KR20100047819A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal aligning agent is provided to form a liquid crystal aligning layer capable of supplying desired voltage holding rate for a liquid crystal display. CONSTITUTION: A liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyamic acid and its derivative. The polyamic acid and its derivative is obtained by reacting more than one diamine marked as the chemical formula N or a mixture of the diamine marked as the chemical formula N and the diamine cannot be marked as the chemical formula N, with tetracarboxylic acid dianhydride.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT LAYER AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to the liquid crystal aligning agent containing the polyamic acid obtained by mainly reacting the diamine containing naphthalene in a principal chain with tetracarboxylic dianhydride.

BACKGROUND ART Liquid crystal display devices are used in various liquid crystal display devices such as monitors of notebook computers and desktop computers, viewfinders of video cameras, projection displays, and the like. Liquid crystal display elements are also used in optoelectronics-related elements such as optical printer heads, optical Fourier transform elements, and light bulbs.

Although various elements are known in the liquid crystal display device, the development of the technology of the liquid crystal display device is achieved not only by the improvement of the driving method of the liquid crystal display device and the structure of the liquid crystal display device but also by the improvement of the constituent members used in the liquid crystal display device. have. The liquid crystal display element usually has a liquid crystal aligning film for orientating the liquid crystal composition in a liquid crystal layer in a specific direction. A liquid crystal aligning film is one of the important factors regarding the display quality of a liquid crystal display element, and the role of a liquid crystal aligning film becomes increasingly important with the quality improvement of a liquid crystal display element.

A liquid crystal aligning film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. After apply | coating such a solution to a board | substrate, a liquid crystal aligning film is formed by forming into a film by means, such as a heating.

A voltage retention is mentioned as an important characteristic requested | required of a liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. When the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may cause normal gray scale display. Further, for example, even when the initial voltage holding ratio is high, it is not preferable when the voltage holding ratio (long-term reliability) after the high temperature acceleration test decreases.

As an attempt to solve the above-mentioned problem, for example, a polyamic acid composition comprising a combination of two or more polyamic acids having different physical properties for forming a liquid crystal alignment film is known (see Patent Documents 1 and 2, for example). . Moreover, the synthesis | combining method of the polyamic acid obtained by making aromatic diamine which has naphthalene, and tetracarboxylic dianhydride react is known (for example, refer patent document 3). However, a recent improvement is required for the recent liquid crystal aligning film, and in the liquid crystal aligning agent which forms this, there exists room for further examination in order to acquire desired electrical characteristics with respect to the obtained liquid crystal aligning film.

[Patent Document 1] Japanese Patent Application Publication No. Hei 11-193345

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-193347

[Patent Document 3] Publication US5886131

The present invention provides a liquid crystal display device in which the expression of the desired voltage holding ratio and its long-term stability are achieved, a liquid crystal aligning film that achieves the expression of the desired voltage holding ratio and its long-term stability in the liquid crystal display, and a liquid crystal aligning agent capable of forming the same. To provide.

MEANS TO SOLVE THE PROBLEM The present inventors, when making the composition containing the polyamic acid which uses the aromatic diamine which has naphthalene, or its derivative as a liquid crystal aligning agent, in the liquid crystal display element which has the liquid crystal aligning film formed using it, the desired voltage retention is expressed, Moreover, it discovered that favorable long-term reliability was provided and completed this invention.

The liquid crystal aligning agent of this invention is described in following [1].

[1] A composition containing at least one polymer selected from the group consisting of polyamic acids and derivatives thereof, wherein the polymer is at least one of diamines represented by formula (N) or diamines represented by formula (N) The liquid crystal aligning agent which is a polyamic acid or its derivative (s) obtained by making the mixture of at least 1 and at least 1 of other diamine which is a diamine which is not represented by Formula (N) react with tetracarboxylic dianhydride.

Wherein A ¹ is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, hydroxy, trifluoromethyl, fluorine, chlorine or bromine; m is independently an integer of 0 to 3; A ² is independently —O—, —NH—, —N (CH ₃ ) —, or —S—; The bonding position of the two amino groups to the benzene ring is any position except for the bonding positions of A ₁ and A ₂ .

According to the present invention, it is possible to provide a liquid crystal display device which can be applied to various driving systems having a high voltage holding ratio and good long-term reliability against its fluctuations over time.

First, the term used by this invention is demonstrated.

