JP2010102159A - Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent for a liquid crystal display element which is lower in residual voltage; to provide a liquid crystal alignment layer formed by using the aligning agent; and to provide the liquid crystal display element including the alignment layer. <P>SOLUTION: In the liquid crystal aligning agent which includes: a polyamic acid or a derivative thereof constructed with a product of a reaction between a tetracarboxylic acid dianhydride or a derivative thereof and a diamine or a derivative thereof; and an epoxy compound having two or more epoxy groups, a tetracarboxylic acid dianhydride having a structure composed of two alicyclic carboxylic acid dianhydrides bonded to each other with a single bond or a divalent group having a silsesquioxane structure is used as the tetracarboxylic acid dianhydride or the derivative thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal aligning agent comprising a polyamic acid having a structure of a reaction product of a specific tetracarboxylic dianhydride and a diamine or a derivative thereof and an epoxy compound, and a liquid crystal aligning film formed from the liquid crystal aligning agent And a liquid crystal display device including the same.

  Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, liquid crystal display elements are also used as optoelectronic-related elements such as optical printer heads, optical Fourier transform elements, and light valves.

  The liquid crystal display element usually has 1) a pair of substrates arranged opposite to each other, 2) electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And 4) a liquid crystal layer formed between the pair of substrates.

  As a conventional liquid crystal display element, a display element using a nematic liquid crystal is a mainstream, and 1) a TN (twisted nematic) type liquid crystal display element twisted by 90 degrees, and 2) a STN (super twisted nematic) twisted usually by 180 degrees or more. 3) A so-called TFT (Thin Film Transistor) type liquid crystal display element using a thin film transistor has been put into practical use. These liquid crystal display elements have a drawback that a viewing angle at which an image can be properly viewed is narrow, and when viewed from an oblique direction, luminance and contrast decrease and luminance inversion occurs in a halftone.

  In recent years, the problem of viewing angle is as follows: 1) TN-TFT type liquid crystal display element using optical compensation film, 2) VA (vertical alignment) type liquid crystal display element using vertical alignment and optical compensation film, 3) vertical MVA (Multi Domain Vertical Alignment) type liquid crystal display element using alignment and protrusion structure technology together, or 4) IPS (In-Plane Switching) type liquid crystal display element of lateral electric field type, 5) ECB (Electrically Controlled Birefringence type) Liquid crystal display element, 6) Optically compensated bend (Optically self-compensated birefringence: OCB) type liquid crystal It has been improved by techniques such as display elements, and the improved techniques have been put into practical use or are being studied.

  The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures, but also by improving the components used in the liquid crystal display element. Among the components used in the liquid crystal display element, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element. Roles are becoming important year after year.

The liquid crystal alignment film is prepared from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution in which polyamic acid or soluble polyimide is dissolved in an organic solvent. After applying such a solution to a substrate, a polyimide-based alignment film is formed by film formation by means such as heating. Various liquid crystal aligning agents other than polyamic acid are also being studied, but they are almost practical in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, etc. It has not been converted.

  An important characteristic required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element is a residual voltage. When the residual voltage is high, an afterimage may occur.

  As an attempt to solve the above-mentioned problem, for example, polyamic acid or a derivative thereof having a structure of a reaction product of tetracarboxylic dianhydride or a derivative thereof and diamine or a derivative thereof, and an epoxy compound having two or more epoxy groups Are known (see, for example, Patent Documents 1 and 2).

However, further improvement in display quality in liquid crystal display elements is required, and development of a liquid crystal aligning agent that can provide a liquid crystal display element with higher performance is still required.
JP 11-119226 A JP 2007-286597 A

  Based on the above situation, the present invention provides a liquid crystal aligning agent for a liquid crystal display element having a lower residual voltage, a liquid crystal alignment film formed using the same, and a liquid crystal display element including the same.

  The inventors of the present invention provide a composition containing a polyamic acid which is a reaction product of a tetracarboxylic dianhydride having a specific structure and a diamine, and an epoxy compound having two or more epoxy groups, and has a low residual voltage. It discovered that it was effective as a liquid crystal aligning agent used for manufacture of a liquid crystal display element, and completed this invention. The present invention has the following configuration.

[1] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof having a structure of a reaction product of tetracarboxylic dianhydride or a derivative thereof and diamine or a derivative thereof, and an epoxy compound having two or more epoxy groups Because
The said tetracarboxylic dianhydride or its derivative contains the compound represented by following formula (I), The liquid crystal aligning agent characterized by the above-mentioned.

In formula (I), —X ¹ — represents a single bond or a divalent group represented by the following formula (II). In formula (II), -Ph represents a phenyl group.

[2] In the formula (I), -X ¹ - is the liquid crystal aligning agent of claim [1], which is a single bond.

[3] The tetracarboxylic dianhydride or a derivative thereof further includes one or both of compounds of the following formulas (1) and (14), or the diamine or a derivative thereof is represented by the following formulas (III) to (IX). ), Or the tetracarboxylic dianhydride or derivative thereof further includes one or both of the compounds of the following formulas (1) and (14), and the diamine Or the derivative contains 1 or more compounds chosen from the group which consists of following formula (III)-(IX), The liquid crystal aligning agent as described in [2] characterized by the above-mentioned.

In formulas (III) and (IV), m and n each represent an integer of 1 to 12,
Wherein (VI) ~ (VIII), -Y 1, -Y 2, and -Y ³ each represent an alkyl from -H or C 1 -C 30,
In the formula (IX), —X ² — independently represents —CH ₂ — or —O—, and —Y ⁴ represents alkyl having 1 to 30 carbon atoms, the following formula (X), or the following formula (XI). To express.

In formulas (X) and (XI), —Y ⁵ and —Y ⁶ each represent alkyl having 1 to 30 carbons.

[4] The diamine or derivative thereof is represented by the following formulas (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), (VIII) -1), (IX-1), (X-1), and the liquid crystal aligning agent as described in [3] characterized by being one or more compounds selected from the group consisting of (XI-1).

[5] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent according to [4], which is characterized.

[6] The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
[5] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), and (IV-1). Liquid crystal aligning agent.

[7] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (IX-1), (X-1), and (XI-1) [4] Liquid crystal aligning agent as described in.

[8] The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
[7] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (IX-1), (X-1), and (XI-1). Liquid crystal aligning agent.

[9] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1), and The liquid crystal aligning agent according to [4], comprising the formula (VI-1) or (VII-1).

[10] The tetracarboxylic dianhydride or a derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to [9], wherein the diamine or a derivative thereof is a compound of the formula (VII-1).

[11] The liquid crystal aligning agent according to [1], wherein —X ¹ — in the formula (I) is a divalent group represented by the formula (II).

[12] The tetracarboxylic dianhydride or derivative thereof further includes one or both of the compounds of the formulas (1) and (14), or the diamine or derivative thereof is represented by the formulas (III) to (VIII). Or the tetracarboxylic dianhydride or derivative thereof further includes one or both of the compounds of the formulas (1) and (14), and the diamine. Or a derivative thereof includes one or more compounds selected from the group consisting of the formulas (III) to (VIII), wherein the liquid crystal aligning agent according to [11] (provided that the formulas (VI) to (VIII) ) -Y ¹ , -Y ² , and -Y ³ each represent -H or alkyl having 1 to 30 carbons.

[13] The diamine or a derivative thereof is represented by the formula (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), and ( VIII-1) The liquid crystal aligning agent according to [12], which is one or more compounds selected from the group consisting of:

[14] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent according to [13], which is characterized in that

[15] The tetracarboxylic dianhydride or a derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). [14
] The liquid crystal aligning agent of a description.

[16] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent according to [13], which is characterized in that

[17] The tetracarboxylic dianhydride or a derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to [16], wherein the diamine or a derivative thereof is the compound of the formula (VII-1).

[18] In the tetracarboxylic dianhydride, in the formula (I), a compound in which —X ¹ — is a single bond, and in the formula (I), —X ¹ — is represented by the formula (II). The liquid crystal aligning agent according to [1], wherein a compound that is a divalent group is used.

[19] The tetracarboxylic dianhydride or a derivative thereof further includes one or both of the compounds of the formulas (1) and (14), or the diamine or a derivative thereof is represented by the formulas (III) to (VIII). Or the tetracarboxylic dianhydride or derivative thereof further includes one or both of the compounds of the formulas (1) and (14), and the diamine. Or a derivative thereof includes one or more compounds selected from the group consisting of the formulas (III) to (VIII), wherein the liquid crystal aligning agent according to [18] (however, the formulas (VI) to (VIII) ) -Y ¹ , -Y ² , and -Y ³ each represent -H or alkyl having 1 to 30 carbons.

[20] The diamine or a derivative thereof is represented by the formula (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), and ( The liquid crystal aligning agent according to [19], which is one or more compounds selected from the group consisting of VIII-1).

[21] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent according to [20], which is characterized.

[22] The tetracarboxylic dianhydride or a derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent as described in [21].

[23] The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent according to [20], which is characterized.

[24] The tetracarboxylic dianhydride or a derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to [23], wherein the diamine or a derivative thereof is the compound of the formula (VII-1).

[25] The epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cycloaliphatic epoxy compound. One or more selected, The liquid crystal aligning agent as described in any one of [1]-[24] characterized by the above-mentioned.

[26] The epoxy compound is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, bisphenol. It is one or more selected from the group consisting of A novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A type epoxy compound, and N, N, O-triglycidyl-p-aminophenol [25] Liquid crystal aligning agent as described in.

