ¹ and A ³ , the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, or the like. . Specific examples of the amino-protecting group include the groups exemplified in the description of R in the chain structure (b). A t-butoxycarbonyl group is preferred.

  Examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, in the present specification, the “chain hydrocarbon group” is as described above. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. The “aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

Specific examples of the monovalent hydrocarbon group in A ¹ and A ³ include a chain hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, C1-C30 alkyl groups, such as nonyl group, decyl group, dodecyl group, tetradecyl group, icosanyl group; C2-C30 alkenyl groups, such as ethenyl group, propenyl group, butenyl group; ethynyl group, propynyl group, etc. The alkynyl group having 2 to 30 carbon atoms can be exemplified, and these may be linear or branched. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a benzyl group, and a phenethyl group; Can be mentioned.

Examples of the divalent organic group in A ² , A ⁴ , B ^1, and B ² include, for example, —O—, —COO—, a carbon-carbon bond in a divalent hydrocarbon group, and a divalent hydrocarbon group. And a divalent group in which a functional group such as —CO—, —NHCO—, —S—, and —NH— is introduced. The hydrogen atom bonded to the carbon atom of each group is a halogen atom or a hydroxyl group. Etc. may be substituted. Specific examples of the divalent hydrocarbon group include groups in which one hydrogen atom has been removed from each group exemplified as the monovalent hydrocarbon group. In the compound represented by the formula (1), the structure surrounding the nitrogen atom in the formula (1) corresponds to the aromatic amine structure (a).
At least one of B ¹ and B ² is preferably a single bond, and both B ¹ and B ² are more preferably a single bond.

（式（２）中、Ｌ^２及びＬ^３は、それぞれ独立に上記構造（ｂ）である。Ｑは、下記式（３）又は式（４）で表される２価の基である。ｎは０〜４の整数である。「＊」は結合手を示す。）

（式（３）中、Ａ^５は、水素原子又は１価の有機基である。Ｒ^１及びＲ^２は置換基であり、互いに同じでも異なっていてもよい。「＊」は結合手を示す。）

（式（４）中、Ａ^６は、水素原子又は１価の有機基である。「＊」は結合手を示す。） L ¹ is a divalent group containing the chain structure (b). Preferable specific examples of L ¹ include, for example, a group represented by the following formula (2).

(In formula (2), L ² and L ³ are each independently the structure (b). Q is a divalent group represented by the following formula (3) or formula (4). Is an integer from 0 to 4. “*” represents a bond.)

(In Formula (3), A ⁵ is a hydrogen atom or a monovalent organic group. R ¹ and R ² are substituents, which may be the same or different from each other. “*” Represents a bond. .)

(In formula (4), A ⁶ is a hydrogen atom or a monovalent organic group. “*” Represents a bond.)

（式中、「＊」は結合手を示す。） The formula (3), in (4), the monovalent organic group ^{A 5} and ^{A 6,} can be applied to the description of the monovalent organic group represented by ^{A 1} and ^{A 3.} N in the above formula (2) is preferably 0 or 1.
Specific examples of the group represented by the above formula (2) include groups represented by the following formulas (2-1) to (2-25).

(In the formula, “*” indicates a bond.)

（式（１−１）中、Ｌ^１１は、炭素数６以上の２価の鎖状炭化水素基における少なくとも１個のメチレン基を−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＯ−、−ＣＯＳ−又は−Ｓｉ（ＣＨ_３）_２−（Ｒは水素原子又は１価の有機基である。）で置き換えた基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は、上記式（１）と同義である。ただし、Ｌ^１１が炭素数１〜５のアルカンジイル基を有する場合、Ａ^１及びＡ^３の少なくともいずれかが水素原子であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

（式（１−２）中、Ｌ^１２は、炭素数６以上の２価の鎖状炭化水素基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は、上記式（１）と同義である。） Preferable specific examples of the compound represented by the formula (1) include, for example, a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).

(In Formula (1-1), L ¹¹ represents at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms as —O—, —S—, —CO—, —NR—, A ¹ is a divalent group including a group replaced by —NRCO—, —COO—, —COS— or —Si (CH ₃ ) ₂ — (R is a hydrogen atom or a monovalent organic group). , A ² , A ³ , A ⁴ , B ¹ and B ² have the same meaning as in the above formula (1), provided that when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, A ¹ and A ³ At least one of them is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group.)

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² has the same meaning as the above formula (1).)

L ¹¹ in the above formula (1-1) represents at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms, —O—, —S—, —CO—, —NR—. , —NRCO—, —COO—, —COS—, or —Si (CH ₃ ) ₂ — may have only one group or plural groups. Preferable specific examples of L ¹¹ include a group represented by the above formula (2) (wherein L ² and L ³ represent at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms). -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or -Si _{(CH 3) 2} -. it is in the replaced group).
If L ¹¹ contains an alkanediyl group having 1 to 5 carbon atoms, at least one of ^{A 1} and ^{A 3} is a hydrogen atom, it is preferred that ^{A 1} and ^{A 3} are both hydrogen atoms.

L ¹² in the above formula (1-2) may have only one or more divalent chain hydrocarbon groups having 6 or more carbon atoms. Preferable specific examples of L ¹² include groups represented by the above formula (2) (wherein L ² and L ³ are divalent chain hydrocarbon groups having 6 or more carbon atoms).
In the compound represented by the formula (1-2), when the alkanediyl group of L ¹² has 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, Alternatively, at least one of B ¹ and B ² is preferably a divalent organic group. When A ¹ and A ³ in the formula (1-1) are hydrogen atoms, L ¹² is a divalent group in which L ² and L ^{3 in the} group represented by the formula (2) are 7 or more carbon atoms. What is a chain hydrocarbon group is preferable, and what is a C11 or more bivalent chain hydrocarbon group is more preferable.

（式中、Ｐｈはフェニル基を示す。） Preferable specific examples of the diamine (C) include, for example, compounds represented by the following formulas (DA-1) to (DA-10) and (DA-41). In addition, the said diamine (C) can be used individually by 1 type or in combination of 2 or more types.

(In the formula, Ph represents a phenyl group.)

（式（１−３）中、Ａ^７は水素原子又は１価の有機基であり、Ａ^８及びＡ^９は、それぞれ独立に単結合又は２価の有機基である。ただし、Ａ^７、Ａ^８及びＡ^９のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^４は上記構造（ｂ１）であり、Ｌ^５は単結合又は２価の有機基である。） ・ Diamine (C1)
The diamine (C1) preferably has a structure capable of introducing the aromatic amine structure (a) and the structure (b1) into the main chain of the polymer (P). It is preferable that it is a compound represented by Formula (1-3).

(In Formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group. However, A ⁷ , A 9 ^At least two of ⁸ and A ⁹ are aromatic rings bonded to a nitrogen atom, L ⁴ is the structure (b1), and L ⁵ is a single bond or a divalent organic group.

In the above formula (1-3), as the monovalent organic group of A ⁷ , the description of the monovalent organic groups of A ¹ and A ³ of the above formula (1) can be applied. The description of A ² and A ^{4 in} the above formula (1) can be applied to the divalent organic group of A ⁸ and A ⁹ . Examples of the divalent organic group represented by L ⁵ include a divalent chain hydrocarbon group having 1 to 20 carbon atoms and at least one methylene group in the chain hydrocarbon group represented by —O—, —S—, — A divalent group substituted by CO—, —NR ⁴ —, —NR ⁴ CO—, —COO—, —COS— or —Si (CH ₃ ) ₂ —, —O—, —S—, —CO—, —NR ⁴ CO—, —COO—, —COS—, and —Si (CH ₃ ) ₂ — (R ⁴ is a hydrogen atom or a monovalent organic group). Of these, L ⁵ is preferably the structure (b1).
Preferable specific examples of the diamine (C1) include, for example, compounds represented by the following formulas (DA-22) to (DA-40). In addition, the said diamine (C1) can be used individually by 1 type or in combination of 2 or more types.

  The diamine used in the synthesis of the polyamic acid (P) may be only the diamine (C ′), but other diamines other than the above may be used in combination with the diamine (C ′).

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

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylamine, 1,7- Bis (4-aminophenoxy) heptane, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropyl Bread, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′- Bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, 1,4-bis -(4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4 -Diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5- Aminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate Lanostaneyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) Cyclohexyl-3,5-di Minobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 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, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- ( 2,4-diaminophenyl) piperazine-4-carboxylic acid, 1,3-bis (N- (4-aminophen L) piperidinyl) propane, α-amino-ω-aminophenylalkylene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- ( 4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 4-aminophenyl-4′-aminobenzoate, 4,4 ′-[4,4′- Propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, the following formula (DA-18)

（式（Ｄ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−（＊は式中のベンゼン環に結合する結合手であることを示す。）であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。ただし、ａ及びｂが同時に０になることはない。）
で表される化合物などを；
ジアミノオルガノシロキサンとして、例えば、１，３−ビス（３−アミノプロピル）−テトラメチルジシロキサンなどを；それぞれ挙げることができるほか、特開２０１０−９７１８８号公報に記載のジアミンを用いることができる。 And a compound represented by the following formula (D-1)

(In Formula (D-1), X ^I and X ^II are each independently a single bond, —O—, * —COO— or * —OCO— (* is a bond bonded to the benzene ring in the formula). R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1; b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP 2010-97188 A can be used.