"Liquid crystal aligning agent" means the composition used for forming a liquid crystal aligning film. The diamine represented by a formula (N) may be called diamine (N). The same applies to the diamine represented by another formula. Tetracarboxylic dianhydride represented by Formula (1) may be called carboxylic acid (1). The same applies to tetracarboxylic dianhydride represented by another formula. Other diamine means diamines other than diamine (N). The term "arbitrary" used when describing the chemical structural formula means that the term is arbitrary with respect to the number as well as the position. For example, the expression "any A may be substituted with B, C, or D" may be used when any A is substituted with B, when any A is substituted with C, and any A In addition to the case where is substituted with D, it means including a case where several A is substituted by at least two of B-D. However, in the case where any -CH ₂ -may be substituted with -O-, those in which a plurality of consecutive -CH ₂ -are replaced with -O- are not included. Substituents which are not specifically bonded to the atoms constituting the ring are substituents which can freely determine the bonding position within a chemically acceptable range. The letter, for example, a symbol enclosing A in hexagon means ring A.

The present invention comprises the above-mentioned [1] and the following [2] to [20].

[2] The liquid crystal aligning agent according to [1], wherein the bonding position of two amino groups in formula (N) is also a para position with respect to A ₂ .

[3] The diamine is formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and formula (N -16) The liquid crystal aligning agent as described in [1] which is a mixture of at least 1 diamine selected from the compound group represented by (16), or its (di) diamine, and other diamine.

In these formulas, Me means methyl.

[4] The liquid crystal aligning according to [3], wherein the diamine is a mixture of at least one of diamines represented by formulas (N-1) and (N-3) or their (they) diamines with other diamines. My.

[5] The diamine is a mixture of at least one of the diamines represented by the formula (N) with other diamines, and the other diamines are selected from the diamine groups represented by the formulas (VIII) and (X) to (XIII). The liquid crystal aligning agent as described in [1] which is at least 1 of the diamine which has a side chain group used.

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX), and having 3 to 30 carbon atoms Any -CH ₂ -in alkyl of may be substituted with -O-, -CH = CH- or -C -C-.

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene.

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms, and R ⁷ and R ⁸ are each independently having 1 to C carbon atoms. 20 alkyl or phenyl and A ⁶ is independently a single bond, -CO- or -CH _2- .

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1;

[6] The diamine is formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and formula (N -16) is a mixture of at least one diamine selected from the group of compounds represented by -16) with other diamines, and other diamines are formulas (VIII-2), (VIII-4) to (VIII-6), The liquid crystal aligning agent of [3] which is at least 1 of the diamine which has a side chain group chosen from diamine represented by a formula (XII-2), a formula (XII-4), and a formula (XII-6).

In these formulae, R ²³ , R ²⁹ and R ³⁰ are each alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, respectively.

[7] The diamine is a mixture which also contains a diamine having no side chain group, wherein at least one diamine having no side chain group is selected from the group of compounds represented by formulas (I) to (VII) and (XV). And liquid crystal aligning agent in any one of [1]-[6].

In these formulas, X is C2-C12 linear alkylene; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms; t is an integer from 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl.

[8] The diamine having no side chain group is formula (IV-1), formula (IV-2), formula (IV-15) to formula (IV-17), formula (V-1) to formula (V-12) At least one of the diamines represented by formula (V-33), formula (V-35) to formula (V-37), formula (VI-7), formula (VII-2) and formula (XV-1), The liquid crystal aligning agent as described in [7].

[9] A mixture of a polymer with at least one of the diamines represented by formula (N) and at least one of diamines having a side chain group selected from the group of diamines represented by formulas (VIII) and (X) to (XIII). Or at least one of diamines having a side chain group selected from at least one of diamines represented by formula (N) and a diamine group represented by formulas (VIII) and (X) to (XIII) and formulas (I) to ( VII) and a polyamic acid or derivative thereof obtained by reacting a mixture consisting of at least one of diamines having no side chain group selected from the diamine group represented by the formula (XV) with tetracarboxylic dianhydride and the diamine having no side chain group described above. Obtained by reacting a mixture of at least one or at least one of the diamines having no side chain groups with at least one of the diamines represented by the formula (N) with tetracarboxylic dianhydride The liquid crystal aligning agent as described in [1] which is a mixture with a polyamic acid or its derivative (s).

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Optional -CH ₂ -in alkyl of 30 may be substituted with -O-, -CH = CH-, or -C≡C-.

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene.

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms, and R ⁷ and R ⁸ are each independently having 1 to C carbon atoms. 20 alkyl or phenyl and A ⁶ is independently a single bond, -CO- or -CH _2- .

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1;

In these formulas, X is C2-C12 linear alkylene; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms, t is an integer from 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl.

[10] the polymer with at least one of the diamines represented by the formula (N) and at least one of the diamines having no side chain group selected from the diamine groups represented by the formulas (I) to (VII) and (XV). At least one or a side chain of the polyamic acid obtained by reacting a mixture with tetracarboxylic dianhydride, or its derivative (s), and the diamine which has a side chain group chosen from the diamine group represented by Formula (VIII) and Formula (X)-Formula (XIII). The liquid crystal aligning agent of [1] which is a mixture of the polyamic acid obtained by making the mixture of at least 1 of the diamine which has a group, and at least 1 of the diamine which does not have the above-mentioned side chain group with tetracarboxylic dianhydride or its derivative (s).