[27] A liquid crystal alignment film formed by baking the film of the liquid crystal aligning agent according to any one of [1] to [26].

[28] A pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and formed on the opposed surfaces of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [27]. element.

  The present invention can provide a liquid crystal display element having a lower residual voltage in various driving methods.

  The liquid crystal aligning agent of the present invention includes a polyamic acid or a derivative thereof having a structure of a reaction product of a tetracarboxylic dianhydride or a derivative thereof containing a compound represented by the following formula (I) and a diamine or a derivative thereof; And an epoxy compound having two or more epoxy groups.

In formula (I), —X ¹ — represents a single bond or a divalent group represented by the following formula (II). In formula (II), -Ph represents a phenyl group.

  The polyamic acid or derivative thereof may be one kind or two or more kinds. The content of the polyamic acid or the derivative thereof in the liquid crystal aligning agent of the present invention is preferably 0.1 to 50% by weight and preferably 1 to 30 from the viewpoint of reducing the residual voltage in the liquid crystal display element. More preferred.

  The epoxy compound may be one type or two or more types. The content of the epoxy compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of polyamic acid or a derivative thereof from the viewpoint of reducing the residual voltage in the liquid crystal display element. 1 to 80 parts by weight is more preferable.

  The polyamic acid or a derivative thereof is a component that dissolves in a solvent when used as a liquid crystal alignment agent, and is a component that forms a liquid crystal alignment film containing polyimide as a main component when used as a liquid crystal alignment film. Moreover, the said polyamic acid or its derivative has the structure of the reaction product of the tetracarboxylic dianhydride containing the compound represented with Formula (I), or its derivative (s), and diamine or its derivative (s).

When the polyamic acid or derivative thereof is a reaction product of the tetracarboxylic dianhydride or derivative thereof and the diamine or derivative thereof, the tetracarboxylic dianhydride in all structural units of the polyamic acid or derivative thereof. The product or derivative thereof and the diamine or derivative thereof are preferably 0.8: 1.2 to 1.2: 0.8 in molar ratio, and 0.9: 1.1 to 1.1: 0. .9 is more preferable.

A part of the tetracarboxylic dianhydride or a derivative thereof may be replaced with a dicarboxylic acid. The ratio of the dicarboxylic acid to the tetracarboxylic dianhydride or derivative thereof is preferably 10 mol% or less.

  Further, a part of the tetracarboxylic dianhydride or a derivative thereof may be replaced with a carboxylic anhydride. By substituting a part of tetracarboxylic dianhydride or derivative thereof with carboxylic anhydride, the polymerization reaction can be terminated in the polymerization reaction for producing polyamic acid or derivative thereof. Therefore, the molecular weight of the resulting polymer (polyamic acid or derivative thereof) can be easily controlled. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride or derivative thereof may be within a range where the effects of the present invention can be obtained, but is preferably 10 mol% or less as a guide.

In addition, a part of the diamine or a derivative thereof may be replaced with a monoamine. By replacing a part of the diamine with a monoamine, it is possible to cause the termination of the polymerization reaction in the polymerization reaction for producing the polyamic acid or its derivative, and to suppress the further progress of the reaction. The molecular weight of the polymer (polyamic acid or derivative thereof) can be easily controlled. Although the ratio of the monoamine with respect to diamine or its derivative (s) should just be a range with which the effect of this invention is acquired, it is preferable to set it as 10 mol% or less as a standard.

The polyamic acid or a derivative thereof can be produced, for example, by reacting a tetracarboxylic dianhydride and a diamine, but other raw materials from which the same structure as the reaction product can be obtained, for example, a tetracarboxylic acid derivative And a diamine derivative.

Examples of the tetracarboxylic acid derivative include a dicarboxylic acid diester compound obtained by esterifying a tetracarboxylic dianhydride represented by the following formula (10000). In the following formula (10000), Y ¹⁰⁰ represents an alkyl having 1 to 4 carbon atoms.

  Examples of the monohydric alcohol and monohydric alcohol derivative that esterify tetracarboxylic dianhydride include methanol, ethanol, propanol, and butanol. Examples of a method for obtaining a dicarboxylic acid diester compound by esterifying tetracarboxylic dianhydride include a method described in JP-A No. 61-72022 and a method analogous thereto.

As a method for obtaining a polyimide derivative from a dicarboxylic acid diester compound and a diamine, for example, a method using carbodiimide as a condensing agent (Japanese Patent Laid-Open No. 61-72022), a method using a carbonic acid diester (Japanese Patent Laid-Open No. 62-72724). And a method using a phosphorus compound (Japanese Patent Laid-Open No. 2002-356554) and a method of heating in a phenol-based solvent (Japanese Patent Laid-Open No. 53-124596).

  Examples of the diamine derivative include a silylated diamine compound obtained by silylating a diamine.

Examples of silylating agents used for silylation of diamines include trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, triethylbromosilane, tripropylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylpropylchlorosilane, and dimethylpropyl. Trialkyl halogenated silanes such as chlorosilane, dimethyloctylchlorosilane, dimethyloctadecylchlorosilane, t-butyldimethylchlorosilane; vinyl group-containing halogenated silanes such as dimethylvinylchlorosilane; dimethylphenylchlorosilane, diphenylmethylchlorosilane, dimethylphenylchlorosilane, diphenylmethylchlorosilane , Methylphenylvinylchlorosilane, etc. Nyl group-containing halogenated silane; Halogenated alkyl group-containing silane such as chloromethyldimethylchlorosilane, 3-chloropropyldimethylchlorosilane, dichloromethyldimethylchlorosilane; Alkoxy group-containing such as trimethoxychlorosilane, triethoxychlorosilane, dimethoxymethylchlorosilane Halogenated silanes; alkyl group-containing dihalogenated silanes such as dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, and dihexyldichlorosilane; disilanes such as hexamethyldisilane, hexaethyldisilane, and hexaphenyldisilane; bis ( Trimethylsilyl) acetamide, bis (triethylsilyl) acetamide, bis (triphenylsilyl) acetamide Silylated acetamide; hexamethyldisilazane such as disilazane; and the like.

Examples of the method for obtaining a silylated diamine compound by silylating diamine include the method described in JP-A-1-217420.

  Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, and polyamic acid amides. More specifically, polyamic acid derivatives include, for example, 1) a polyimide in which all amino acids and carboxyls of the polyamic acid have undergone a dehydration ring-closing reaction, 2) a partial polyimide in which a partial dehydration ring-closing reaction has occurred, and 3) a carboxyl of polyamic acid. 4) a polyamic acid-polyamide copolymer obtained by reacting a part of the acid dianhydride contained in the tetracarboxylic dianhydride compound with an organic dicarboxylic acid, And 5) Polyamideimide obtained by subjecting part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction.

The polyamic acid or derivative thereof may have any weight average molecular weight. The weight average molecular weight of the polyamic acid or derivative thereof is not particularly limited, but is preferably 5 × 10 ³ or more and more preferably 1 × 10 ⁴ or more from the viewpoint of use as a component of a liquid crystal aligning agent. The polyamic acid or derivative thereof having a weight average molecular weight of 5 × 10 ³ or more does not evaporate in the step of baking the liquid crystal alignment film, and has preferable physical properties as a component of the liquid crystal alignment agent.

  The weight average molecular weight of the polyamic acid or derivative thereof is measured by gel permeation chromatography (GPC). For example, the obtained polyamic acid or a derivative thereof is diluted with dimethylformamide (DMF) so that the polyamic acid concentration is about 1% by weight, and DMF is used as a developing solvent using Chromatopack C-R7A (manufactured by Shimadzu Corporation). As measured by gel permeation chromatographic analysis (GPC) and converted to polystyrene. Furthermore, in order to perform GPC measurement of polyamic acid, polyacrylic acid, etc. with high accuracy, a developing solvent in which inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc. and inorganic salt such as lithium bromide, lithium chloride, etc. are dissolved in DMF solvent. May be prepared.

The polyamic acid or a derivative thereof has a structure of a reaction product of a compound represented by the formula (I) and a diamine or a derivative thereof. That is, the tetracarboxylic dianhydride or a derivative thereof includes a compound of the following formula (I-1) in which -X ^1- in the formula (I) is a single bond, and -X ^1- in the formula (I). One or both of the compounds of the following formula (I-2), which is a group represented by the formula (II), are included. When the liquid crystal aligning agent of the present invention contains two or more kinds of polyamic acids or derivatives thereof, the compound represented by the formula (I) may be used only in one polyamic acid or derivatives thereof, It may be used for both polyamic acids or their derivatives.

Of the structure derived from the tetracarboxylic dianhydride or its derivative, the ratio of the compound represented by the formula (I) is 0.1 to 100 mol%, which reduces the residual voltage in the liquid crystal display device. From a viewpoint, it is more preferable that it is 0.5-100 mol%, and it is further more preferable that it is 1-100 mol%.

  The tetracarboxylic dianhydride or a derivative thereof may contain a compound other than the compound represented by the formula (I). Examples of the tetracarboxylic dianhydride or derivative thereof used in combination with the compound represented by the formula (I) include known tetracarboxylic dianhydrides and derivatives thereof used for liquid crystal aligning agents, and more specifically. Examples thereof include aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and alicyclic tetracarboxylic dianhydrides. The tetracarboxylic dianhydride can be selected, for example, from the viewpoint of solubility of polyamic acid or a derivative thereof in a solvent.