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

なお、上記ポリアミック酸の合成に使用するその他のジアミンとしては、これらの化合物の１種を単独で又は２種以上を適宜選択して使用することができる。 Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

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

  In the diamine used for the synthesis of the polyamic acid (P) of the present invention, the ratio of the diamine (C ′) used is preferably 0.5 mol% or more based on the total amount of the diamine used for the synthesis. If it is less than 0.5 mol%, the effects of the present invention tend not to be sufficiently obtained. More preferably, it is 2 mol% or more, More preferably, it is 5 mol% or more, Especially preferably, it is 10 mol% or more. Moreover, the upper limit of the usage-amount of the said diamine (C ') can be arbitrarily set in the range of 100 mol% or less with respect to the whole quantity of the diamine used for a synthesis | combination. When the improvement effect (for example, printability, voltage holding ratio, liquid crystal orientation, etc.) by addition of other diamines is aimed at, it is preferable that the usage-amount of the said diamine (C ') shall be 95 mol% or less.

When the liquid crystal aligning agent of the present invention is used for production of a TN type, STN type or vertical alignment type liquid crystal display element, at least a part of the polymer (P) contained in the liquid crystal aligning agent is pretilt with respect to the coating film. A polymer having a group capable of imparting an angle development ability (hereinafter also referred to as a “pretilt angle expression group”) may be used. Examples of the pretilt angle-expressing group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, And a group having a ring structure.
In order to obtain the polyamic acid (P) having a pretilt angle-expressing group, it is preferable to carry out polymerization by including a diamine having a pretilt angle-expressing group in the monomer composition from the viewpoint of easy introduction of the pretilt angle-expressing group. . Specifically, it can be synthesized by using a diamine having a pretilt angle developing group as another diamine.
When a diamine having a pretilt angle-expressing group is used in the synthesis of the polyamic acid (P), the amount used is 5 moles relative to the total diamine used in the synthesis in terms of expressing a sufficiently high pretilt angle characteristic. % Or more, and more preferably 10 mol% or more.

  When the liquid crystal aligning ability is imparted to the coating film prepared using the liquid crystal aligning agent of the present invention by a photo-alignment method, at least a part of the polymer (P) contained in the liquid crystal aligning agent is used as a photo-alignment structure. It is good also as a polymer which has. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment part. Specifically, as the photoalignment structure, a group that exhibits photoalignment by photoisomerization, photodimerization, photolysis, or the like can be employed. For example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton. A group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof Examples include a coumarin-containing group containing a derivative as a basic skeleton, a polyimide-containing structure containing polyimide or a derivative thereof as a basic skeleton, and the like.

  For example, when the polyamic acid, polyimide, and polyamic acid ester as the polymer (P) have a photo-alignment structure, it is preferable that the photo-alignment structure has a decomposable photo-alignment part, specifically, bicyclo [ 2.2.2] A polymer having an octene skeleton or a cyclobutane skeleton is preferable. By having such a specific skeleton, the liquid crystal orientation of the coating film can be further improved. For example, a polyamic acid (P) having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton is obtained by dicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid. It can be obtained by reacting a tetracarboxylic dianhydride containing at least one of an anhydride and cyclobutanetetracarboxylic dianhydride with a diamine containing the diamine (C ′).

[Molecular weight regulator]
In synthesizing the polyamic acid (P), a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and diamine as described above. By using such a terminal-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples thereof include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic. Acid anhydrides, n-hexadecyl succinic acid anhydrides; monoamine compounds such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

  The diamine (C) and diamine (C1) can be synthesized by appropriately combining organic chemistry methods. As an example thereof, for example, for a compound represented by the above formula (1), a dinitro intermediate having a nitro group is synthesized instead of the primary amino group in the formula, and then the nitro group of the obtained dinitro intermediate is synthesized. A method of amination using an appropriate reduction system can be mentioned.

The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. As an example, for the compound represented by the above formula (1), for example, a method of reacting a corresponding secondary amine compound having A ¹ , A ² and L ¹ with a halogenated nitrobenzene; ¹ , a method of reacting a halide having A ² and L ¹ with a secondary amine compound containing a nitrophenyl group; a corresponding carboxylic acid having an aminophenyl group and a nitro group, and a diol having a corresponding L ¹ A method of reacting; a method of reacting a corresponding diamine compound having A ¹ , A ² and L ¹ with a halogenated nitrobenzene having a corresponding B ¹ ; a hydroxyl group-containing compound having a corresponding aminophenyl group and nitro group; And a method of reacting with a corresponding halide having L ¹ .

The reaction for obtaining the nitro intermediate is preferably carried out in an organic solvent. Here, the organic solvent may be any solvent that does not affect the reaction, and examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. . Moreover, you may perform the said reaction in catalyst presence as needed.
The reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis procedure of diamine (C) and diamine (C1) is not limited to the said method.

[Synthesis of polyamic acid (P)]
The proportion of tetracarboxylic dianhydride and diamine used in the synthesis reaction of the polyamic acid (P) of the present invention is such that the acid anhydride group of tetracarboxylic dianhydride is equivalent to 1 equivalent of amino group of diamine Is preferably a ratio of 0.2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Hexamethylphosphortriamide and the like; phenolic solvents such as phenol, m-cresol, xylenol, halogenated phenol and the like;
Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .; ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, etc .; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl Propionate, isoamyl isobutyrate and the like; ethers such as diethyl ether, diisopentyl ether, ethylene glycol methyl Ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o- The Rorubenzen the like; as the hydrocarbon, e.g., hexane, heptane, octane, benzene, toluene, xylene and the like; may be mentioned, respectively.

  Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group of organic solvents), or one or more selected from the first group of organic solvents, It is preferable to use a mixture with one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less. The amount of organic solvent used (α) is such that the total amount (β) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight with respect to the total amount (α + β) of the reaction solution. It is preferable.

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

[Polyamic acid ester (P)]
The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) is, for example, [I] a polyamic acid (P) obtained by the above synthesis reaction, a hydroxyl group-containing compound, a halogen Obtained by reacting a compound, an epoxy group-containing compound, etc., [II] a method of reacting a tetracarboxylic acid diester and a diamine, and [III] a method of reacting a tetracarboxylic acid diester dihalide and a diamine. be able to.
In this specification, “tetracarboxylic acid diester” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are carboxyl groups. “Tetracarboxylic acid diester dihalide” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are halogenated.

  Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and as an epoxy group-containing compound, Examples thereof include propylene oxide. The tetracarboxylic acid diester used in Method [II] can be obtained by ring-opening tetracarboxylic dianhydride using the above alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. The diamine used in the methods [II] and [III] preferably contains the diamine (C ′), and other diamines may be used as necessary. The polyamic acid ester (P) may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

[Polyimide (P)]
The polyimide (hereinafter also referred to as polyimide (P)) as the polymer (P) can be obtained, for example, by dehydrating and ring-closing and imidizing the polyamic acid (P) synthesized as described above. .

  The polyimide (P) may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure of the polyamic acid (P) that is the precursor, and only a part of the amic acid structure is dehydrating and ring-closing. Alternatively, it may be a partially imidized product in which an amic acid structure and an imide ring structure coexist. As for the polyimide contained in the liquid crystal aligning agent of this invention, it is preferable that the imidation ratio is 30% or more, It is more preferable that it is 40 to 99%, It is still more preferable that it is 50 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

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

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

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

The polyamic acid, polyamic acid ester and polyimide as the polymer (P) obtained as described above have a solution viscosity of 20 to 1,800 mPa · s when this is a 15% by weight solution. It is preferable that it has a solution viscosity of 50 to 1,500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 15% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer.
The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ~ 300,000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above polymers (P), you may contain another component as needed. Examples of such other components include other polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”), and functional silane compounds. , Metal chelate compounds, curing accelerators, surfactants and the like.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. Examples of such other polymers include polymers obtained without using the above compound (C ′), and the main skeleton is not particularly limited. Specifically, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, etc. as the main skeleton And the like.
When adding another polymer to a liquid crystal aligning agent, it is preferable that the mixture ratio shall be 50 weight part or less with respect to a total of 100 weight part of the polymer contained in a liquid crystal aligning agent, The amount is more preferably 40 parts by weight, and still more preferably 0.1 to 30 parts by weight.

  Moreover, when providing liquid crystal aligning ability with the photo-alignment method with respect to the coating film formed using the liquid crystal aligning agent of this invention, you may use the polymer which has a photo-alignment structure as said other polymer. For example, in the case of a liquid crystal aligning agent for a retardation film, a polymer having a photoalignable group can be preferably used as the photoalignable structure, and specifically has a cinnamic acid structure (cinnamic acid or a derivative thereof). And polymers having a group introduced therein. Among them, a polyorganosiloxane having a cinnamic acid structure can be preferably used because it is easy to introduce a photoalignable group into the polymer.