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Optional -CH ₂ -in alkyl of 30 may be substituted with -O-, -CH = CH-, or -C≡C-.

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxy alkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene.

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms, and R ⁷ and R ⁸ are each independently having 1 to C carbon atoms. 20 alkyl or phenyl and A ⁶ is independently a single bond, -CO- or -CH _2- .

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1;

In these formulas, X is C2-C12 linear alkylene; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms, t is an integer from 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl.

[11] The diamine represented by formula (N) is formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), or formula (N -15) or a diamine represented by formula (N-16), wherein the diamine having a side chain group is represented by formula (VIII-2), formula (VIII-4) to formula (VIII-6), formula (XII-2), Diamine represented by Formula (XII-4) or Formula (XII-6), and the diamine which does not have a side chain group is Formula (IV-1), Formula (IV-2), Formula (IV-15)-Formula (IV) -17), formula (V-1) to formula (V-12), formula (V-33), formula (V-35) to formula (V-37), formula (VI-7), formula (VII- 2) or liquid crystal aligning agent as described in [9] or [10] which is diamine represented by Formula (XV-1).

In these formulas, Me means methyl.

In these formulae, R ²³ , R ²⁹ and R ³⁰ are each alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, respectively.

[12] The liquid crystal aligning agent according to any one of [1] to [11], wherein the tetracarboxylic dianhydride is a mixture of an aromatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride with tetracarboxylic dianhydride other than aromatic.

[13] at least one aromatic tetracarboxylic dianhydride selected from the group of compounds represented by formulas (1), (2), (5) to (7), (11) and (14); The liquid crystal aligning agent as described in [12].

[14] The liquid crystal aligning agent according to [13], wherein the aromatic tetracarboxylic dianhydride is a compound represented by formula (1).

[15] The liquid crystal aligning agent according to [12], wherein tetracarboxylic dianhydrides other than aromatics are alicyclic tetracarboxylic dianhydrides and / or aliphatic tetracarboxylic dianhydrides.

[16] The aromatic tetracarboxylic dianhydride is at least one selected from the group of compounds represented by formulas (1), (2), (5) to (7), (11) and (14). And tetracarboxylic dianhydrides other than aromatics from the group of compounds represented by formulas (19), (23), (25), (35) to (39), (44) and (49). The liquid crystal aligning agent of [12] which is at least 1 selected.

[17] The liquid crystal aligning agent according to [16], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (1), and tetracarboxylic dianhydride other than the aromatic is a compound represented by the formula (19).

[18] [1] to [17], further containing at least one compound selected from an alkenyl substituted naziimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. The liquid crystal aligning agent in any one of them.

[19] A liquid crystal alignment film formed by heating the coating film of the liquid crystal aligning agent according to any one of [1] to [18].

[20] a liquid crystal layer containing a pair of substrates, liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for orienting the liquid crystal molecules in a predetermined direction. The liquid crystal display element which has a liquid crystal display element WHEREIN: The said liquid crystal aligning film is a liquid crystal aligning film as described in [19].

The liquid crystal aligning agent of this invention contains the polyamic acid or its derivative which is a reaction product of tetracarboxylic dianhydride and diamine. Examples of the derivative of this polyamic acid are soluble polyimide, polyamic acid ester, polyamic acid amide, and the like. More specifically, (1) a polyimide in which the polyamic acid is completely dehydrated and closed, (2) a partial polyimide subjected to a partially dehydrating and ring closing reaction, (3) a polyamic acid ester in which the carboxyl of a polyamic acid is converted to an ester, and (4) The polyamic acid-polyamide copolymer obtained by making the mixture of tetracarboxylic dianhydride and an organic dicarboxylic acid react, and (5) the polyamideimide which dehydrated and closed part or all of this polyamic acid-polyamide copolymer is mentioned. And a preferable example of the derivative of polyamic acid is polyimide. The liquid crystal aligning agent of this invention is a composition containing at least 1 polymer chosen from the group which consists of a polyamic acid and derivatives of such a polyamic acid.

In the present invention, at least one of the diamines represented by formula (N) is used.

In formula (N), A <^1> is independently C1-C10 alkyl, C1-C10 alkoxy, hydroxy, trifluoromethyl, fluorine, chlorine, or bromine. Preferred examples of A ¹ are alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, hydroxy and trifluoromethyl. More preferred examples of A ¹ are methyl, methoxy, hydroxy and trifluoromethyl. m is an integer of 0-3 independently, Preferably all are 0 or 1. A ² is independently —O—, —NH—, —N (CH ₃ ) —, or —S—. It is preferable that two A ² are the same bonding group. The bonding position of two amino groups to the benzene ring is any position except the bonding position of A <^1> and A <^2> , and it is preferable that all are couple | bonded with the para position with respect to A <^2> .