  Examples of the aromatic tetracarboxylic dianhydride include acid dianhydrides represented by the following formulas (1) to (13). The aromatic tetracarboxylic dianhydride is preferably an acid dianhydride represented by the following formulas (1), (2), (5), (6) and (7). It is more preferable that it is a pyromellitic dianhydride represented by these.

  Examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include acid dianhydrides represented by the following formulas (14) to (59), (61), and (62): Is mentioned.

  The aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are preferably acid dianhydrides represented by formulas (14) to (29), and are represented by formula (14). More preferred is 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

  From the viewpoint of making polyamic acid or a derivative thereof a polyimide soluble in a solvent, the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are represented by the formulas (19), (20), and It is preferable that it is an acid dianhydride represented by (27)-(29).

  The tetracarboxylic dianhydride or a derivative thereof includes the aromatic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride (for example, pyromellitic dianhydride). Liquid crystal display having a liquid crystal alignment film formed using a liquid crystal aligning agent containing the polyamic acid or a derivative thereof, including an anhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride) This is preferable from the viewpoint of imparting a good voltage holding ratio to the device.

Furthermore, as said tetracarboxylic dianhydride, the tetracarboxylic dianhydride which has a side chain structure is mentioned, for example. The tetracarboxylic dianhydride having the side chain structure is preferable from the viewpoint of increasing the pretilt angle in a liquid crystal display device having a liquid crystal alignment film formed using a liquid crystal aligning agent containing the polyamic acid or a derivative thereof.

  Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having a steroid skeleton represented by the following formulas (63) and (64).

  The tetracarboxylic dianhydride is not limited to the tetracarboxylic dianhydrides described above, and includes other tetracarboxylic dianhydrides within the scope of achieving the object of the present invention. Tetracarboxylic dianhydride can also be used in the present invention as the tetracarboxylic dianhydride.

  Examples of the diamine include known diamines and derivatives thereof used for liquid crystal alignment agents. More specifically, for example, a diamine having a linear structure, a diamine having a side chain structure, a siloxane diamine having a siloxane bond, Examples thereof include naphthalene diamine having a naphthalene structure, and fluorene diamine having a fluorene structure.

  The kind and amount of the diamine having the linear structure can be determined from the viewpoint of adjusting the voltage holding ratio when the liquid crystal display device is used to a desired range. From the above viewpoint, for example, the proportion of the diamine having the linear structure in the diamine or derivative thereof is preferably 1 to 100 mol%, and more preferably 5 to 80 mol%. Examples of the diamine having a linear structure include diamines represented by the following formulas (X) to (XVI).

In formula (X), A ¹ represents — (CH ₂ ) _m —. Here, m represents an integer of 1 to 12. In formulas (XII), (XIV), and (XVI), A ¹ is independently a single bond, —O—, —S—, —SS—, —SO ₂ —, —CO—, or —CONH. -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - S- (CH 2 ) represents the _m -S-. Here, m represents an integer of 1 to 12.

In the formulas (XV) and (XVI), A ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —. Or it represents C1-C3 alkylene. Further hydrogen bonded to a cyclohexane ring or a benzene ring in the formula (XI) ~ (XVI) is, -F _{independently, -CH 3, -OH, -COOH,} -SO 3 H, -PO 3 H 2 , Benzyl or 4-hydroxybenzyl may be substituted.

  Examples of the diamine represented by the formula (X) include diamines of the formulas (X-1) to (X-3).

  Examples of the diamine represented by the formula (XI) include diamines of the formulas (XI-1) and (XI-2).

  Examples of the diamine represented by the formula (XII) include diamines of the formulas (XII-1) to (XII-3).

  Examples of the diamine represented by the formula (XIII) include diamines of the formulas (XIII-1) to (XIII-16).

  Examples of the diamine represented by the formula (XIV) include diamines of the formulas (XIV-1) to (XIV-32).

  Examples of the diamine represented by the formula (XV) include diamines of the formulas (XV-1) to (XV-6).

  Examples of the diamine represented by the formula (XVI) include diamines of the formulas (XVI-1) to (XVI-12).

The diamine having the side chain structure is preferably used in applications that require a large pretilt angle, such as VA liquid crystal display elements, OCB liquid crystal display elements, STN liquid crystal display elements, and TN liquid crystal display elements. it can. Here, the diamine having a side chain structure refers to a substituent (side chain) that is branched from the main chain and can exhibit a desired pretilt angle when the substituent that connects two amino groups is the main chain. Means a diamine. That is, a diamine having a side chain structure reacts with tetracarboxylic dianhydride to provide a polyamic acid or polyimide (branched polyamic acid or branched polyimide) having a side chain group with respect to the polymer main chain. Can do. A liquid crystal alignment film formed from a liquid crystal alignment agent containing a polyamic acid or a polyimide having a side chain group with respect to such a polymer main chain can increase the pretilt angle in the liquid crystal display element. This is described, for example, in JP-A-11-193345.

Therefore, the side chain in the diamine having a side chain structure may be appropriately selected according to the required pretilt angle. For example, the side chain is preferably a group having 3 or more carbon atoms. In particular,
1) phenyl which may have a substituent, cyclohexylphenylene which may have a substituent, bis (cyclohexyl) phenylene which may have a substituent, alkyl having 3 or more carbon atoms, alkenyl or Alkynyl,
2) phenyloxy which may have a substituent, cyclohexyloxy which may have a substituent, bis (cyclohexyl) oxy which may have a substituent, which may have a substituent Phenylcyclohexyloxy, optionally substituted cyclohexylphenyloxy, or alkyloxy, alkenyloxy or alkynyloxy having 3 or more carbon atoms,
3) phenylcarbonyl, or alkylcarbonyl, alkenylcarbonyl or alkynylcarbonyl having 3 or more carbon atoms,
4) Phenylcarbonyloxy, or alkylcarbonyloxy, alkenylcarbonyloxy or alkynylcarbonyloxy having 3 or more carbon atoms,
5) phenyloxycarbonyl which may have a substituent, cyclohexyloxycarbonyl which may have a substituent, bis (cyclohexyl) oxycarbonyl which may have a substituent, which has a substituent Bis (cyclohexyl) phenyloxycarbonyl which may be substituted, cyclohexylbis (phenyl) oxycarbonyl which may have a substituent, or alkyloxycarbonyl, alkenyloxycarbonyl or alkynyloxycarbonyl having 3 or more carbon atoms,
6) phenylaminocarbonyl, or alkylaminocarbonyl having 3 or more carbon atoms, alkenylaminocarbonyl or alkynylaminocarbonyl,
7) Cyclic alkylene having 3 or more carbon atoms,
8) Cycloalkylalkylene which may have a substituent, phenylalkylene which may have a substituent, bis (cyclohexyl) alkylene which may have a substituent, which may have a substituent Cyclohexyl phenylalkylene, optionally substituted bis (cyclohexyl) phenylalkylene, optionally substituted phenylalkyloxy, alkylphenyloxycarbonyl, or alkylbiphenylyloxycarbonyl,
9) phenyl or cyclohexyl substituted by alkyl, fluorine-substituted alkyl, or alkoxy, and
10) Alkyl or fluorine in which two or more benzene rings or cyclohexane rings are bonded through a single bond, or bonded through —O—, —COO—, —OCO—, —CONH—, or alkylene having 1 to 3 carbon atoms. Examples include, but are not limited to, a substituted alkyl group, a ring assembly group substituted by alkoxy, or a group having a steroid skeleton.

  Here, examples of the “substituent” include alkyl, alkoxy, alkoxyalkyl and the like.

  Moreover, bis (cyclohexyl) or bis (phenyl) may be interrupted by alkylene.

  In the present specification, the terms “alkyl”, “alkenyl”, and “alkynyl” may be linear or branched.

  The kind and amount of the diamine having the side chain structure can be determined from the viewpoint of adjusting the pretilt angle in the liquid crystal display element to a desired range. The ratio of the diamine having the side chain structure in the diamine or a derivative thereof is, for example, preferably from 1 to 100 mol%, and more preferably from 10 to 100 mol% from the above viewpoint. Examples of the diamine having a side chain structure include diamines represented by the following formulas (XVII) and (XIX) to (XXII).

In Formula (XVII), A ³ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —. Here, m represents an integer of 1 to 6. R ⁷ represents a group having a steroid skeleton, a group represented by the following general formula (XVIII), or alkyl having 1 to 30 carbon atoms. In the alkyl, any —CH ₂ — may be independently replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, ₃ may be replaced by —CH ₂ F, —CHF ₂ or —CF ₃ . However, -O- is not adjacent in the alkyl.

In Formula (XVIII), A ⁴ and A ⁵ each independently represents a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 20 carbon atoms. To express. R ⁸ and R ⁹ each independently represents —F or —CH ₃ . Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Represents diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl. R ¹⁰ represents -F, alkyl having 1 to 30 carbon atoms, a fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, a -OCH ₂ F, -OCHF ₂ or -OCF _3. A and b each independently represent an integer of 0 to 4, and when a or b is 2 to 4, adjacent A ⁴ or A ⁵ are different groups, and c, d and e are each independently Represents an integer of 0 to 3, and when e is 2 or 3, the plurality of rings S may be the same group or different groups. f and g are each independently 0 to
Represents an integer of 2 and c + d + e ≧ 1.