In addition, the polymer which has a photoalignment group is compoundable by a conventionally well-known method. For example, the polyorganosiloxane having a photo-alignment group as another polymer is a polyorganosiloxane having an epoxy group and a carboxylic acid having a photo-alignment group, preferably an organic solvent such as ether, ester or ketone. It can synthesize | combine by making it react in presence of catalysts, such as a quaternary ammonium salt.
When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment method, the use ratio of the polymer having the photo-alignment structure (when the polymer (P) and other polymers have the photo-alignment structure, those The total amount) is preferably 3% by weight or more, more preferably 5 to 100% by weight, more preferably 10 to 100%, based on the total amount of the polymer used for the preparation of the liquid crystal aligning agent of the present invention. It is still more preferable to set it as weight%.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylene diene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamy Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.
When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferably, the content is ˜30 parts by weight.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3,6- Methyl azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it to -0.2 weight part.

[Metal chelate compounds]
When the polymer component of the liquid crystal aligning agent has an epoxy structure, the metal chelate compound is a liquid crystal aligning agent (particularly a liquid crystal for a retardation film) for the purpose of ensuring the mechanical strength of the film formed by low-temperature treatment. Contained in the alignment agent). As the metal chelate compound, it is preferable to use an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonate) Examples thereof include titanium, tri-n-butoxyethyl acetoacetate zirconium, and di-n-butoxybis (ethyl acetoacetate) zirconium. When the metal chelate compound is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, with respect to a total of 100 parts of the components including the epoxy structure, More preferably, it is 1-30 weight part.

[Curing accelerator]
When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is a liquid crystal in order to ensure the mechanical strength of the liquid crystal alignment film to be formed and the stability over time of the liquid crystal alignment. It is contained in an aligning agent (particularly, a liquid crystal aligning agent for a retardation film). As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group, or the like can be used. A compound having is preferred. Specific examples thereof include compounds having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol; compounds having a silanol group such as trimethylsilanol, triethylsilanol, 1 , 1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, etc. be able to. When the curing accelerator is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total components including the epoxy structure, and further Preferably it is 1-30 weight part.

[Surfactant]
The surfactant can be contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) for the purpose of improving the applicability of the liquid crystal aligning agent to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. be able to. The proportion of the surfactant used is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the total amount of the liquid crystal aligning agent.
In addition to the above, other components include compounds having at least one oxetanyl group in the molecule, antioxidants, and the like.

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

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

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

  The particularly preferable solid content concentration range varies depending on the use of the liquid crystal aligning agent and the method used when the liquid crystal aligning agent is applied to the substrate. For example, when a liquid crystal aligning agent for a liquid crystal aligning film is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC. Moreover, about the liquid crystal aligning agent for retardation films, the solid content density | concentration of a liquid crystal aligning agent is 0.2 to 10 weight% from a viewpoint which makes the applicability | paintability of a liquid crystal aligning agent, and the film thickness of the coating film formed moderate. It is preferable that it is the range of 3-10 weight%.

  In addition, as a result of examination of the present inventors, it is clear that a coating film having a flat surface (good surface irregularity) can be formed by using the liquid crystal aligning agent containing the polymer (P). The reason is not necessarily clear, but is presumed as follows. When the aromatic amine structure (a) is introduced to improve the performance of DC residual relaxation, it is considered that in addition to the increase in crystallinity, the polymer becomes rigid so that it is easily aggregated (crystallized). In this case, it is assumed that the polymer chains are entangled during the formation of the coating film, resulting in a decrease in the surface roughness of the coating film. On the other hand, in the polymer (P) obtained by using the compound (C) for the reaction, a chain structure (b) having a sufficiently long chain length is introduced as a spacer unit together with the aromatic amine structure (a). Thus, the entanglement of the polymer chains is released by heating (post-baking) at the time of forming the coating film, and it is considered that the surface unevenness is improved in the coating film after heating. Moreover, it is estimated that the said effect was acquired also for the polymer (P) obtained by using a compound (C1) for reaction for the same reason.

<Liquid crystal display element and retardation film>
By using the liquid crystal aligning agent of the present invention described above, a liquid crystal aligning film can be produced. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention is preferably applicable to the liquid crystal aligning film for liquid crystal display elements, and the liquid crystal aligning film for retardation films. Below, the liquid crystal display element and retardation film of this invention are demonstrated.

[Liquid crystal display element]
The liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. It can be applied to the driving method. The liquid crystal display element of the present invention can be produced, for example, by the following steps (I-1) to (I-3). In step (I-1), the substrate to be used varies depending on the desired operation mode. Steps (I-2) and (I-3) are common to each operation mode.

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

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

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

  In both cases (I-1A) and (I-1B), after applying a liquid crystal aligning agent on the substrate, a coating film to be an alignment film is formed by removing the organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, It is good also as a more imidized coating film by advancing the dehydration ring-closing reaction by further heating after the coating film formation.

[Step (I-2): Orientation ability imparting treatment]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the coating film formed in the step (I-1) is subjected to a treatment for imparting liquid crystal alignment ability. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the treatment include rubbing treatment in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. Is mentioned. On the other hand, when manufacturing a VA type liquid crystal display element, the coating film formed in the step (I-1) can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment ability imparting treatment. May be.

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

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

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

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

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

[Phase difference film]
When producing a retardation film using the liquid crystal aligning agent of the present invention, it is possible to form a uniform liquid crystal aligning film while suppressing the generation of dust and static electricity during the process, suitable for irradiation with radiation. It is preferable to use a photo-alignment method in that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate by using a simple photomask. Specifically, it can be produced through the following steps (II-1) to (II-3).

[Step (II-1): Formation of coating film by liquid crystal aligning agent]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and a coating film is formed. As the substrate used here, a transparent substrate made of a synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, etc. is preferably exemplified. Can do. Of these, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display device. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film in that the hygroscopicity of the solvent is low, the optical properties are good, and the cost is low. In addition, for the substrate used for the application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment is performed on the surface of the substrate surface on which the coating film is formed. May be implemented.

  In many cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to attach the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction so that the desired optical characteristics can be exhibited. Accordingly, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction on a substrate such as a TAC film or polymethyl methacrylate, the angle of the retardation film is controlled on the polarizing film. The step of bonding can be omitted. Thereby, it can contribute to the improvement of productivity of a liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferable to carry out by a photo alignment method using the liquid crystal aligning agent of the present invention.

The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber. Doctor coater method, offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method A positive rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB reverse coater method, and the like can be employed.
After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (II-2): Light irradiation step]
Next, the coating film formed on the substrate as described above is irradiated with light to impart liquid crystal alignment ability to the coating film. Here, the description of the photo-alignment process in the step (I-2) can be applied to the description of the wavelength of light to be irradiated, the type of light, and the light source to be used. The dose of light is preferably in a 0.1~1,000mJ / cm ^2, more preferably to 1 to 500 mJ / cm ^2, and more preferably be 2~200mJ / cm ^2.

[Step (II-3): Formation of Liquid Crystal Layer]
Next, a polymerizable liquid crystal is applied and cured on the coating film after the light irradiation as described above. Thereby, the coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such polymerizable liquid crystal, conventionally known ones can be used. Specifically, for example, Non-Patent Document 1 (“UV curable liquid crystal and its application”, Liquid Crystal, Vol. 3, No. 1 (1999) ), Pp 34-42). Further, cholesteric liquid crystal; discotic liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, an appropriate solvent, and the like.
In order to apply the polymerizable liquid crystal as described above onto a coating film formed using a liquid crystal aligning agent, for example, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, an ink jet method or the like is used. Can be adopted.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained.
The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.
As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2.
The thickness of the liquid crystal layer to be formed is appropriately set depending on desired optical characteristics. For example, when manufacturing a half-wave plate in visible light having a wavelength of 540 nm, a thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm. The thickness is selected such that the phase difference is 120 to 150 nm. The thickness of the liquid crystal layer from which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for manufacturing a quarter-wave plate is in the range of 0.6 to 1.5 μm.

  The retardation film obtained as described above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal aligning agent of the present invention is applied is not limited in its driving system, and for example, known types such as TN type, STN type, IPS type, FFS type, VA type, etc. It can be applied to various methods. The retardation film is used by attaching the substrate-side surface of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the retardation film substrate is made of TAC or an acrylic base, and the retardation film substrate also functions as a protective film for the polarizing film.

  Here, there is a roll-to-roll method as a method for producing a retardation film on an industrial scale. In this method, a film is unwound from a wound body of a long base film, a liquid crystal alignment film is formed on the unwound film, and a polymerizable liquid crystal is applied and cured on the liquid crystal alignment film. It is the method of performing the process and the process which laminates | stacks a protective film as needed in the continuous process, and collect | recovering the film after passing through these processes as a wound body. The retardation film formed using the liquid crystal aligning agent of the present invention has good adhesion to the substrate, and the liquid crystal alignment film and the substrate are hardly peeled even when stored as a wound body. Therefore, it is possible to suppress a decrease in product yield when the retardation film is manufactured by the roll-to-roll method.