Preferred examples of the diamine (N) are as follows.

Me in these formulas means methyl.

Among the diamines described above, diamines (N-1) to diamines (N-5), diamines (N-7), diamines (N-8), diamines (N-13), diamines (N-15), and diamines ( N-16) is preferable, and diamine (N-1) and diamine (N-3) are more preferable.

When manufacturing a polymer in the liquid crystal aligning agent of this invention, only diamine (N) may be used and you may mix and use this diamine and other diamine, ie, the diamine which is not represented by Formula (N). The use ratio of diamine (N) is 5-100 mol with respect to the total amount of the diamine used when manufacturing the said polymer from a viewpoint of expressing a desired ion density in a liquid crystal display element, and realizing its long-term stability. It is preferable that it is%, and it is more preferable that it is 5-50 mol%.

By the way, the other diamine can be divided into two types according to the difference of the structure. That is, when the backbone which links two amino groups is seen by the main chain, it is the diamine which has the branch branched from the main chain, ie, the diamine which has a side chain group, and a side chain group. By reacting diamine which has a side chain group with tetracarboxylic dianhydride, the polyamic acid or polyimide which has many side chain groups with respect to the main chain of a polymer can be obtained. When using the polyamic acid or polyimide which has a side chain group with respect to such a polymer main chain, the liquid crystal aligning film formed from the liquid crystal aligning agent containing this polymer can enlarge the pretilt angle in a liquid crystal display element. That is, this side chain group is group which has an effect which enlarges a pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms, and specific examples include a group having 3 or more carbon atoms, alkoxy having 3 or more alkoxy, an alkoxyalkyl having 3 or more carbon atoms, and a steroid skeleton. It is a group which has one or more rings, and the ring of the terminal has an effect as an airway side chain group which has any one of a C1 or more alkyl, a C1 or more alkoxy, and a C2 or more alkoxyalkyl as a substituent. The side chain groups in the present invention are selected from these groups. In the following description, the diamine which has such a side chain group may be called a side chain type diamine.

And the diamine which does not have a C3 or more side chain group may be called non-branched diamine. By appropriately using the branched diamine and the non-branched diamine, it is possible to cope with the pretilt angles necessary for the various display elements individually. That is, since a relatively large pretilt angle is required in the longitudinal electric field system represented by TN system or VA system, branched diamine is mainly used. At this time, in order to control the pretilt angle, non-branched diamine may be used together. What is necessary is just to determine the compounding ratio of a non-branched diamine and a branched diamine according to the magnitude | size of the target pretilt angle. Of course, by appropriately selecting a side chain group, it can also respond using only a side chain type diamine. In the electric field system, since the pretilt angle is small and high liquid crystal orientation is required, at least one of the non-branched diamines may be used. Thus, the liquid crystal aligning agent of this invention can be applied to the liquid crystal display element of arbitrary types.

Specific examples of the side chains are as follows.

First, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyl Oxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like. And alkyl, alkenyl, and alkynyl in these groups are all C3 or more groups. However, in alkyloxyalkyl, what is necessary is just three or more carbon atoms as a whole. In addition, these groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy, provided that the terminal ring has, as substituents, alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms or alkoxyalkyl having 2 or more carbon atoms. Phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyl Oxy, bis (cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) phenyl, bis (cyclohexyl) phenylalkyl, bis (cyclohexyl) oxycarbonyl, bis (cyclohexyl) phenyloxycarbonyl, And groups having a ring structure such as cyclohexylbis (phenyl) oxycarbonyl.

Moreover, it is group which has two or more benzene rings, group which has two or more cyclohexane rings, or two or more rings which consist of a benzene ring and a cyclohexane ring, and a bond group is independently a single bond, -O-, -COO -, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, wherein the terminal ring has, as a substituent, an alkyl having 1 or more carbon atoms, a fluorine-substituted alkyl having 1 or more carbon atoms, an alkoxy having 1 or more carbon atoms, or an alkoxyalkyl having 2 or more carbon atoms And a ring collector. Of course, it is effective as an airway side chain group having a steroid skeleton.

Preferred examples of the branched diamine are diamines represented by formulas (VIII) and (X) to (XIII).