In formula (XIX), the hydrogen bonded to the carbon forming the steroid skeleton may be independently replaced with —CH ₃ . In formulas (XIX) and (XX), R ¹¹ each independently represents —H or —CH ₃ , and R ¹² represents —H or an alkyl or alkenyl having 1 to 20 carbon atoms. A ⁶ each independently represents a single bond, —C (═O) — or —CH ₂ —. In formula (XII), R ¹³ and R ¹⁴ each independently represent —H, alkyl having 1 to 20 carbons or phenyl.

In Formula (XXI), R ¹⁵ represents —H or alkyl having 1 to 30 carbons. Arbitrary —CH ₂ — in the alkyl having 2 to 30 carbon atoms out of the alkyl may be independently replaced by —O—, —CH═CH— or —C≡C—. However, -O- is not adjacent in the alkyl. In formulas (XXI) and (XXII), A ⁷ independently represents —O— or alkylene having 1 to 6 carbons. In formula (XXI), A ⁸ represents a single bond or an alkylene having 1 to 3 carbon atoms. Ring T represents 1,4-phenylene or 1,4-cyclohexylene. h represents 0 or 1; In the formula (XXII), R ¹⁶ represents alkyl having 6 to 22 carbon atoms, and R ¹⁷ represents —H or alkyl having 1 to 22 carbon atoms.

Examples of the diamine represented by the formula (XVII) include diamines represented by the following formulas (XVII-1) to (XVII-11). In the formula (XVII), the two amino groups are bonded to the carbon of the phenyl ring. Preferably, the bonding positional relationship between the two amino groups is meta or para. Further, each of the two amino groups is preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions when the bonding position of “R ⁷ —A ³ —” is the 1st position.

In the formula, R ¹⁸ is preferably alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, more preferably alkyl having 5 to 25 carbons or alkoxy having 5 to 25 carbons. R ¹⁹ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, more preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

  Examples of the diamine represented by the formula (XVII) include diamines represented by the following formulas (XVII-12) to (XVII-17).

In the formulas (XVII-12) to (XVII-15), R ²⁰ is preferably alkyl having 4 to 30 carbons, and more preferably alkyl having 6 to 25 carbons. In the formulas (XVII-16) and (XVII-17), R ²¹ is preferably alkyl having 6 to 30 carbons, and more preferably alkyl having 8 to 25 carbons.

  Examples of the diamine represented by the formula (XVII) include diamines represented by the following formulas (XVII-18) to (XVII-38).

In the formulas (XVII-18) to (XVII-38), R ²² is preferably alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons. Is more preferable. R ²³ is -H, -F, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, are -OCH ₂ F, -OCHF ₂ or -OCF ₃ preferably alkyl of 3 to 25 carbon atoms Alternatively, alkoxy having 3 to 25 carbon atoms is more preferable. A ⁹ represents an alkylene having 1 to 20 carbon atoms.

  Examples of the diamine represented by the formula (XVII) include diamines represented by the following formulas (XVII-39) to (XVII-48).

Examples of the diamine represented by the formula (XIX) include diamines of the formulas (XIX-1) to (XIX-4). In formula (XIX), it is preferable that one of the two “NH ₂ —Ph—A ⁶ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. The two amino groups are each bonded to a phenyl ring carbon, and preferably bonded to meta or para with respect to the bonding position of A ⁶ .

Examples of the diamine represented by the formula (XX) include diamines of the formulas (XX-1) to (XX-8). In formula (XX), two “NH ₂ — (R ¹⁴ —) Ph—A ⁶ —O—” are each bonded to the carbon of the phenyl ring, but preferably to the carbon to which the steroid nucleus is bonded. In contrast, it is bound to meta or para carbon. The two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to meta or para to A ⁶ .

Examples of the diamine represented by the formula (XXI) include diamines represented by the formulas (XXI-1) to (XXI-9). In formula (XXI), the two amino groups are each bonded to the carbon of the phenyl ring, but are preferably bonded to meta or para to A ⁷ .

Wherein, R ²⁴ is -H, preferably an alkyl group having 1 to 30 carbon atoms, R ²⁵ is -H, further preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the diamine represented by the formula (XXII) include diamines represented by the formulas (XXII-1) to (XXII-3). In formula (XXII), the two amino groups are each bonded to the carbon of the phenyl ring, but are preferably bonded to meta or para to A ⁷ .

In the formula, R ²⁶ is preferably an alkyl group having 6 to 20 carbon atoms, and R ²⁷ is preferably —H and an alkyl group having 1 to 10 carbon atoms.

  Examples of the siloxane-based diamine include diamines represented by the following formula (XXIII).

In the formula, R ²⁸ and R ²⁹ independently represent alkyl having 1 to 3 carbon atoms or phenyl, and A ¹⁰ independently represents methylene, phenylene or alkyl-substituted phenylene. i represents an integer of 1 to 6, and j represents an integer of 1 to 10.

Examples of the diamine represented by the formula (XXIII) include diamines represented by the following formulas (XXIII-1) to (XXIII-7).

  Furthermore, diamines other than those described above can be used for the diamine or derivative thereof. Examples of such other diamines include diamines represented by the following formulas (1 ') to (8').

In the formula, R ³⁰ and R ³¹ independently represent an alkyl group having 3 to 30 carbon atoms.

  Needless to say, the diamine or derivative thereof is not limited to the diamine, and other diamines existing in various forms can be used within the scope of achieving the object of the present invention.

  The diamine can give a suitable pretilt angle to the liquid crystal display element formed using the liquid crystal aligning agent of the present invention by appropriately selecting the kind of diamine and the combination thereof.

  For example, in the case of a VA type liquid crystal display element, a large pretilt angle of about 80 to 90 °, and in the case of an OCB type liquid crystal display element, a pretilt angle of about 7 to 20 ° has a TN type liquid crystal display element or STN type liquid crystal display. In the case of an element, a pretilt angle of about 3 to 10 ° is often required, and in the case of an IPS liquid crystal display element, a small pretilt angle of about 0 to 3 ° is often required. Therefore, the liquid crystal aligning agent of the present invention in which the pretilt angle can be appropriately adjusted using a diamine having a side chain structure can be applied to any kind of liquid crystal display element.

  The tetracarboxylic dianhydride or derivative thereof and the diamine or derivative thereof can be appropriately selected according to the form of the applied liquid crystal display element. Examples of the diamine or derivatives thereof that are preferable from such a viewpoint include the diamines shown below.

In the formula (III) and (IV), m and n from each 1 represents an integer of 12, in the formula (VI) ~ (VIII), -Y 1, -Y 2, and -Y ³ are each - H or alkyl having 1 to 30 carbon atoms, in the formula (IX), -X ^2- independently represents -CH ₂ -or -O-, -Y ⁴ is alkyl having 1 to 30 carbon atoms, The following formula (X) or the following formula (XI) is represented.

Each of said formula (X) and (XI), -Y ⁵ and -Y ⁶ represents an alkyl having 1 to 30 carbon atoms.

  Examples of the diamines of the formulas (III) to (IX) include the following formulas (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII- 1), (VIII-1), (IX-1), (X-1), and (XI-1) compounds.

For example, when the tetracarboxylic dianhydride of the formula (I) or the derivative thereof contained in the tetracarboxylic dianhydride or a derivative thereof is a compound of the formula (I-1), the IPS type liquid crystal display element The tetracarboxylic dianhydride or derivative thereof preferably further includes one or both of the compounds of the formulas (1) and (14). The diamine or derivative thereof preferably contains one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). More preferably, it is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), and (IV-1).

  In the case where the tetracarboxylic dianhydride or derivative thereof of the formula (I) contained in the tetracarboxylic dianhydride or derivative thereof is a compound of the formula (I-1), a TN type liquid crystal display element is used. The tetracarboxylic dianhydride or derivative thereof preferably further includes one or both of the compounds of the formulas (1) and (14). Moreover, it is preferable that the said diamine or its derivative (s) is one or more compounds chosen from the group which consists of said Formula (IX-1), (X-1), and (XI-1).

In the case where the tetracarboxylic dianhydride or derivative thereof of the formula (I) contained in the tetracarboxylic dianhydride or derivative thereof is a compound of the formula (I-1), the VA type liquid crystal display element is used. The tetracarboxylic dianhydride or derivative thereof preferably further includes one or both compounds of the formulas (1) and (14), and more preferably further includes a compound of the formula (14). The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1), and the formula (VI-1) or (VII-1) is preferably included, and the compound of the formula (VII-1) is more preferable.

In the case where the tetracarboxylic dianhydride of the formula (I) or the derivative thereof contained in the tetracarboxylic dianhydride or a derivative thereof is a compound of the formula (I-2), the IPS type liquid crystal display element includes The tetracarboxylic dianhydride or derivative thereof preferably further includes one or both compounds of the formulas (1) and (14). The diamine or derivative thereof is preferably one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1).

Further, when the tetracarboxylic dianhydride of the formula (I) or the derivative thereof contained in the tetracarboxylic dianhydride or a derivative thereof is a compound of the formula (I-2), the VA type liquid crystal display element is used. The tetracarboxylic dianhydride or derivative thereof preferably further includes one or both compounds of the formulas (1) and (14), and more preferably further includes a compound of the formula (14). The diamine or derivative thereof is preferably one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). More preferably, it is a compound of the formula (VII-1).

In the case where the tetracarboxylic dianhydride or derivative thereof of the formula (I) contained in the tetracarboxylic dianhydride or derivative thereof is a compound of both the formulas (I-1) and (I-2) In the IPS type liquid crystal display element, it is preferable that the tetracarboxylic dianhydride or a derivative thereof further includes one or both compounds of the formulas (1) and (14). The diamine or derivative thereof is preferably one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1).