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

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

In the following Examples and Synthesis Examples, the polymer weight average molecular weight Mw, imidization rate and epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene equivalent value measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidation rate of polymer]
A solution containing polyimide is poured into pure water, and the resulting precipitate is sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidation ratio was determined using the following formula (EX-1).
Imidation ratio (%) = (1-E ¹ / E ² × α) × 100 (EX-1)
(In Formula (EX-1), E ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, E ² is a peak area derived from other protons, and α is a precursor of a polymer ( It is the number ratio of other protons to one NH group proton in the polyamic acid).
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of Compound (C)>
[Synthesis Example 1-1; Synthesis of Compound (DA-1)]
Compound (DA-1) was synthesized according to the following scheme 1. In the formula, Bn represents a benzyl group (hereinafter the same).

The first stage reaction was synthesized by the Williamson reaction. First, in a 2 L three-necked flask equipped with a dropping funnel, 83.7 g (0.2 mol) of N-benzyl-4-hydroxyaniline, 46 g (0.42 mol) of 1,5-dibromopentane, cesium fluoride 121. 5 g (0.8 mol) and 800 mL of dimethylformamide were mixed and dissolved, and the reaction was performed by stirring at 60 ° C. for 4 hours. After the reaction, 2000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for separation and purification. The extraction and purification were repeated 5 times, and then the solvent was removed from the organic layer by distillation under reduced pressure to obtain 76.4 g (0. 0. compound) of a dibenzyl intermediate (compound represented by the above formula (DA-1-1)). 16 mol).
The second stage reaction was synthesized by the Ullmann condensation reaction. Under a nitrogen stream, 76.4 g (0.16 mol) of the above dibenzyl intermediate (DA-1-1), 81.5 g (0.33 mol) of 4-iodonitrobenzene, 59 g of phenanthroline (0) .33 mol), 139 g (0.65 mol) of tripotassium phosphate, 9.4 g (0.05 mol) of copper iodide and 600 mL of dimethylacetamide were mixed and dissolved, and the reaction was stirred for 24 hours under reflux. went. After completion of the reaction, the reaction solution was filtered to remove the catalyst, and then the filtrate was poured into 2000 mL of distilled water to precipitate crystals. The precipitated solid was collected by filtration, sufficiently washed with ethanol, and recrystallized from tetrahydrofuran to obtain 35 g (0.05 mol) of a nitro intermediate (compound represented by the above formula (DA-1-2)). .
The third stage reaction was synthesized by a hydrogen reduction reaction. Under a nitrogen stream, 35 g of the above nitro intermediate (DA-1-2), 3 g of 5% Pd / C, 50 mL of ethanol, 50 mL of tetrahydrofuran and 35 mL of hydrazine monohydrate were added to a 500 mL three-necked flask and then hydrogenated. Substitution was carried out and the reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. Ethyl acetate (1000 mL) was added to the filtrate, and distilled water (100 mL) was added for separation and purification. After the extraction and purification were repeated 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to precipitate a solid. The precipitated solid was recrystallized from a mixed solvent of tetrahydrofuran and ethanol to obtain 18.5 g (0.04 mol) of Compound (DA-1).

[Synthesis Example 1-2; Synthesis of Compound (DA-2)]
According to the following scheme 2, compound (DA-2) was obtained using the same synthetic reaction formulation as compound (DA-1).

[Synthesis Example 1-3; Synthesis of Compound (DA-3)]
According to the following scheme 3, compound (DA-3) was obtained using the same synthetic reaction formulation as compound (DA-1). The second stage reaction was synthesized using the technique described in Non-Patent Document 2 (The Journal of Organic Chemistry, 2002, 67, 6479).

[Synthesis Example 1-4; Synthesis of Compound (DA-4)]
According to the following scheme 4, compound (DA-4) was obtained using the same synthetic reaction formulation as compound (DA-1). The second stage reaction was synthesized by a hydrolysis reaction, and the third stage was synthesized by a condensation reaction with 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.

[Synthesis Example 1-5; Synthesis of Compound (DA-5)]
According to the following scheme 5, compound (DA-5) was obtained using the same synthetic reaction formulation as compound (DA-1).

[Synthesis Example 1-6; Synthesis of Compound (DA-6)]
According to the above scheme 6, compound (DA-6) was obtained using the same synthetic reaction formulation as compound (DA-1).

[Synthesis Example 1-7; Synthesis of Compound (DA-7)]
According to the following scheme 7, compound (DA-7) was obtained using the same synthetic reaction formulation as compound (DA-1).

[Synthesis Example 1-8; Synthesis of DA-8]
According to the following scheme 8, compound (DA-8) was obtained using the same synthetic reaction formulation as compound (DA-1). The first step in the synthesis of the mononitromonoiodo intermediate (compound represented by the above formula (DA-8-1)) is synthesized by Friedel-Crafts reaction, and the second step is trifluoromethanesulfone, which is a strong acid. The synthesis was carried out using a reduction reaction of a silane carbonyl group with triethylsilane in the presence of an acid.

[Synthesis Example 1-9; Synthesis of Compound (DA-9)]
According to the following scheme 9, compound (DA-9) was obtained using the same synthetic reaction formulation as compound (DA-1).

[Synthesis Example 1-10; Synthesis of Compound (DA-10)]
According to the following scheme 10, compound (DA-10) was obtained using the same synthetic reaction formulation as compound (DA-1). The first step in the synthesis of the mononitromonohydroxy intermediate (compound represented by the above formula (DA-10-1)) is synthesized by Friedel-Crafts reaction, and the second step is desorption of the methoxy group with lithium bromide. The third step was synthesized using a reduction reaction of the silane carbonyl group with triethylsilane in the presence of trifluoromethanesulfonic acid, which is a strong acid.

［合成例１−１２；化合物（ＤＡ−２３）の合成］
下記スキーム１２に従い、化合物（ＤＡ−２２−１）を亜鉛存在下、水を触媒として還元することにより化合物（ＤＡ−２３）を得た。

<Synthesis of Compound (C1)>
[Synthesis Example 1-11; Synthesis of Compound (DA-22)]
According to the following scheme 11, compound (DA-22) was obtained. In addition, the synthesis | combination of the 1st step obtained the intermediate body (compound represented by a following formula (DA-22-1)) by Kunafenergel reaction. In the second step, reduction was performed in the same manner as for compound (DA-1).

[Synthesis Example 1-12; Synthesis of Compound (DA-23)]
According to the following scheme 12, compound (DA-22-1) was reduced using water as a catalyst in the presence of zinc to obtain compound (DA-23).

<Synthesis of polymer>
Synthesis of polyamic acid [Synthesis Example 2-1; Synthesis of polymer (PAm-1)]
In a reaction vessel, tetracarboxylic dianhydride and diamine are charged so as to have a mixing ratio (mol part) shown in Table 1 below and a total weight of 30 g, and further N-methyl-2-pyrrolidone (NMP). 170g was added and melt | dissolved, and reaction was performed at 60 degreeC for 6 hours. The resulting reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain a polymer (PAm-1). In addition, the numerical value of Table 1 shows the use ratio (mol%) with respect to the whole quantity of the tetracarboxylic dianhydride used for reaction about the tetracarboxylic dianhydride, About the diamine, the diamine used for reaction The use ratio (mol%) with respect to the total amount of is shown. Subsequently, the polymer (PAm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the viscosity of each solution was measured. The measurement results are also shown in Table 1 below. Further, the polymer solution obtained above was allowed to stand at 20 ° C. for 3 days, so that it did not gel and the storage stability was good.

[Synthesis Example 2-2 to Synthesis Example 2-18; Synthesis of Polymer (PAm-2) to Polymer (PAm-18)]
The same operation as in Synthesis Example 2-1 was performed except that the mixing ratio of tetracarboxylic dianhydride and diamine was changed to the numerical values described in Table 1 and Table 2 below, and the polymer (PAm-2) to the polymer (PAm -18) were obtained respectively. The results of measuring the solution viscosity of each polymer in the same manner as in Synthesis Example 2-1 are shown in Tables 1 and 2 below. Further, each of the polymer solutions obtained above was allowed to stand at 20 ° C. for 3 days, and none of the polymer solution (PAm-14) was gelled, and the storage stability was good. . The polymer (PAm-14) was gelled and lost fluidity.

Synthesis of polyimide [Synthesis Example 3-1; Synthesis of polymer (PIm-1)]
A tetracarboxylic dianhydride and a diamine were mixed at the mixing ratio (mole part) shown in Table 2 below so that the total weight was 30 g. Further, 170 g of NMP was added, and polyamic acid was prepared in the same manner as in Synthesis Example 2-1. An acid was synthesized. Next, 200 g of NMP was added, and pyridine and acetic anhydride were added in the amounts shown in Table 2 below (the numerical values indicate mole parts relative to 100 mole parts of the total acid dianhydride), followed by dehydration ring closure reaction at 80 ° C. for 6 hours. Went. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain a polymer (PIm-1).
Subsequently, the polymer (PIm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the viscosity of each solution was measured. Moreover, it measured also about the imidation ratio. The measurement results are shown in Table 2 below. Furthermore, when the polymer solution obtained above was allowed to stand at 20 ° C. for 3 days, it did not gel and the storage stability was good.