In formula (VIII), A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or 1 to 6 carbon atoms. Is alkylene, and arbitrary -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH-, or -C≡C-. Preferred examples of A ³ are a single bond, —O—, —COO—, —OCO—, —CH ₂ O—, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are single bond, —O—, —COO -, -OCO-, -CH ₂ O-, -CH _2- , and -CH ₂ CH _2- . R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Optional -CH ₂ -in alkyl of 30 may be substituted with -O-, -CH = CH- or -C≡C-. Preferred examples of R ¹ are phenyl having alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, and a group represented by formula (IX). The position where the two amino groups are bonded to the benzene ring is preferably at positions 3 and 5 or positions 2 and 5 when the bond position of A ³ is set to position 1;

In formula (IX), A <^4> and A <^5> are independently a single bond, -O-, -COO-, -OCO-, -CONH-, C1-C4 alkylene, C1-C3 oxyalkylene Or alkyleneoxy having 1 to 3 carbon atoms, preferably a single bond or alkylene having 1 to 4 carbon atoms. Ring B and Ring C are independently 1,4-phenylene or 1,4-cyclohexylene. R ² and R ³ are independently fluorine or methyl. f and g are independently 0, 1 or 2, Preferably it is 0. c, d, and e are the integers of 0-3 independently, and these sum total is one or more. R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxy alkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene. Preferred examples of R ⁴ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl. R ⁶ is hydrogen, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons. R ⁷ and R ⁸ are each independently alkyl or phenyl having 1 to 20 carbon atoms. A ⁶ is independently a single bond, -CO- or -CH _2- . In the formula (X), the two ^{_{"NH 2 -Ph-A 6 -O-}} " one side is bonded to position 3 of the steroid skeleton and the other one is preferably bonded to the 6-position. In addition, it is preferable that the bonding position of two amino groups with the benzene ring is a meta position or a para position with respect to the bonding position of A <^6> all. In formula (XI), the bonding positions of the two "NH _2- (R ^6- ) Ph-A ⁶ -O-" benzene rings are both meta or para positions with respect to the carbon to which the steroid skeleton is bonded. It is preferable. In addition, it is preferable that the bonding position of two amino groups with the benzene ring is a meta position or a para position with respect to the bonding position of A <^6> all.

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. It may be substituted. R ¹⁰ is alkyl having 6 to 22 carbons, and R ¹¹ is alkyl having 1 to 22 carbons. A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms. A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms. Ring T is 1,4-phenylene or 1,4-cyclohexylene. h is 0 or 1; In Formula (XII), it is preferable that the bonding position of two amino groups with the benzene ring is a meta position or a para position with respect to the bonding position of A <^7> . In Formula (XIII), it is preferable that all the bonding positions of the two amino groups with the benzene ring are metaposition or paraposition with respect to the bonding position of A <^7> .

Specific examples of the diamine (VIII) are as follows.

In formulas (VIII-1) to (VIII-11), R ²³ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms or alkoxy having 5 to 25 carbon atoms. to be. R <^24> is C1-C30 alkyl or C1-C30 alkoxy, Preferably it is C3-C25 alkyl or C3-C25 alkoxy.

In formulas (VIII-12) to (VIII-17), R ²⁵ is alkyl having 4 to ³⁰ carbon atoms, preferably alkyl having 6 to ²⁵ carbon atoms. R ²⁶ is alkyl having 6 to 30 carbon atoms, preferably alkyl having 8 to 25 carbon atoms.

In formulas (VIII-18) to (VIII-37), R ²⁷ is alkyl having 1 to 30 carbon atoms, or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 25 carbon atoms or 3 to 25 carbon atoms. Is alkoxy. R ²⁸ is hydrogen, fluorine, alkyl of 1 to 30 carbon atoms, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF _3, of 1 to 30 carbon atoms, preferably alkyl having a carbon number of 3 to 25 carbon atoms or a 3 -25 is alkoxy.

Among the diamines (VIII-1) to diamine (VIII-43), diamines (VIII-1) to diamines (VIII-11) are preferable, and diamines (VIII-2) and diamines (VIII-4) to diamines (VIII). -6) is more preferable.

The specific example of diamine (X) is shown next.

The specific example of diamine (XI) is shown next.

The specific example of diamine (XII) is shown next.

In formulas (XII-1) to (XII-3), R ²⁹ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. to be. In formulas (XII-4) to (XII-8), R ³⁰ is alkyl having 1 to ³⁰ carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms. to be.

The specific example of diamine (XIII) is shown next.

In formulas (XIII-1) to (XIII-3), R ³¹ is alkyl having 6 to 22 carbon atoms, and preferably alkyl having 6 to 20 carbon atoms. R ³² is alkyl having 1 to 22 carbons, preferably alkyl having 1 to 10 carbons.

Among the specific examples of the above branched diamine, diamine (VIII-2), diamine (VIII-4) to diamine (VIII-6), diamine (XII-2), diamine (XII-4) and diamine (XII-6) Is preferred.