When the tetracarboxylic dianhydride or derivative thereof of the formula (I) contained in the tetracarboxylic dianhydride or derivative thereof is a compound of both the formulas (I-1) and (I-2) Then, in the VA liquid crystal display element, the tetracarboxylic dianhydride or a derivative thereof preferably further includes one or both compounds of the formulas (1) and (14), and the compound of the formula (14) Is more preferable. The diamine or derivative thereof is
Preferably, the compound is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). More preferably, it is a compound.

  The polyamic acid or a derivative thereof can be produced using a known method. For example, a desired amount of the diamine and, if necessary, monoamine is charged into a reaction vessel equipped with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser.

  Next, a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide, which is an amide polar solvent), the tetracarboxylic dianhydride, and, if necessary, a carboxylic anhydride are introduced into the reaction vessel. At this time, it is preferable that the total charge amount of tetracarboxylic dianhydride is approximately equal to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

  A polyamic acid solution can be obtained by reacting at a temperature of 0 to 70 ° C. for 1 to 48 hours under stirring. Moreover, the polyamic acid with a small molecular weight can also be obtained by heating and raising reaction temperature (for example, 50-80 degreeC).

  The polyamic acid or a derivative thereof can be identified by precipitating with a large amount of a poor solvent, completely separating a solid content and a solvent by filtration or the like, and analyzing by IR or NMR. Furthermore, after decomposing solid polyamic acid or its derivative with an aqueous solution of strong alkali such as KOH or NaOH, it is extracted with an organic solvent and analyzed by GC, HPLC or GC-MS, and used for polymerization of this polymer. Monomers can be identified.

  The obtained polyamic acid solution can be used by stirring or diluting with a solvent in order to adjust to a desired viscosity.

  When the polyamic acid or a derivative thereof is a soluble polyimide, for example, a polyamic acid solution is prepared by using an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride as a dehydrating agent, and triethylamine as a dehydrating ring-closing catalyst. And a tertiary amine such as pyridine and collidine can be obtained by imidization reaction at a temperature of 20 to 150 ° C.

  Alternatively, when the polyamic acid or its derivative is a soluble polyimide, for example, the polyamic acid is precipitated from a polyamic acid solution using a large amount of a poor solvent (alcohol solvent or glycol solvent such as methanol, ethanol, isopropanol). The precipitated polyamic acid can be obtained by imidization reaction at a temperature of 20 to 150 ° C. in a solvent such as toluene and xylene together with the same dehydrating agent and dehydrating ring-closing catalyst as described above.

  In the imidization reaction, the ratio of the dehydrating agent to the dehydrating ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount used of both is preferably 1.5 to 10 times the total molar amount of acid dianhydride contained in the tetracarboxylic dianhydride used. By adjusting the dehydrating agent, catalyst amount, reaction temperature and reaction time of this chemical imidization, the degree of imidization can be controlled to obtain a partial polyimide.

  Furthermore, polyamideimide can be produced by chemically imidizing the polyamic acid-polyamide copolymer.

  The obtained polyimide can be separated from the solvent and re-dissolved with the epoxy compound described later to be used as a liquid crystal aligning agent, or added as an liquid crystal aligning agent without being separated from the solvent. You can also

  The said epoxy compound is used by the kind and content which form the solution of an epoxy compound and the said polyamic acid or its derivative (s) in a liquid crystal aligning agent. The epoxy resin means a resin having an epoxy group.

  Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

  Examples of the glycidyl ether include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol-A type epoxy compounds, hydrogenated bisphenol-F type epoxy compounds, and hydrogenated compounds. Bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolac type epoxy Compounds, brominated cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, naphthalene skeleton-containing epoxy compounds, aromatic Polyglycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

  Examples of the glycidyl ester include diglycidyl ester compounds and glycidyl ester epoxy compounds.

  Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

  Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

  Examples of the glycidyl amide include glycidyl amide type epoxy compounds.

  Examples of the chain aliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

  Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

  Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, and 1010 (all manufactured by Japan Epoxy Resin), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331, and DER-332. , DER-324 (all manufactured by Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by Dainippon Ink), Epomic R-140, Epomic R-301, and Epomic R-304 (all Mitsui) Chemical).

Examples of the bisphenol F type epoxy compound include 806, 807, and 4004P (all manufactured by Japan Epoxy Resin), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all manufactured by Toto Kasei Co., Ltd.), DER-354. (
Dow Chemical Co.), Epicron 830, and Epicron 835 (all manufactured by Dainippon Ink).

  Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rica Resin HBE-100 (manufactured by Shin Nippon Chemical Co., Ltd.), and Denacol EX-252 (manufactured by Nagase ChemteX Corporation). .

  Examples of the hydrogenated bisphenol type epoxy compound include epoxidized products of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of the brominated bisphenol-A type epoxy compound include 5050, 5051 (all manufactured by Japan Epoxy Resin), Epototo YDB-360, Epototo YDB-400 (all manufactured by Toto Kasei Co., Ltd.), DER-530, DER-538. (All manufactured by Dow Chemical Co., Ltd.), Epicron 152, and Epicron 153 (all manufactured by Dainippon Ink).

  Examples of the phenol novolac type epoxy compound include 152, 154 (all manufactured by Japan Epoxy Resin), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (all manufactured by Dow Chemical Co., Ltd.), Epicron N-770 ( Dainippon Ink & Chemicals, Inc.), EPPN-201, and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Japan Epoxy Resin), YDCN-701, YDCN-702 (all manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, Epicron N-695 (all Dainippon Ink and Chemicals). Kogyo Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the naphthalene skeleton-containing epoxy compound include Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all manufactured by Dainippon Ink and Chemicals), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). Can be mentioned.

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following structural formula 101), catechol diglycidyl ether (the following structural formula 102), resorcinol diglycidyl ether (the following structural formula 103), 2- [4- (2 , 3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (Structural Formula 104 below), Tris (4 -Glycidyloxyphenyl) methane (the following structural formula 105), 1031S, 1032H60 (all manufactured by Japan Epoxy Resin), TACTIX-742 (manufactured by Dow Chemical), Denacol EX-201 (manufactured by Nagase ChemteX), DPPN- 503, DPP
N-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals), a compound represented by the following structural formula 106, and a compound represented by the following structural formula 107 Is mentioned.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX.
-556 (manufactured by Dow Chemical Company) and Epicron HP-7200 (manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (manufactured by Shin Nippon Rika).

  Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula 108), diethylene glycol diglycidyl ether (the following structural formula 109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (the following structural formula 110). ), Tripropylene glycol diglycidyl ether (the following structural formula 111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula 112), 1,4-butanediol diglycidyl ether (the following structural formula 113), 1,6-hexanediol diglycidyl ether (the following structural formula 114), dibromoneopentyl glycol diglycidyl ether (the following structural formula 115), Denaco EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all Nagase ChemteX Co., Ltd.), DD-503 (Asahi Denka Co., Ltd.), Rica Resin W-100 (Nippon Nippon Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (the following structural formula 116), glycerin poly Glycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all Nagaseke Made-Tex), and the like.

  Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toraythiol Coal).

  Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all manufactured by Japan Epoxy Resin), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula 118), bis (2-methyloxiranylmethyl) phthalate (the following structural formula 119), and diglycidyl hexa. Examples include hydrophthalate (the following structural formula 120), a compound represented by the following structural formula 121, a compound represented by the following structural formula 122, and a compound represented by the following structural formula 123.

  Examples of the glycidyl ester epoxy compound include 871, 872 (all manufactured by Japan Epoxy Resin), Epicron 200, Epicron 400 (all manufactured by Dainippon Ink & Chemicals, Inc.), Denacol EX-711, and Denacol EX-721. (Both manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (the following structural formula 124), N, N-diglycidyl-o-toluidine (the following structural formula 125), N, N-diglycidyl-m-toluidine (the following). Structural formula 126), N, N-diglycidyl-2,4,6-tribromoaniline (the following structural formula 127), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following structural formula 128), N, N, O-triglycidyl-p-aminophenol (the following structural formula 129), N, N, O-triglycidyl-m-aminophenol (the following structural formula 130), N, N, N ′, N′-tetraglycidyl -4,4'-diaminodiphenylmethane (the following structural formula 131), N, N, N ', N'-tetraglycidyl-m-xylylenediamine (TETR) DX (Mitsubishi Gas Chemical), structural formula 132 below, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (Mitsubishi Gas Chemical), structural formula 133 below), 1,4 -Bis (N, N-diglycidylaminomethyl) cyclohexane (the following structural formula 134), 1,3-bis (N, N-diglycidylamino) cyclohexane (the following structural formula 135), 1,4-bis (N, N-diglycidylamino) cyclohexane (the following structural formula 136), 1,3-bis (N, N-diglycidylamino) benzene (the following structural formula 137), 1,4-bis (N, N-diglycidylamino) Benzene (the following structural formula 138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (the following structural formula 139), N, N, N ′, N′-te Laglycidyl-4,4′-diaminodicyclohexylmethane (the following structural formula 140), 2,2′-dimethyl- (N, N, N ′, N′-tetraglycidyl) -4,4′-diaminobiphenyl (the following structure) Formula 141), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (Structure 142 below), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy ) Benzene (the following structural formula 143), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (the following structural formula 144), tris (4- (N, N-diglycidyl) aminophenyl) methane ( The following structural formula 145), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (the following structural formula 146), 3,4,3 ′, 4′-tetrakis (N, N— Glycidyl amino) diphenyl ether (Formula 147), a compound represented by the following structural formula 148, and compounds represented by the following structural formula 149.

  Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include, for example, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Examples include polymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymers, and styrene-glycidyl methacrylate copolymers.

  Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Examples of the monomer other than the oxiranyl-containing monomer in the oxiranyl-containing monomer copolymer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Examples of the glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following structural formula 150), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following structural formula 151), and glycidyl isocyanurate type epoxy resin.

  Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.), the following structural formula 152), 2 -Methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (the following structural formula 153), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane Ether (the following structural formula 154), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (Daicel Chemical Industries ( Co., Ltd.), the following structural formula 155), the following structural formula 56, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY), EHPD-3150 (manufactured by Daicel Chemical Industries, Ltd.), and cyclic aliphatic epoxy resins. It is done.

  The epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, bisphenol A It is preferably at least one selected from the group consisting of a novolak type epoxy compound, a cresol novolak type epoxy compound, a bisphenol A type epoxy compound, and N, N, O-triglycidyl-p-aminophenol.

  You may select suitably the content rate of the polyamic acid or its derivative (s) in the liquid crystal aligning agent of this invention with the coating method to the board | substrate of a liquid crystal aligning agent. For example, a polyamic acid in a liquid crystal aligning agent used in a printing machine (including an offset printing machine and an ink jet printing machine, which may be abbreviated as “printing machine” hereinafter) used in a manufacturing process of a normal liquid crystal display element. The content of the derivative is preferably 0.5 to 30% by weight and more preferably 1 to 15% by weight, but is appropriately adjusted in relation to the viscosity of the liquid crystal aligning agent.

  The liquid crystal aligning agent of this invention may further contain other components other than the said polyamic acid or its derivative (s), and an epoxy compound. Examples of such other components include a solvent that dissolves the polyamic acid or a derivative thereof and an epoxy compound.

The said solvent contains the solvent normally used in the manufacturing process and use of polymer components, such as a polyamic acid, a soluble polyimide, and a polyamideimide, and can be suitably selected according to the intended purpose. Preferred examples of the solvent include an aprotic polar organic solvent that is easily soluble in polyamic acid and soluble polyimide, other solvents for improving coating properties by changing the surface tension, and mixtures thereof. A solvent is mentioned.

  The aprotic polar organic solvent is generally a good solvent for polyamic acid and soluble polyimide. Examples of such aprotic polar organic solvents include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, Examples thereof include N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, and γ-valerolactone. Of these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, and γ-valerolactone are more preferred.

  Examples of other solvents for improving the coatability by changing the surface tension include, for example, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, Diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, propylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, dialkyl malonates such as diethyl malonate, dipropylene glycol Examples include dipropylene glycol monoalkyl ethers such as monomethyl ether and ester compounds such as acetates. That. Of these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like are more preferred.

  The types and ratios of the aprotic polar solvent and the other solvent can be appropriately set in consideration of the printability, coatability, solubility, storage stability, and the like of the liquid crystal aligning agent. Aprotic polar solvents are relatively superior in solubility and storage stability to other solvents, and other solvents tend to be excellent in printability and coatability.

  The liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include high molecular compounds other than polyamic acid or derivatives thereof, or low molecular compounds, and these can be selected and used according to each purpose.

  For example, the additive includes a polymer compound that is soluble in an organic solvent. This polymer compound is preferable from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of such a polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

  Examples of the low molecular weight compound include 1) a surfactant in accordance with the purpose when improvement in coatability is desired, 2) an antistatic agent when improvement in antistatic is required, and 3) adhesion to the substrate. Silane coupling agents and titanium-based coupling agents when improving the properties and rubbing resistance, and 4) imidization catalysts when imidization proceeds at low temperatures.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyl. Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N , N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatics such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. Cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, hydroxy-substituted imidazole; Is mentioned. In particular, N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline are more preferable.

  The addition amount of the silane coupling agent is usually 0 to 30 parts by weight and preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the polyamic acid or derivative thereof.

  The amount of the imidization catalyst added is usually 0 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.

  The addition amount of other additives varies depending on the application, but is usually 0 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of polyamic acid or a derivative thereof. .

  The viscosity of the liquid crystal aligning agent of the present invention varies depending on the application method, the concentration of the polyamic acid or derivative thereof, the type of polyamic acid or derivative thereof used, and the type and ratio of the solvent. For example, in the case of application by a printing press, it is preferably 5 to 100 mPa · s (more preferably 10 to 80 mPa · s). If it is less than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa · s, printing unevenness may increase. In the case of application by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable.

  The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, and is measured using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).

  The liquid crystal aligning agent of this invention may contain 2 or more types of polyamic acid or its derivative (s). For example, the liquid crystal aligning agent of the present invention may contain a polyamic acid containing the compound of the formula (I) as a constituent unit and other polyamic acid or a derivative thereof, and the compound of the formula (I) as a constituent unit. Two or more kinds of polyamic acids may be included. For example, the liquid crystal aligning agent of this invention may contain the polyamic acid which contains the compound of the said formula (I-1) in a structural unit, another polyamic acid, or its derivative (s), or the said formula (I-2) A polyamic acid containing a compound as a constituent unit and other polyamic acid or a derivative thereof may be contained, or a polyamic acid containing a compound of the formula (I-1) as a constituent unit and a compound of the formula (I-2) May be included in the structural unit.

  When the liquid crystal aligning agent of this invention contains 2 or more types of polyamic acid or its derivative (s), these polyamic acid or its derivative (s) can be mix | blended according to the desired characteristic. For example, in the case of using a polyamic acid I that does not contain a diamine having a side chain structure as a constituent unit and a polyamic acid II that contains a diamine having a side chain structure as a constituent unit, the polyamic acids I and II are converted into the desired pretilt. Depending on the angle, for example, I / II = 99/1 to 50/50, more preferably 95/5 to 80/20. The pretilt angle can be increased by increasing the ratio of polyamic acid II.

  In this way, by combining (blending) two or more kinds of polyamic acids or derivatives thereof, it is possible to impart and improve characteristics preferable as the liquid crystal aligning agent of the present invention. Such preferable characteristics include, for example, a voltage holding ratio other than the pretilt angle.

  The liquid crystal alignment film of the present invention is formed by baking the film of the liquid crystal aligning agent of the present invention described above.

  The liquid crystal alignment film is, for example, a liquid crystal display element substrate or a measurement substrate such as calcium fluoride or silicon applied to the liquid crystal alignment agent of the present invention. Preferably it can form by heating at 180-280 degreeC. Here, the film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 100 nm. The liquid crystal alignment film is preferably rubbed.

  The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal aligning agent and the application method of the liquid crystal aligning agent. The film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Furthermore, the components in the liquid crystal alignment film can be analyzed using a normal analysis means such as IR or MS after performing a treatment such as hydrolysis as necessary.

  The liquid crystal display element according to the present invention includes a pair of substrates disposed opposite to each other, electrodes formed on one or both of the surfaces opposed to each of the pair of substrates, and each of the pair of substrates opposed to each other. The liquid crystal alignment film of the present invention described above, and the liquid crystal layer formed between the pair of substrates.

  As the substrate, a substrate usually used in a display element can be used. The substrate is preferably a transparent substrate (for example, a glass substrate).

  The electrode is provided on the surface of at least one or both of the pair of substrates. The electrode is preferably provided according to the form of the liquid crystal display element, and is not particularly limited as long as the electrode is formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. The electrode may be formed on the entire surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. In the liquid crystal display element of the present invention, generally, the substrate on which the electrode is not provided has the liquid crystal alignment film of the present invention formed on the surface of the substrate, and the substrate on which the electrode is provided has the electrode of the present invention on the electrode. A liquid crystal alignment film is formed. The formation of the liquid crystal alignment film of the present invention is as described above.

  The liquid crystal layer is formed between a pair of substrates. The liquid crystal layer can be formed by supplying and holding a liquid crystal composition between a pair of substrates separated by a predetermined distance. Here, the liquid crystal composition is not particularly limited, and either a liquid crystal composition having a positive dielectric anisotropy or a liquid crystal composition having a negative dielectric anisotropy may be used depending on the driving mode. it can.

  Examples of preferable liquid crystal compositions having a positive dielectric anisotropy are disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8- No. 231960, JP-A-9-241644 (EP882722A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556. JP, 9-241643 (EP882711A1), JP 10-204016 (EP844229A1), JP 10-204436, JP 10-231482, JP 2000-087040, JP It is disclosed in 2001-48822 gazette etc. .

The liquid crystal composition used in the VA liquid crystal display element can be various liquid crystal compositions having negative dielectric anisotropy. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No.
-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11- No. 080049, JP-A No. 2000-256307, JP-A No. 2001-019965, JP-A No. 2001-072626, JP-A No. 2001-192657, and the like.

  One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  Of course, the liquid crystal display element of the present invention may have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on a first transparent substrate, and the second transparent substrate is formed. A black matrix, a color filter, a planarization film, a pixel electrode, and the like that block light outside the pixel region may be included.

  Further, in a VA liquid crystal display element, in particular, an MVA liquid crystal display element, a minute protrusion called a domain is formed on a first transparent substrate. A spacer may be formed for adjusting the cell gap between the substrates.