[Synthesis Example 3-2; Synthesis of Polymer (PIm-2)]
Except having changed the mixing ratio of tetracarboxylic dianhydride and diamine into the numerical values shown in Table 2 below, the same operation as in Synthesis Example 3-1 was performed to obtain a polymer (PIm-2). The results of measuring the solution viscosity of the polymer (PIm-2) in the same manner as in Synthesis Example 3-1 and the measurement results of the imidization ratio are shown in Table 2 below. Further, the polymer solution obtained above was allowed to stand at 20 ° C. for 3 days, so that it did not gel and the storage stability was good.

Abbreviations of the compounds in Table 1 and Table 2 have the following meanings. Moreover, about the numerical value of a pyridine and acetic anhydride in Table 2, the molar part with respect to a total of 100 molar parts of the tetracarboxylic dianhydride used for reaction is shown.
(Tetracarboxylic dianhydride)
AN-1, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride AN-2; pyromellitic dianhydride AN-3; 2,3,5-tricarboxycyclopentylacetic dianhydride AN-4; Ethylenediaminetetraacetic acid dianhydride AN-5; 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione AN-6; bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride AN-7; 1,3-propylene glycol Bis (anhydro trimellitate)
AN-8; 1,2,3,4-cyclopentanetetracarboxylic dianhydride

(Diamine)
DA-11; 1,7-bis (4-aminophenoxy) heptane DA-12; 4,4′-diaminodiphenylamine DA-13; compound DA-14 represented by the following formula (DA-13); Compound DA-15 represented by DA-14); Compound DA-16 represented by the following formula (DA-15); 4,4′-diaminodiphenylmethane DA-17; 4-aminophenyl-4′-aminobenzoate DA-18; Compound DA-19 represented by the above formula (DA-18); 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine DA-20; 4- (tetradecaoxy) Benzene-1,3-diamine DA-21; cholestanyl 3,5-diaminobenzoate

Synthesis of photoalignable group-containing polyorganosiloxane [Synthesis Example 4-1; Synthesis of polymer (PSi-1)]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. Mixed. 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an oxiranyl group. Polyorganosiloxane was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on the polyorganosiloxane having an oxiranyl group, a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. The epoxy equivalent of the polyorganosiloxane having an oxiranyl group was measured and found to be 186 g / equivalent.
Next, in a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having the oxiranyl group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid and UCAT 18X (trade name, manufactured by San Apro Co., Ltd.) 0.10 g Was reacted at 80 ° C. for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into methanol to recover a precipitate formed, which was dissolved in ethyl acetate to form a solution. 6.3 g of polyorganosiloxane (PSi-1) having a cinnamic acid structure was obtained as a white powder. The weight average molecular weight Mw in terms of polystyrene measured by GPC for this polyorganosiloxane (PSi-1) was 3,500.

[Example 1-1: Photo-alignment FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, 50 parts by weight of the polymer (PAm-4) obtained in Synthesis Example 2-4 and 50 parts by weight of the polymer (PAm-11) obtained in Synthesis Example 2-11 were used. Dissolved in a mixed solvent (GBL: NMP: BC = 40: 40: 20 (weight ratio)) consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC), and the solid content concentration Was a 3.5 wt% solution. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore size of 0.2 μm.

(2) Evaluation of surface irregularity of coating film The liquid crystal aligning agent prepared above was applied onto a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then the inside of the chamber was replaced with nitrogen. A coating film having an average film thickness of 1,000 mm was formed by heating (post-baking) in an oven at 200 ° C. for 1 hour. This coating film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. In the evaluation, the surface roughness was “good” when Ra was less than 2.0 nm, “good” when it was 2.0 nm or more and less than 5.0 nm, and “bad” when it was 5.0 nm or more. In this example, Ra = 0.8 nm, and the surface unevenness was “good”.
(3) Evaluation of transmittance The light transmittance (%) at a wavelength of 400 nm was evaluated using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.) for the coating film obtained above. . In the evaluation, a case where the light transmittance was 97% or more was judged as “good”, a case where it was 95% or more and less than 97% was judged “good”, and a case where it was less than 95% was judged “bad”. As a result, this coating film was 99.0% and the permeability was “good”.
(4) Evaluation of orientation The coating film obtained above was irradiated with polarized ultraviolet light 300 J / m ² containing a 313 nm emission line from the normal direction of the substrate using an Hg-Xe lamp and a Grand Taylor prism. Was given. The refractive index anisotropy (nm) of this glass substrate with an alignment film was measured using a liquid crystal alignment film inspection apparatus (RayScan) manufactured by MORITEX. The evaluation was “good” when 0.020 nm or more, “good” when less than 0.020 nm and 0.010 nm or more, and “bad” when less than 0.010 nm. As a result, the refractive index anisotropy of this substrate was 0.037 nm, and the orientation was “good”.

(5) Production of FFS type liquid crystal display element using photo-alignment method FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape are formed in this order, and an electrode The liquid crystal aligning agent prepared in the above (1) is used on a surface of the glass substrate 11a having a transparent electrode and one surface of the counter glass substrate 11b using a spinner. It was applied to form a coating film. Next, this coating film was pre-baked for 1 minute on a hot plate at 80 ° C., and then heated (post-baked) at 230 ° C. for 15 minutes in an oven in which the inside of the chamber was replaced with nitrogen, so that the average film thickness was 1,000 mm. A coating film was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 2A is a top view of the top electrode 13, and FIG. 2B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2A. In this example, a substrate having a top electrode having a line width d1 of electrodes of 4 μm and a distance d2 between the electrodes of 6 μm was used. Further, as the top electrode 13, four types of drive electrodes of electrode A, electrode B, electrode C, and electrode D were used. FIG. 3 shows the configuration of the drive electrodes of this liquid crystal display element. In this case, the bottom electrode 15 functions as a common electrode that acts on all of the four drive electrodes, and each of the four drive electrode regions serves as a pixel region.

Next, each surface of these coating films is irradiated with polarized ultraviolet rays 300 J / m ² containing a 313 nm emission line from the substrate normal direction using a Hg—Xe lamp and a Grand Taylor prism, respectively, and has a liquid crystal alignment film. A substrate was obtained. At this time, the irradiation direction of polarized ultraviolet rays is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment in which the polarization plane of polarized ultraviolet rays is projected onto the substrate is the direction of the double-headed arrow in FIG. The light irradiation process was performed.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, and then the liquid crystal alignment film surfaces of a pair of substrates Were placed so that the planes of polarization of polarized ultraviolet rays projected onto the substrate were parallel and pressure bonded, and the adhesive was heat cured at 150 ° C. for 1 hour. Next, a liquid crystal “MLC-6221” manufactured by Merck & Co. was filled into the gap between the liquid crystal injection port and the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature.
Next, an FFS type liquid crystal display element was manufactured by laminating polarizing plates on both outer surfaces of the substrate. At this time, one of the polarizing plates is stuck so that the polarization direction thereof is parallel to the direction of projection of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film onto the substrate surface, and the other one has the polarization direction first. The polarizing plate was stuck so as to be orthogonal to the polarization direction of the polarizing plate.
The above method was repeated to produce a total of 5 FFS type liquid crystal display elements, one for each of the following evaluation of liquid crystal orientation, evaluation of heat resistance, resistance to bezel unevenness, afterimage characteristics and contrast characteristics. However, ultraviolet irradiation under voltage application was not performed in any case. Moreover, the polarizing plate was not bonded together about the liquid crystal cell used for evaluation of contrast characteristics.

(6) Evaluation of liquid crystal orientation For the FFS type liquid crystal display device manufactured as described above, the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with a microscope at a magnification of 50 times. did. In the evaluation, when the abnormal domain was not observed, the liquid crystal alignment was “good”, and when the abnormal domain was observed, the liquid crystal alignment was “bad”. In this liquid crystal display element, the liquid crystal orientation was “good”.
(7) Evaluation of voltage holding ratio For the FFS type liquid crystal display device manufactured as described above, a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and 167 milliseconds after the release of application. When the voltage holding ratio (VHR) was measured, the voltage holding ratio was 99.4%. In addition, as a measuring apparatus, Toyo Technica Co., Ltd. make and VHR-1 were used.
(8) Evaluation of heat resistance The voltage holding ratio was measured in the same manner as in the evaluation of the above (7) voltage holding ratio, and the value was defined as the initial VHR (VHR _BF ). Next, the liquid crystal display element after the initial VHR measurement was left in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was left at room temperature and allowed to cool to room temperature, and then the voltage holding ratio was measured in the same manner as described above, and the value was designated as VHR _AF . Further, the rate of change in voltage holding ratio (ΔVHR (%)) before and after application of thermal stress was determined by the following mathematical formula (EX-2).
ΔVHR (%) = ((VHR _BF −VHR _AF ) ÷ VHR _BF ) × 100 (EX−2)
In the evaluation of heat resistance, when the change rate ΔVHR is less than 4%, the heat resistance is “good”, when it is 4% or more and less than 5%, the heat resistance is “good”, and when it is 5% or more, the heat resistance is It was done as a sex “bad”. As a result, ΔVHR was 2.9%, and the heat resistance of this liquid crystal display element was “good”.