When the above-mentioned side chain type diamine aims at expressing a large pretilt angle in a liquid crystal display element, when manufacturing the polymer used for the liquid crystal aligning agent of this invention, the ratio in diamine total amount is 1 It is preferable to set it as -90 mol%, and it is more preferable to set it as 5-70 mol%.

As a preferable example of the diamine which does not have the same side chain group mentioned above, ie, a non-branched diamine, the compound represented by Formula (I)-Formula (VII) and Formula (XV) is mentioned.

In these formulas, X is C2-C12 linear alkylene. Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms, t is an integer of 1-12. Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- You may form a single bond. Ring D is phenylene or 1,4-diazacyclohexylene. R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms. A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms. m is an integer of 1-10. Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl.

An example of diamine (I) is shown next.

The specific example of diamine (II) is shown next.

The specific example of diamine (III) is shown next.

The specific example of diamine (IV) is shown next.

The specific example of diamine (V) is shown next.

The specific example of diamine (VI) is shown next.

The specific example of diamine (VII) is shown next.

The specific example of diamine (XV) is shown next.

Among the above non-branched diamines, diamines (IV-1) to diamines (IV-5), diamines (IV-15) to diamines (IV-17), diamines (V-1) to diamines (V-12), Diamine (V-26), Diamine (V-27), Diamine (V-31), Diamine (V-33), Diamine (V-35) to Diamine (V-37), Diamine (VI-1), Diamine (VI-2), diamine (VI-6), diamine (VII-1) to diamine (VII-5) and diamine (XV-1) are preferable, and diamine (IV-1) and diamine (IV-2) Diamine (IV-15) to diamine (IV-17), diamine (V-1) to diamine (V-12), diamine (V-33), diamine (V-35) to diamine (V-37) , Diamine (VI-7), diamine (VII-2) and diamine (XV-1) are more preferred.

Such non-branched diamine contains 1 to 98% in molar ratio in the total amount of diamine as a raw material of polyamic acid in the liquid crystal aligning agent of the present invention from the viewpoint of expressing desired electrical properties such as ion density in the liquid crystal display device. It is preferable to become it, and it is more preferable to contain 10 to 95%.

Diamines other than the diamine (I)-diamine (VIII), diamine (X)-diamine (XIII), and diamine (XV) which were mentioned above can be used for the diamine used by this invention. As such diamine, the side chain type diamine other than fluorene type diamine which has a fluorene ring, and diamine (VIII)-diamine (XII) is mentioned, for example.

Examples of branched diamines other than diamine (VIII) to diamine (XII) are diamine (1 ') to diamine (8').

In these formulas, R ³⁵ and R ³⁶ each independently represent an alkyl group having 3 to 30 carbon atoms. These diamines can be used in the range of the grade which does not impair the effect of this invention, when manufacturing a polyamic acid in the liquid crystal aligning agent of this invention.

When manufacturing a polyamic acid, you may add a monoamine to diamine. By adding a monoamine, termination of the polymerization reaction at the time of producing the polyamic acid can be caused, and further progress of the polymerization reaction can be suppressed. That is, the molecular weight of the polymer (polyamic acid or its derivative) obtained can be easily controlled, for example, the coating property of a liquid crystal aligning agent can be improved, without the effect of this invention being impaired. What is necessary is just to adjust the addition ratio of monoamine in consideration of the molecular weight of the polyamic acid made into the objective. As long as the effect of this invention is not impaired, you may add 2 or more types of monoamines. Examples of monoamines are aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decyl Amines, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, And n-eicosylamine.

In the following description except for the examples, "polyamic acid" is used as a generic name of polyamic acid and its derivatives unless otherwise specified.

In the present invention, when a diamine is reacted with tetracarboxylic dianhydride to obtain a polyamic acid, a mixture of diamine (N) and other diamines can be used as described above. At this time, one of the preferable examples of other diamine is at least 1 of the side chain type diamine selected from the group of diamine (VIII) and diamine (X)-diamine (XIII). Still other preferred examples of other diamines include at least one of branched diamines selected from the group of diamines (VIII) and diamines (X) to diamines (XIII), diamines (I) to diamines (VII) and diamines ( XV) and a mixture with at least one of the unbranched diamines selected from the group. [5] to [8] mentioned above are preferable examples of the combination of diamine (N), branched diamine and non-branched diamine.

In this invention, the polyamic acid obtained by making mixed diamine react with tetracarboxylic acid as mentioned above may be used as a polymer component, and the mixture of polyamic acid from which a raw material differs may be used as a polymer component. One preferred example of a mixture of polyamic acids is a mixture of at least one of diamines (N) with at least one of branched diamines selected from the group of diamines (VIII) and diamines (X) to diamines (XIII) or mixtures of these diamines The polyamic acid obtained by reacting the mixture which further added at least 1 of the non-branched diamine selected from the group of diamine (I)-diamine (VII) and diamine (XV) with tetracarboxylic dianhydride, and the above-mentioned non-side chain A mixture of polyamic acid obtained by reacting at least one of the diamines or at least one of the non-branched diamines with at least one of the diamines (N) with tetracarboxylic dianhydride.