  The liquid crystal display element of the present invention can be produced by any method. For example, 1) a step of applying a liquid crystal alignment agent on the two transparent substrates, 2) a step of drying the applied liquid crystal alignment agent, 3 ) A step of performing a heat treatment necessary for dehydration and ring-closing reaction of the dried liquid crystal alignment agent, 4) a step of aligning the obtained alignment film, and 5) after bonding the two substrates together, The liquid crystal is manufactured by a method including a step of encapsulating liquid crystal in the substrate, or a step of dropping the liquid crystal on one substrate and then attaching the liquid crystal to the other substrate.

  As a coating method in the step of applying the liquid crystal aligning agent, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are also applicable in the present invention.

  Further, as a method of the drying step and the step of performing the heat treatment necessary for the dehydration reaction, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are also applicable in the present invention. The drying step is preferably performed at a relatively low temperature (50 to 140 ° C.) within a range where the solvent can be evaporated. In general, the heat treatment step is preferably performed at a temperature of about 150 to 300 ° C.

  The alignment treatment for the liquid crystal alignment film is usually a rubbing treatment for IPS liquid crystal display elements, OCB liquid crystal display elements, TN liquid crystal display elements, and STN liquid crystal display elements. In many cases, the VA liquid crystal display element is not subjected to the rubbing treatment.

  Next, an adhesive is applied onto one substrate, and the liquid crystal is injected in a vacuum. In the case of the dropping injection method, the liquid crystal is dropped on the substrate before bonding, and then bonded on the other substrate. The liquid crystal display element of the present invention is produced by curing the adhesive used for bonding with heat or ultraviolet rays.

  A polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, and the like may be mounted on the liquid crystal display element of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.

<Tetracarboxylic dianhydride>
Compound: pyromellitic dianhydride (formula (1)): PMDA
Compound: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (formula (14)): CBDA
Compound: Butanetetracarboxylic dianhydride (formula (I-1)): BT100
Compound: 18,21-bis (3- (2,5-dioxotetrahydrofuran-3-yl) propyl) -18,21-dimethyl-1,3,5,7,9,11,13,15-octaphenyl -Pentacyclo [10.5.1.25, 13.17, 11.19,15] decasiloxane (formula (I-2)): PSQ1

<Diamine>
Compound: 4,4′-diaminodiphenylmethane (formula (III-1)): DDM
Compound: 4,4′-diaminodiphenylethane (formula (III-2)): DDET
Compound: 4,4′-diaminodiphenyl ether (formula (V-1)): DDE
Compound: 1,3-bis [4- (4-aminophenylmethyl) phenyl] propane (formula (IV-1)): BABZP3
Compound: 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (trans-4-n-pentylcyclohexyl) cyclohexane (formula (X-1)): 5HHBA
Compound: 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethyl-1,3-diaminobenzene (formula (VI-1)): 5HHP1PDA
Compound: 1-phenylmethyl-2,5-diaminobenzene (formula (VIII-1)): 2,5-P1PDA
Compound: 5- [4- (n-hexadecyl) phenylmethyl] -1,3-diaminobenzene (formula (VII-1)): 16P1PDA

<Epoxy compound>
Compound: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane: TGDDM
Compound: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate: Celoxide 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.)
Compound: Bisphenol A novolac type epoxy compound: 157S70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)
Compound: Cresol novolac type epoxy compound: EOCN-104S (trade name, manufactured by Nippon Kayaku Co., Ltd.)
Compound: Bisphenol A type epoxy compound: 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)
Compound: N, N, O-triglycidyl-p-aminophenol: TGAP

<Solvent>
N-methyl-2-pyrrolidone: NMP
γ-butyrolactone: GBL
Butyl cellosolve (ethylene glycol monobutyl ether): BC

<1. Synthesis of polyamic acid>
[Synthesis Example 1]
2.927 g of DDM and 54.0 g of dehydrated NMP were placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging charge port and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. Next, 1.610 g of PMDA, 1.463 g of BT100, and 15.0 g of dehydrated GBL were added and reacted for 30 hours in a room temperature environment. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. BC25.0g was added to the obtained solution, and the polyamic acid solution with a density | concentration of 6 weight% was obtained. This polyamic acid solution is designated as PA1.

[Synthesis Examples 2 to 11]
Polyamic acid solutions PA2 to PA11 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1. The results are summarized in Table 1 including Synthesis Example 1.

<2. Production of liquid crystal display element>
[Example 1]
In a solution obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA1 and diluting the whole so that the concentration of polyamic acid becomes 4% by weight, TGDDM is added to 100 parts by weight of polyamic acid. The liquid crystal aligning agent 1 was obtained by dissolving 20 parts by weight. Using the obtained liquid crystal aligning agent 1, a liquid crystal display element was produced as follows.

<Method for Producing Liquid Crystal Display Elements (Examples 1 to 5, Comparative Examples 1 to 6)>
The liquid crystal aligning agent 1 was apply | coated to the glass substrate with two ITO electrodes with the spinner, and the film | membrane with a film thickness of 70 nm was formed. After coating, the film was heated and dried at 80 ° C. for about 3 minutes, and then heat-treated at 210 ° C. for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the liquid crystal alignment film was formed was rubbed with a rubbing apparatus to perform the alignment treatment. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

One glass substrate was sprayed with a 7 μm gap material, and the surface on which the liquid crystal alignment film was formed was placed inside so as to face each other so that the rubbing direction was anti-parallel, and then sealed with an epoxy curing agent, and the gap was 7 μm. A parallel cell was produced. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

[Comparative Example 1]
A liquid crystal aligning agent 2 was obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA1 and diluting the whole so that the concentration of polyamic acid was 4% by weight. Using the obtained liquid crystal aligning agent 2, a liquid crystal display element was produced in the same manner as in Example 1.

[Comparative Example 2]
A mixed solvent of NMP / BC = 1/1 (weight ratio) is added to PA2 to dilute the whole so that the concentration of polyamic acid is 4% by weight, and 20 parts by weight of TGDDM is dissolved in 100 parts by weight of polyamic acid. Thus, a liquid crystal aligning agent 3 was obtained. A liquid crystal display device was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent 3.

[Example 2]
In a solution obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA3 and diluting the whole so that the concentration of polyamic acid becomes 4% by weight, 2021P in 100 parts by weight of polyamic acid The liquid crystal aligning agent 4 was obtained by dissolving 20 parts by weight. Using the obtained liquid crystal aligning agent 4, a liquid crystal display element was produced in the same manner as in Example 1.

[Comparative Example 3]
A liquid crystal aligning agent 5 was obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA3 and diluting the whole so that the concentration of polyamic acid was 4% by weight. Using the obtained liquid crystal aligning agent 5, a liquid crystal display element was produced in the same manner as in Example 1.

[Example 3]
To a solution obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA4 and diluting the whole so that the concentration of polyamic acid is 4% by weight, 157S70 is added to 100 parts by weight of polyamic acid. The liquid crystal aligning agent 6 was obtained by dissolving 20 parts by weight. A liquid crystal display element was produced using the obtained liquid crystal aligning agent 6 in the same manner as in Example 1.

[Comparative Example 4]
A liquid crystal aligning agent 7 was obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA4 and diluting the whole so that the concentration of polyamic acid was 4% by weight. Using the obtained liquid crystal aligning agent 7, a liquid crystal display element was produced in the same manner as in Example 1.

[Example 4]
In a solution obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA5 and diluting the whole so that the concentration of polyamic acid is 4% by weight, EOCN104S is added to 100 parts by weight of polyamic acid. The liquid crystal aligning agent 8 was obtained by dissolving 20 parts by weight. A liquid crystal display element was produced using the obtained liquid crystal aligning agent 8 in the same manner as in Example 1.

[Comparative Example 5]
A liquid crystal aligning agent 9 was obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to PA5 and diluting the whole so that the concentration of polyamic acid was 4% by weight. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal aligning agent 9.

[Example 5]
PA6 and PA7 were mixed at a weight ratio of 9/1. A solution obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to the obtained mixture and diluting the whole so that the concentration of polyamic acid becomes 4% by weight was added to 828 with polyamic acid 100. The liquid crystal aligning agent 10 was obtained by dissolving 20 parts by weight with respect to parts by weight. Using the obtained liquid crystal aligning agent 10, a liquid crystal display element was produced in the same manner as in Example 1.

[Comparative Example 6]
PA6 and PA7 were mixed at a weight ratio of 9/1. A liquid crystal aligning agent 11 was obtained by adding a mixed solvent of NMP / BC = 1/1 (weight ratio) to the obtained mixture and diluting the whole so that the concentration of polyamic acid was 4% by weight. Using the obtained liquid crystal aligning agent 11, a liquid crystal display element was produced in the same manner as in Example 1.

[Example 6]
PA8 and PA9 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. 20 parts by weight of TGDDM was dissolved in 100 parts by weight of polyamic acid in the diluted solution to obtain a liquid crystal aligning agent 12. Using the obtained liquid crystal aligning agent 12, a liquid crystal display element was produced as follows.