(9) Unevenness around sealant (bezel unevenness resistance)
The FFS type liquid crystal display device manufactured above was stored for 30 days under conditions of 25 ° C. and 50% RH, and then driven with an AC voltage of 5 V to observe the lighting state. The evaluation is “excellent” if the luminance difference (more black or more white) is not visually recognized around the sealant, but “good” if the luminance difference disappears within 5 minutes after lighting. The case where the luminance difference disappeared within the super 20 minutes was judged “good”, and the case where the luminance difference was visually recognized even after 20 minutes passed was judged as “bad”. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and was determined to be “excellent”.
(10) Evaluation of afterimage characteristics (DC afterimage evaluation)
The photo-alignment type liquid crystal display element produced above was placed in an environment of 25 ° C. and 1 atmosphere. The bottom electrode was set as a common electrode for all four drive electrodes, 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 with the common electrode to be in a 0 V application state, and a composite voltage composed of an AC voltage of 3.5 V and a DC voltage of 1 V was applied to the electrodes A and C for 2 hours. Immediately after 2 hours, an AC voltage of 1.5 V was applied to all of the electrodes A to D. Then, from the start of applying an AC voltage of 1.5 V to all drive electrodes, a drive stress application region (pixel region of electrode A and electrode C) and a drive stress non-application region (pixel region of electrode B and electrode D) The time until the difference in brightness with the eye could not be visually confirmed was measured, and this was defined as the afterimage erasing time. Note that the shorter this time, the less likely an afterimage is generated. The case where the afterimage erasing time was less than 30 seconds was evaluated as “good”, the case where it was 30 seconds or more and less than 120 seconds was evaluated as “good”, and the case where it was 120 seconds or more was evaluated as “bad”. The afterimage erasing time of the liquid crystal display element was 1 second, and the afterimage characteristics were evaluated as “good”.
(11) Evaluation of contrast characteristics after driving stress (AC afterimage evaluation)
After driving the FFS type liquid crystal cell manufactured above (without a polarizing plate) at an AC voltage of 10 V for 30 hours, using a device in which a polarizer and an analyzer are arranged between a light source and a light quantity detector. The minimum relative transmittance (%) represented by the following mathematical formula (EX-3) was measured.
Minimum relative transmittance (%) = (β−B ₀ ) / (B ₁₀₀ −B ₀ ) × 100 (EX-3)
(In Formula (EX-3), B ₀ is a transmission amount of light under blank and crossed Nicols. B ₁₀₀ is a transmission amount of light under blank and paranicols. Β is polarized light under crossed Nicols. (This is the minimum amount of light transmission with the liquid crystal display element sandwiched between the optical element and the analyzer.)
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 characteristics. A sample having a minimum relative transmittance of less than 0.5% was evaluated as “good”, a sample having a minimum relative transmittance of less than 0.5% and less than 1.0% was evaluated as “good”, and a sample having a minimum relative transmittance of 1.0% or more was determined as “bad”. As a result, the minimum relative transmittance of this liquid crystal display element was 0.2%, and the contrast characteristics were determined to be “good”.

[Example 1-2, Example 1-3, and Comparative Example 1-1]
A liquid crystal aligning agent was prepared in the same manner as in Example 1-1, except that the type and amount of the polymer used for preparing the liquid crystal aligning agent were as described in Table 3 below. Were manufactured and evaluated. The evaluation results are shown in Table 3 below.

[Example 2-1: rubbing FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent The polymer (PAm-1) obtained in Synthesis Example 2-1 as a polymer was converted to γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), and butyl cellosolve (BC). Was dissolved in a mixed solvent (GBL: NMP: BC = 40: 40: 20 (weight ratio)) to obtain a solution having a solid content concentration of 3.5% by weight. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore size of 0.2 μm.

(2) Evaluation of surface irregularity of coating film The liquid crystal aligning agent prepared above was applied onto a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then the inside of the chamber was replaced with nitrogen. A coating film having an average film thickness of 1,000 mm was formed by heating (post-baking) in an oven at 200 ° C. for 1 hour. The surface roughness of the coating film was evaluated in the same manner as in Example 1-1 (2). As a result, the Ra of this coating film was 0.9 nm, and the surface roughness was “good”.
(3) Evaluation of transmittance The transmittance of the coating film obtained above was evaluated in the same manner as in Example 1-1 (3). As a result, the transmittance of this coating film was 98.5%, and the permeability was “good”.

(4) Evaluation of rubbing resistance The coating film obtained above was rubbed at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec, and a hair foot indentation length of 0.4 mm by a rubbing machine having a roll wrapped with a cotton cloth. The treatment was performed 7 times. Foreign matter (a piece of coating film) due to rubbing scraping on the obtained substrate was observed with an optical microscope, and the number of foreign matters in a 500 μm × 500 μm region was measured. In the evaluation, the rubbing resistance was “good” when the number of foreign matters was 3 or less, “good” when 4 or more and 7 or less, and the rubbing resistance “bad” when 8 or more. As a result, no foreign matter was observed, and the rubbing resistance of this coating film was “good”.
(5) Evaluation of orientation The orientation of the glass substrate with an orientation film subjected to the rubbing orientation treatment obtained above was evaluated in the same manner as in Example 1-1 (4). As a result, this substrate had a refractive index anisotropy of 0.031 nm and was “good”.
(6) Production of FFS type liquid crystal display element using rubbing method The FFS type liquid crystal display element shown in FIG. 1 was produced in the same manner as in Example 1-1 (5). A schematic plan view of the top electrode 13 used here is shown in FIG. 4A is a top view of the top electrode 13, and FIG. 4B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 4A. In this example, a substrate having a top electrode having a line width d1 of electrodes of 4 μm and a distance d2 between the electrodes of 6 μm was used.

  Next, a rubbing process was performed on each surface of the coating film formed on the glass substrate with cotton to obtain a liquid crystal alignment film 12. In FIG.4 (b), the rubbing direction with respect to the coating film formed on the glass substrate 11a is shown by the arrow. These substrates are bonded through a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b are antiparallel, and liquid crystal MLC-6221 (manufactured by Merck) is injected, and the liquid crystal layer 16 is injected. Formed. Furthermore, the liquid crystal display element 10 was produced by bonding a polarizing plate (not shown) on both outer surfaces of the substrates 11a and 11b so that the polarization directions of the two polarizing plates were orthogonal to each other.

(7) Evaluation of liquid crystal orientation About the rubbing FFS type | mold liquid crystal display element manufactured above, liquid crystal orientation was evaluated like (6) of the said Example 1-1. As a result, this liquid crystal display element had “good” liquid crystal alignment.
(8) Evaluation of voltage holding ratio and heat resistance For the rubbing FFS type liquid crystal display device produced above, the voltage holding ratio (VHR _BF ) was measured in the same manner as (7) of Example 1-1, and the above In the same manner as in Example 1-1 (8), the heat resistance of the liquid crystal display element was evaluated based on the rate of change in voltage holding ratio before and after application of thermal stress. As a result, VHR _BF was 99.4%. Further, ΔVHR was 1.6%, and the heat resistance was judged as “good”.
(9) Unevenness around sealant (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as in Example 1-1 (9). As a result, the luminance difference of the liquid crystal display element was not visually recognized, and the bezel unevenness resistance was determined to be “excellent”.

(10) Evaluation of afterimage characteristics (DC afterimage evaluation)
DC afterimage evaluation was performed in the same manner as in Example 1-1 (10). As a result, the afterimage erasing time of this liquid crystal display element was 2 seconds and was evaluated as “good”.
(11) Evaluation of contrast characteristics after driving stress (AC afterimage evaluation)
AC afterimage evaluation was performed in the same manner as in Example 1-1 (10). In this case, the evaluation was performed using a liquid crystal cell without a polarizing plate. As a result, the minimum relative transmittance was 0.1%, and the contrast characteristics were judged as “good”.

[Example 2-2 to Example 2-15 and Comparative Examples 2-1 to 2-5]
A liquid crystal aligning agent was prepared in the same manner as in Example 2-1 except that the type and amount of the polymer used for the preparation of the liquid crystal aligning agent were as described in Table 4 below. Manufactured and evaluated. However, Comparative Example 2-4 was poor in liquid crystal alignment and was not evaluated for the liquid crystal cell. The evaluation results are shown in Tables 4 and 5 below.

  As shown in Tables 3 to 5, in the liquid crystal aligning agent containing the polymer obtained by using the compound (C ′), good results are obtained for the surface irregularity, permeability, rubbing resistance and orientation of the coating film. was gotten. Moreover, the liquid crystal display element produced using these liquid crystal aligning agents is all favorable about the orientation of a liquid crystal molecule, voltage holding ratio, heat resistance, bezel unevenness tolerance, afterimage characteristics (DC afterimage), and contrast characteristics (AC afterimage). As a result, various characteristics were well balanced.