Another preferred example of a mixture of polyamic acids is a mixture of at least one of diamines (N) with at least one of non-branched diamines selected from the group of diamines (I) to diamines (VII) and diamines (XV). At least one of polyamic acid obtained by reacting with tetracarboxylic dianhydride and branched diamines selected from the group of diamines (VIII) and diamines (X) to diamines (XIII), or at least one of these branched diamines and the aforementioned ratio A mixture with a polyamic acid obtained by reacting a mixture with at least one of the branched diamines with tetracarboxylic dianhydride. [9] to [11] above describe preferred examples in which the polymer component is a mixture of polyamic acid.

The tetracarboxylic dianhydride used in the present invention may be one kind of compound or two or more kinds of compounds. As tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride are mentioned.

An example of aromatic tetracarboxylic dianhydride is shown below.

Among the aromatic tetracarboxylic dianhydrides, carboxylic acid (1), carboxylic acid (2), carboxylic acid (5) to carboxylic acid (7), carboxylic acid (11) and carboxylic acid (14) are preferable, and carboxylic acid (1) is particularly preferable. .

An example of an alicyclic tetracarboxylic acid dianhydride is shown next.

Of the alicyclic tetracarboxylic dianhydrides, carboxylic acid (19), carboxylic acid (25), carboxylic acid (35) to carboxylic acid (37), carboxylic acid (39), carboxylic acid (44) and carboxylic acid (49) are preferred, and carboxylic acid ( 19) is more preferable.

Examples of aliphatic tetracarboxylic dianhydride are shown below. Carboxylic acid (23) is preferable in the following examples.

In this invention, tetracarboxylic dianhydride other than said carboxylic acid (1)-carboxylic acid (67) can also be used. Examples thereof include tetracarboxylic dianhydride having a side chain group. By using tetracarboxylic dianhydride which has a side chain group, the pretilt angle in a liquid crystal display element can be enlarged. As tetracarboxylic dianhydride which has a side chain group, the carboxylic acid 68 and carboxylic acid 69 which have a steroid skeleton are mentioned, for example.

When manufacturing a polyamic acid, you may add and use a dicarboxylic anhydride to tetracarboxylic dianhydride. By doing so, termination of the polymerization reaction at the time of producing the polyamic acid can be caused, and further progress of the polymerization reaction can be suppressed. That is, the molecular weight of the polymer (polyamic acid) obtained can be easily controlled, for example, the coating characteristic of a liquid crystal aligning agent can be improved, without the effect of this invention being impaired. What is necessary is just to adjust the addition ratio of dicarboxylic anhydride suitably in consideration of the molecular weight of the target polyamic acid. Moreover, the kind of dicarboxylic acid anhydride to add may be 2 or more types, unless the effect of this invention is impaired. Examples of the dicarboxylic acid anhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic acid Anhydride and cyclohexanoic anhydride.

In this invention, when manufacturing a polyamic acid, you may add a monoisocyanate compound further. By adding a monoisocyanate compound, the terminal of the obtained polyamic acid is modified and molecular weight is adjusted. By using this terminal modified polyamic acid, the effect of this invention can be improved, for example, without impairing the effect of this invention. The addition amount of the monoisocyanate compound is preferably 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride, from the above viewpoint. As a monoisocyanate compound, phenyl isocyanate and naphthyl isocyanate are mentioned, for example.

The polyamic acid used by this invention can be manufactured similarly to the well-known polyamic acid used for formation of the film of a polyimide. It is preferable to make the total amount of tetracarboxylic acid dianhydride into the mole (molar ratio about 0.9-1.1) almost the same as the total mole number of diamine.

It is preferable that it is 10,000-500,000, and, as for the molecular weight of polyamic acid, it is the weight average molecular weight (Mw) of polystyrene conversion, and it is more preferable that it is 20,000-200,000. The molecular weight of polyamic acid can be calculated | required from the measured value by gel permeation chromatography (GPC) method.

The presence of a polyamic acid can be confirmed by analyzing IR and NMR of the solid content obtained by precipitating with a large amount of poor solvents. The raw material used can be confirmed by decomposing a polyamic acid by the aqueous solution of strong alkalis, such as KOH and NaOH, and analyzing the extract by the organic solvent of the decomposition product by GC, HPLC, or GC-MS.