<Method for Producing Liquid Crystal Display Elements (Examples 6 to 8, Comparative Examples 7 to 10)>
The liquid crystal aligning agent 12 was apply | coated to the glass substrate with two ITO electrodes with a spinner, and the film | membrane with a film thickness of 70 nm was formed. After coating, the film was heated and dried at 80 ° C. for about 3 minutes, and then heat-treated at 210 ° C. for 20 minutes to form a liquid crystal alignment film. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  A 7 μm gap material was sprayed on one glass substrate, and the surface on which the liquid crystal alignment film was formed was placed inside, and then sealed with an epoxy curing agent to produce a cell with a gap of 7 μm. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

[Example 7]
PA8 and PA9 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. In the solution obtained by dilution, 20 parts by weight of TGAP was dissolved with respect to 100 parts by weight of the polyamic acid to obtain a liquid crystal aligning agent 13. Using the obtained liquid crystal aligning agent 13, a liquid crystal display element was produced in the same manner as in Example 6.

[Comparative Example 7]
PA8 and PA9 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. The liquid crystal aligning agent 14 was obtained by diluting. Using the obtained liquid crystal aligning agent 14, a liquid crystal display element was produced in the same manner as in Example 6.

[Comparative Example 8]
PA10 and PA9 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. In a solution obtained by dilution, 20 parts by weight of TGDDM was dissolved in 100 parts by weight of polyamic acid to obtain a liquid crystal aligning agent 15. Using the obtained liquid crystal aligning agent 15, a liquid crystal display element was produced in the same manner as in Example 6.

[Example 8]
PA8 and PA11 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. In a solution obtained by dilution, 20 parts by weight of 157S70 was dissolved with respect to 100 parts by weight of polyamic acid to obtain a liquid crystal aligning agent 16. A liquid crystal display device was produced in the same manner as in Example 6 using the obtained liquid crystal aligning agent 16.

[Comparative Example 9]
PA8 and PA11 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. The liquid crystal aligning agent 17 was obtained by diluting. A liquid crystal display element was produced in the same manner as in Example 6 using the obtained liquid crystal aligning agent 17.

[Comparative Example 10]
PA2 and PA11 are mixed at a weight ratio of 9/1, and a mixed solvent of NMP / BC = 1/1 (weight ratio) is added to the resulting mixture so that the concentration of polyamic acid becomes 4% by weight as a whole. In a solution obtained by dilution, 20 parts by weight of TGDDM was dissolved in 100 parts by weight of polyamic acid to obtain a liquid crystal aligning agent 18. A liquid crystal display element was produced in the same manner as in Example 6 using the obtained liquid crystal aligning agent 18.

<3. Evaluation of residual voltage>
The residual voltage was measured about the liquid crystal display element produced in Examples 1-8 and Comparative Examples 1-10. In the measurement, the liquid crystal display element was applied with a 30 Hz, 1.62 V rectangular wave biased with 3 V DC in Examples 1 to 5 and Comparative Examples 1 to 6, and 3 V DC in Examples 6 to 8 and Comparative Examples 7 to 10. A biased 30 Hz, 3.20 V rectangular wave was applied for 30 minutes, and the voltage remaining in the liquid crystal cell immediately after turning off the DC voltage was determined by the flicker erasing method. It can be said that the seizure phenomenon is less likely to occur as the residual voltage value is smaller. The results are shown in Table 2.

  As shown in Table 2, in the liquid crystal display device using the liquid crystal aligning agents of Examples 1 to 8 in which an epoxy compound was added to the polyamic acid solution using either BT100 or PSQ1, or both, the residual voltage Was able to be reduced.

Claims (28)

A liquid crystal aligning agent comprising a polyamic acid or a derivative thereof having a structure of a reaction product of tetracarboxylic dianhydride or a derivative thereof and a diamine or a derivative thereof, and an epoxy compound having two or more epoxy groups. ,
The said tetracarboxylic dianhydride or its derivative contains the compound represented by following formula (I), The liquid crystal aligning agent characterized by the above-mentioned.

(In the formula (I), -X ¹ -represents a single bond or a divalent group represented by the following formula (II). In the formula (II), -Ph represents a phenyl group.)

The liquid crystal aligning agent according to claim 1, wherein —X ¹ — in the formula (I) is a single bond. The tetracarboxylic dianhydride or derivative thereof further includes one or both of the compounds represented by the following formulas (1) and (14), or the diamine or derivative thereof comprises the following formulas (III) to (IX). One or more compounds selected from the group, or the tetracarboxylic dianhydride or derivative thereof further comprises one or both of the compounds of the following formulas (1) and (14), and the diamine or derivative thereof: The liquid crystal aligning agent according to claim 2, comprising one or more compounds selected from the group consisting of the following formulas (III) to (IX).

(In the formulas (III) and (IV), m and n each represents an integer of 1 to 12,
Wherein (VI) ~ (VIII), -Y 1, -Y 2, and -Y ³ each represent an alkyl from -H or C 1 -C 30,
In the formula (IX), —X ² — independently represents —CH ₂ — or —O—, and —Y ⁴ represents alkyl having 1 to 30 carbon atoms, the following formula (X), or the following formula (XI). To express. )

(In the formulas (X) and (XI), -Y ⁵ and -Y ⁶ each represent alkyl having 1 to 30 carbon atoms.) The diamine or a derivative thereof is represented by the following formulas (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), (VIII-1) The liquid crystal aligning agent according to claim 3, wherein the liquid crystal aligning agent is one or more compounds selected from the group consisting of: (IX-1), (X-1), and (XI-1).

The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent of Claim 4. The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or a derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), and (IV-1). Liquid crystal aligning agent. The diamine or a derivative thereof is one or more compounds selected from the group consisting of the formulas (IX-1), (X-1), and (XI-1). Liquid crystal aligning agent. The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or a derivative thereof is one or more compounds selected from the group consisting of the formulas (IX-1), (X-1), and (XI-1). Liquid crystal aligning agent. The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1), and the formula (III) VI-1) or (VII-1) is included, The liquid crystal aligning agent of Claim 4 characterized by the above-mentioned. The tetracarboxylic dianhydride or a derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to claim 9, wherein the diamine or a derivative thereof is the compound of the formula (VII-1). 2. The liquid crystal aligning agent according to claim 1, wherein —X ¹ — in the formula (I) is a divalent group represented by the formula (II). The tetracarboxylic dianhydride or a derivative thereof further includes one or both of compounds of the following formulas (1) and (14), or the diamine or a derivative thereof consists of the following formulas (III) to (VIII): One or more compounds selected from the group, or the tetracarboxylic dianhydride or derivative thereof further comprises one or both of the compounds of the following formulas (1) and (14), and the diamine or derivative thereof: The liquid crystal aligning agent according to claim 11, comprising one or more compounds selected from the group consisting of the following formulas (III) to (VIII).

(In the formulas (III) and (IV), m and n each represents an integer of 1 to 12,
Wherein (VI) ~ (VIII), -Y 1, -Y 2, and -Y ³ each represent an alkyl from -H or C 1 -C 30. ) The diamine or a derivative thereof is represented by the following formulas (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent according to claim 12, which is one or more compounds selected from the group consisting of:

The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent of Claim 13. The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent of Claim 14. The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent of Claim 13. The tetracarboxylic dianhydride or derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to claim 16, wherein the diamine or a derivative thereof is the compound of the formula (VII-1). In the tetracarboxylic dianhydride, a compound in which —X ¹ — is a single bond in the formula (I), and —X ¹ — in the formula (I) is represented by the formula (II) 2 The liquid crystal aligning agent according to claim 1, wherein a compound that is a valent group is used. The tetracarboxylic dianhydride or a derivative thereof further includes one or both of compounds of the following formulas (1) and (14), or the diamine or a derivative thereof consists of the following formulas (III) to (VIII): One or more compounds selected from the group, or the tetracarboxylic dianhydride or derivative thereof further comprises one or both of the compounds of the following formulas (1) and (14), and the diamine or derivative thereof: The liquid crystal aligning agent according to claim 18, comprising one or more compounds selected from the group consisting of the following formulas (III) to (VIII):

(In the formulas (III) and (IV), m and n each represents an integer of 1 to 12,
Wherein (VI) ~ (VIII), -Y 1, -Y 2, and -Y ³ each represent an alkyl from -H or C 1 -C 30. ) The diamine or a derivative thereof is represented by the following formulas (III-1), (III-2), (IV-1), (V-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent according to claim 19, wherein the liquid crystal aligning agent is one or more compounds selected from the group consisting of:

The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent of Claim 20. The tetracarboxylic dianhydride or derivative thereof includes one or both compounds of the formulas (1) and (14),
The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (III-2), (IV-1), and (V-1). The liquid crystal aligning agent of Claim 21. The diamine or derivative thereof is one or more compounds selected from the group consisting of the formulas (III-1), (VI-1), (VII-1), and (VIII-1). The liquid crystal aligning agent of Claim 20. The tetracarboxylic dianhydride or derivative thereof includes the compound of the formula (14),
The liquid crystal aligning agent according to claim 23, wherein the diamine or a derivative thereof is a compound of the formula (VII-1).   The epoxy compound is selected from the group consisting of glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. It is the above, The liquid crystal aligning agent as described in any one of Claims 1-24 characterized by the above-mentioned.   The epoxy compound is N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, bisphenol A novolak type The one or more selected from the group consisting of an epoxy compound, a cresol novolac-type epoxy compound, a bisphenol A-type epoxy compound, and N, N, O-triglycidyl-p-aminophenol, Liquid crystal aligning agent.   The liquid crystal aligning film formed by baking the film | membrane of the liquid crystal aligning agent as described in any one of Claims 1-26.   A pair of substrates disposed opposite to each other, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and liquid crystal formed on the opposed surfaces of the pair of substrates. 28. A liquid crystal display element having an alignment film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to claim 27.