On the other hand, in Comparative Example 2-1, which uses a diamine having only a chain structure without having an aromatic amine structure, the afterimage characteristics are “poor”, and the results are inferior to Examples in terms of bezel unevenness resistance and heat resistance. Therefore, it was insufficient to achieve the object of the present invention.
In Comparative Examples 1-1, 2-2, and 2-3 using a diamine having only an aromatic amine structure, the heat resistance, bezel unevenness resistance, and contrast characteristics of the liquid crystal display element were “poor”. In addition, Comparative Example 4 using PAm-14 was not worth using as a liquid crystal display element because the storage stability of the polymer, the surface irregularity of the coating film, the transmittance was poor, and the orientation of the liquid crystal was poor. It was. Furthermore, in Comparative Example 2-5, the heat resistance and the bezel unevenness resistance were “bad”. In addition, when comparing the transmittance of the coating film, the rubbing resistance and the orientation, and the orientation of the liquid crystal in the liquid crystal display element, the voltage holding ratio, the heat resistance, the bezel unevenness resistance, the afterimage characteristics and the contrast characteristics, any comparative example The results were also inferior to those of the examples.

[Example 3-1: TN liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, 50 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 and 50 parts by weight of the polymer (PAm-16) obtained in Synthesis Example 2-16, It was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering with a filter having a pore size of 0.2 μm.
(2) Evaluation of printability The liquid crystal aligning agent prepared in the above (1) is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). Apply and heat for 1 minute on a hot plate at 80 ° C (pre-bake) to remove the solvent, then heat on a hot plate at 200 ° C for 10 minutes (post-bake) to form a coating film with an average film thickness of 600 mm did. This coating film was observed with a microscope having a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. In the evaluation, when neither printing unevenness nor pinhole was observed, the printability was “good”, and when at least one of printing unevenness and pinhole was slightly observed, printability was “good”, printing unevenness and pin The case where at least one of the holes was frequently observed was regarded as “printing failure”. In this example, neither printing unevenness nor pinholes were observed, and the printability was “good”.
(3) Evaluation of transmittance The transmittance of the coating film obtained above was evaluated in the same manner as in Example 1-1 (3). As a result, the transmittance of this coating film was 98.4%, which was “good”.

(4) Manufacture of TN type liquid crystal cell Transparent electrode of glass substrate with transparent electrode made of ITO film using liquid crystal aligning agent prepared in (1) above using liquid crystal alignment film printer (Nissha Printing Co., Ltd.) After coating on the surface and heating (pre-baking) on a hot plate at 80 ° C. for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to obtain a coating film with an average film thickness of 600 mm Formed. This coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm to give liquid crystal alignment ability. . Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. The above operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to one of the pair of substrates on the outer edge of the surface having the liquid crystal alignment film, and the pair of substrates is then aligned with the liquid crystal alignment film surface. The adhesives were cured by overlapping and pressing them so that they face each other. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive to produce a TN type liquid crystal cell. did.

(5) Evaluation of liquid crystal orientation About the liquid crystal cell manufactured by said (4), the presence or absence of the abnormal domain when the voltage of 5V was turned on / off under crossed Nicols was observed with the microscope at 50 time magnification. Evaluation was performed in the same manner as in Example 1-1 (6). As a result, this liquid crystal display element had “good” liquid crystal alignment.

(6) Pretilt angle stability evaluation For the liquid crystal cell produced in (4) above, the angle of inclination of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He—Ne laser light, and this value was used as the initial pretilt. The angle was θ _IN . Non-Patent Document 3 (TJScheffer et.al., J. Appl. Phys. Vol. 48, p1783 (1977)) and Non-Patent Document 4 (F. Nakano et.al., JPN. J. Appl). Phys. Vol. 19, p2013 (1980)).
Then, an AC voltage of 5V was applied for 100 hours to the liquid crystal cell was measured for initial pretilt angle theta _IN. Thereafter, the pretilt angle was measured again by the same method as described above, and this value was defined as the pretilt angle θ _AF after voltage application. By substituting these measured values into the following formula (EX-4), the amount of change in the pretilt angle (Δθ (°)) before and after voltage application was determined.
Δθ = | θ _AF −θ _IN | (EX-4)
Pretilt angle stability is “good” when Δθ is less than 3%, pretilt angle stability is “good” when it is 3% or more and less than 4%, and pretilt angle stability is when it is 4% or more. As a result of evaluation as “defective”, the pretilt angle change rate of this liquid crystal display element was 1.6%, and it was determined that the pretilt angle stability was “good”.

(7) Evaluation of voltage holding ratio and heat resistance The voltage holding ratio (VHR _BF ) was measured in the same manner as (7) in Example 1-1, and the same as in (8) in Example 1-1. Thus, the heat resistance of the liquid crystal display element was evaluated based on the change rate of the voltage holding ratio before and after application of thermal stress. As a result, VHR _BF was 98.6%. Further, ΔVHR was 2.1%, and the heat resistance was judged as “good”.
(8) Uneven resistance around the sealant (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as in Example 1-1 (9). As a result, the luminance difference of the liquid crystal display element was not visually recognized, and was determined to be “excellent”.
(9) Evaluation of afterimage characteristics (DC afterimage evaluation)
DC afterimage evaluation was performed in the same manner as in Example 1-1 (10). As a result, the afterimage erasing time of this liquid crystal display element was 12 seconds and was evaluated as “good”.

[Example 4-1: VA liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, 20 parts by weight of the polymer (PIm-2) obtained in Synthesis Example 3-2 and 80 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 were mixed with NMP. And BC were added to obtain a solution having a solid concentration of 6.5% by weight and a solvent mixing ratio of NMP: BC = 50: 50 (weight ratio). After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering with a filter having a pore size of 0.2 μm.
(2) Evaluation of printability Using the liquid crystal aligning agent prepared in (1) above, the printability was examined in the same manner as in Example 3-1 (2). It was not observed and the printability was “good”.
(3) Evaluation of transmittance The transmittance of the coating film obtained above was evaluated in the same manner as in Example 1-1 (3). As a result, the coating film was 99.2% and the permeability of the coating film was “good”.

(4) Manufacture of VA type liquid crystal cell The liquid crystal aligning agent prepared above is liquid crystal aligning film printer (Nissha Printing Co., Ltd.) on the transparent electrode surface of a glass substrate with a transparent electrode (thickness 1 mm) made of ITO film. Applied). Subsequently, it was heated (prebaked) for 1 minute on a hot plate at 80 ° C., and further heated (post bake) for 60 minutes on a hot plate at 200 ° C. to form a coating film (liquid crystal alignment film) having an average film thickness of 800 mm. . This operation was repeated to obtain a pair (two) of glass substrates having a liquid crystal alignment film on the transparent conductive film. Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates is aligned with the liquid crystal alignment film surface. The adhesives were cured by overlapping and pressing so that they face each other. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a VA liquid crystal cell. .

(5) Evaluation of liquid crystal orientation, voltage holding ratio and heat resistance The liquid crystal cell produced in (4) above was evaluated for liquid crystal orientation in the same manner as in Example 1-1 (6). The liquid crystal alignment of the cell was “good”. Further, the voltage holding ratio (VHR _BF ) is measured in the same manner as (7) in Example 1-1, and the heat resistance (voltage before and after applying thermal stress) is measured in the same manner as (8) in Example 1-1. The rate of change in retention was evaluated. As a result, VHR _BF was 99.0%. Further, ΔVHR was 2.3%, and the heat resistance was judged as “good”.
(6) Unevenness around sealant (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as in Example 1-1 (9). As a result, the luminance difference of the liquid crystal cell was not visually recognized, and was judged as “good”.

[Example 5-1: retardation film]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of the polymer (PAm-1) obtained in Synthesis Example 2-1 and 10 parts by weight of the polymer (PSi-1) obtained in Synthesis Example 4-1 were mixed with NMP and It melt | dissolved in the mixed solvent (NMP: BC = 50: 50 (weight ratio)) which consists of BC, and set it as the solution whose solid content concentration is 3.5 weight%. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
(2) Manufacture of retardation film The liquid crystal aligning agent prepared above is applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C. for 2 minutes for coating with a film thickness of 100 nm. A film was formed. Next, the surface of the coating film was irradiated perpendicularly from the substrate normal line with polarized ultraviolet rays of 10 mJ / cm ² containing an emission line of 313 nm using a Hg—Xe lamp and a Grand Taylor prism. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck & Co., Inc.) was filtered through a filter having a pore size of 0.2 μm, and the polymerizable liquid crystal was applied onto the coated film after light irradiation by a bar coater. A film was formed. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C., an unpolarized ultraviolet ray containing 365 nm emission line was irradiated at 1,000 mJ / cm ² from a direction perpendicular to the coating surface using an Hg-Xe lamp. A retardation film was produced by curing a polymerizable liquid crystal to form a liquid crystal layer.

(3) Evaluation of liquid crystal orientation About the retardation film manufactured by said (2), the presence or absence of an abnormal domain is observed by visual observation under a cross Nicol and a polarizing microscope (2.5 times magnification). Photo-alignment) was evaluated. The evaluation was that the alignment was good visually and the abnormal domain was not observed with a polarizing microscope, the liquid crystal orientation was “good”, and the abnormal domain was not observed with the polarizing microscope, but the abnormal domain was observed with a polarizing microscope. The case where the liquid crystal orientation was “possible”, and the case where an abnormal domain was observed visually and with a polarizing microscope was regarded as “Poor”. As a result, this retardation film was evaluated as “good” for liquid crystal alignment.

(4) Adhesiveness Using the retardation film produced in (2) above, the adhesiveness of the coating film formed with the liquid crystal aligning agent to the substrate was evaluated. First, using an equally spaced spacer with a guide, a cutter knife was used to cut from the surface on the liquid crystal layer side of the retardation film to form 10 × 10 lattice patterns in a range of 1 cm × 1 cm. The depth of each cut was made to reach the middle of the substrate thickness from the surface of the liquid crystal layer. Next, after attaching a cellophane tape so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. The notches in the lattice pattern after peeling were observed visually under crossed Nicols to evaluate the adhesion. The evaluation was that the adhesion was “good” when no peeling was observed at the portion along the cut line and at the intersection of the lattice pattern, and the number of lattices where peeling was observed in the above portion was the number of the entire lattice pattern. On the other hand, when the amount is less than 15%, the adhesion is “possible”, and when the number of lattices where peeling is observed in the above portion is 15% or more with respect to the total number of lattice patterns, the adhesion is “bad”. went. As a result, this retardation film had good adhesion.

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

Claims (19)

The compound (C) having the following structure (a) and the following structure (b), and the following structure (a) and the following structure (b1) and polymerized to the aromatic ring group in the structure (a) A liquid crystal aligning agent containing a polymer (P) obtained by using at least one compound (C ′) selected from the group consisting of the compound (C1) in which the reactive group involved in is not bonded, and the group consisting of:
(A) An aromatic amine structure in which two or three aromatic ring groups are bonded to the same nitrogen atom.
(B) a divalent chain hydrocarbon group having 6 or more carbon atoms and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO. A chain structure selected from the group consisting of a divalent group substituted with —, —COO—, —COS—, or —Si (CH ₃ ) ₂ — (R represents a hydrogen atom or a monovalent organic group).
(B1) a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is represented by —O—, —S—, —CO—, —NR ³ —, — ^{NR 3 CO -, - COO -} , - COS- or -Si _{(CH 3) 2} - a divalent group obtained by replacing, -O -, - S -, - CO -, - NR 3 CO- (R 3 is A hydrogen atom or a monovalent organic group), a structure selected from the group consisting of —COO—, —COS—, and —Si (CH ₃ ) ₂ —.   The liquid crystal aligning agent according to claim 1, wherein the compound (C) is a compound having two or more aromatic amine structures in the molecule.   The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (P) is at least one selected from the group consisting of a polyamic acid, a polyamic acid ester, and a polyimide. The said compound (C) is a liquid crystal aligning agent as described in any one of Claims 1-3 which is a compound represented by following formula (1).

(In Formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. In the case where B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings bonded to a nitrogen atom, and when B ² is a single bond, A ³ And A ⁴ is an aromatic ring bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and a nitrogen atom L ¹ is a divalent group containing the structure (b). At least one of the B ¹ and the B ² is a single bond, the liquid crystal aligning agent of claim 4. The liquid crystal alignment agent according to the L ¹ is expressed by the following formula (2), according to claim 4 or 5.

(In formula (2), L ² and L ³ are each independently the structure (b). Q is a divalent group represented by the following formula (3) or formula (4). Is an integer from 0 to 4. “*” represents a bond.)

(In Formula (3), A ⁵ is a hydrogen atom or a monovalent organic group. R ¹ and R ² are substituents, which may be the same or different from each other. “*” Represents a bond. .)

(In formula (4), A ⁶ is a hydrogen atom or a monovalent organic group. “*” Represents a bond.) The liquid crystal aligning agent according to claim 4 or 5, wherein the compound (C) is a compound represented by the following formula (1-1).

(In Formula (1-1), L ¹¹ represents at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms as —O—, —S—, —CO—, —NR—, A ¹ is a divalent group including a group replaced by —NRCO—, —COO—, —COS— or —Si (CH ₃ ) ₂ — (R is a hydrogen atom or a monovalent organic group). , A ² , A ³ , A ⁴ , B ¹ and B ² have the same meaning as in the above formula (1), provided that when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, A ¹ and A ³ At least one of them is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group.) The liquid crystal aligning agent according to claim 4 or 5, wherein the compound (C) is a compound represented by the following formula (1-2).

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² has the same meaning as the above formula (1).) The liquid crystal aligning agent according to any one of claims 1 to 8, wherein the compound (C1) is a compound represented by the following formula (1-3).

(In Formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group. However, A ⁷ , A 9 ^At least two of ⁸ and A ⁹ are aromatic rings bonded to a nitrogen atom, L ⁴ is the structure (b1), and L ⁵ is a single bond or a divalent organic group. The polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide obtained by reacting tetracarboxylic dianhydride with a diamine containing the compound (C ′). ,
The tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b. -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, 3,5 6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8, 10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic dianhydride, 1,3-propylene The liquid crystal aligning agent as described in any one of Claims 1-9 containing at least 1 type chosen from the group which consists of glycol bis (anhydro trimellitate) and pyromellitic dianhydride.   The liquid crystal aligning agent as described in any one of Claims 1-10 whose molecular weight of the said compound (C ') is 1,000 or less.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-11.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 12.   A retardation film comprising the liquid crystal alignment film according to claim 12.   The process of apply | coating the liquid crystal aligning agent as described in any one of Claims 1-11 on a board | substrate, forming a coating film, the process of irradiating the said coating film, and on the coating film after the said light irradiation A method for producing a retardation film, comprising: applying a polymerizable liquid crystal thereon and curing the liquid crystal. A polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide,
At least one compound selected from the group consisting of a tetracarboxylic dianhydride, a tetracarboxylic acid diester compound, and a tetracarboxylic acid diester dihalide, a compound represented by the following formula (1-1), and a formula (1-2) ) And a diamine containing at least one selected from the group consisting of compounds represented by the following formula (1-3) and a polymer obtained by the reaction.

(In Formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. And when B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are bonded to the nitrogen atom through an aromatic ring, and when B ² is a single bond, When at least one of A ³ and A ⁴ is an aromatic ring bonded to a nitrogen atom, and B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings. .L ¹¹ attached to the nitrogen atom, at least one of the divalent chain hydrocarbon group having 6 or more carbon atoms Methylene -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group Or a divalent group including a group replaced by (wherein when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom). Or at least one of B ¹ and B ² is a divalent organic group.)

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² has the same meaning as the above formula (1-1), provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group. Or at least one of B ¹ and B ² is a divalent organic group.)

(In Formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group. However, A ⁷ , A 9 ^At least two of ⁸ and A ⁹ are aromatic rings and bonded to a nitrogen atom, L ⁴ is a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one of the chain hydrocarbon groups. Divalent group in which the methylene group is replaced with —O—, —S—, —CO—, —NR ³ —, —NR ³ CO—, —COO—, —COS— or —Si (CH ₃ ) ₂ —. , —O—, —S—, —CO—, —NR ³ CO— (R ³ is a hydrogen atom or a monovalent organic group), —COO—, —COS—, or —Si (CH ₃ ). _2- L ⁵ is a single bond or a divalent organic group.) A compound represented by the following formula (1-1).

(In Formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. And when B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are bonded to the nitrogen atom through an aromatic ring, and when B ² is a single bond, When at least one of A ³ and A ⁴ is an aromatic ring bonded to a nitrogen atom, and B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings. .L ¹¹ attached to the nitrogen atom, at least one of the divalent chain hydrocarbon group having 6 or more carbon atoms Methylene -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group In the case where L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom. Or at least one of B ¹ and B ² is a divalent organic group.) A compound represented by the following formula (1-2).

(In Formula (1-2), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group. B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom. And when B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are bonded to the nitrogen atom through an aromatic ring, and when B ² is a single bond, When at least one of A ³ and A ⁴ is an aromatic ring bonded to a nitrogen atom, and B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings. .L bonded to the nitrogen atom ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. ^However, if ^{L 12} is an alkanediyl group having 6 to 10 carbon atoms, at least one of ^{A 1} and ^{A 3} is a monovalent organic group, or ^{B 1} and at least one divalent ^{B 2} Organic group.) A compound represented by the following formula (1-3).

(In Formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group. However, A ⁷ , A 9 ^At least two of ⁸ and A ⁹ are aromatic rings and bonded to a nitrogen atom, L ⁴ is a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one of the chain hydrocarbon groups. Divalent group in which the methylene group is replaced with —O—, —S—, —CO—, —NR ³ —, —NR ³ CO—, —COO—, —COS— or —Si (CH ₃ ) ₂ —. , —O—, —S—, —CO—, —NR ³ CO— (R ³ is a hydrogen atom or a monovalent organic group), —COO—, —COS—, or —Si (CH ₃ ). _2- L ⁵ is a single bond or a divalent organic group.)

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