The liquid crystal aligning agent of this invention may further contain other components other than the said polyamic acid. For example, the liquid crystal aligning agent of this invention may contain the alkenyl substituted naziimide compound further from a viewpoint of long-term stabilizing the electrical characteristics of a liquid crystal display element. The preferable example of this alkenyl substituted naziimide compound is shown next.

The liquid crystal aligning agent of this invention may also contain the compound which has a radically polymerizable unsaturated double bond from the viewpoint of long-term stabilization of the electrical characteristic of a liquid crystal display element, for example. As a compound which has a radically polymerizable unsaturated double bond, (meth) acrylic acid derivatives, such as (meth) acrylic acid ester and (meth) acrylic acid amide, and bismaleimide, and have two or more radically polymerizable unsaturated double bonds. More preferred are (meth) acrylic acid derivatives.

For example, the liquid crystal aligning agent of this invention may contain the oxazine compound further from a viewpoint of the long-term stability of the electrical characteristic in a liquid crystal display element. As an oxazine compound, the compound represented, for example by Formula (a)-Formula (f) is mentioned.

In formula (a)-formula (f), R <^1> and R <^2> is a C1-C30 organic group; R ³ to R ⁶ are hydrogen or a hydrocarbon group of 1 to 6 carbon atoms; X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -S- (CH ₂ ) _m -S-, wherein m is an integer from 1 to 6; Y is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or alkylene having 1 to 3 carbon atoms.

The liquid crystal aligning agent of this invention may further contain the epoxy compound which has 1 or 2 or more epoxy rings in a molecule | numerator from a viewpoint of the long-term stability of the electrical property in a liquid crystal display element, for example. The epoxy compound may be a monomer, oligomer or polymer having an epoxy ring. The liquid crystal aligning agent of this invention may contain the various additives further. As various additives, a polymer other than a polyamic acid and its derivatives, and a low molecular weight compound are mentioned, for example, It can select and use according to each objective. As this polymer, the polymer soluble in the organic solvent is mentioned. It is preferable to add such a polymer to the liquid crystal aligning agent of this invention from a viewpoint of controlling the electrical characteristic and orientation of the liquid crystal aligning film formed. Examples of the polymer include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone modified polyurethane, and silicone modified polyester.

As the low molecular weight compound, for example, 1) a surfactant according to this purpose is desired when the applicability is improved, 2) an antistatic agent is required when the antistatic property is required, and 3) an adhesion or rubbing resistance with the substrate is desired. In this case, an imidation catalyst may be mentioned when the silane coupling agent or the titanium-based coupling agent and 4) imidation are advanced at low temperature.

As the silane coupling agent, for example, vinyl trimethoxy silane, vinyl triethoxy silane, N- (2-aminotyl) -3-aminopropylmethyldimethoxy silane, N- (2-aminoethyl) -3-amino Propylmethyltrimethoxy silane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxy silane, metaaminophenyltriethoxy silane, 3-aminopropyltrimethoxy silane, 3- Aminopropyltriethoxy silane, 3-chloropropylmethyl dimethoxy silane, 3-chloropropyltrimethoxy silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy silane, N- (1 And 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

As an imidation catalyst, For example, aliphatic amines, such as trimethylamine, triethylamine, tripropylamine, and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline and hydroxy substituted aniline; 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, etc. Cyclic amines may be mentioned. The imidation catalyst may be N, N-dimethyl aniline, o-hydroxy aniline, m-hydroxy aniline, p-hydroxy aniline, o-hydroxy pyridine, m-hydroxy pyridine, p-hydroxy pyridine, and It is preferable that it is 1 type, or 2 or more types chosen from isoquinoline.

The liquid crystal aligning agent of this invention may contain the solvent further from a viewpoint of adjustment of the applicability | paintability of a liquid crystal aligning agent, and the said density | concentration of the said polyamic acid. This solvent can be applied without particular limitation as long as it is a solvent having the ability to dissolve a polymer component. The said solvent contains the solvent normally used by the manufacturing process of a polymer component, such as a polyamic acid and a soluble polyimide, and a use viewpoint widely, and can be suitably selected according to a use purpose. The solvent may be one kind or a mixed solvent of two or more kinds. As such a solvent, the solvent for the said polyamic acid and the other solvent for the purpose of improving applicability | paintability are mentioned.

As an aprotic polar organic solvent which is a solvent for a polyamic acid, N-methyl-2-pyrrolidone, dimethyl imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N, N-dimethylacetamide And lactones such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and γ-butyrolactone.

Examples of other solvents for the purpose of improving the coatability include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol mono Diethylene glycol monoalkyl ethers such as ethyl ether, ethylene glycol monoalkyl or phenyl acetate, propylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethyl malonic acid, and the like. And ester compounds such as dipropylene glycol monoalkyl ethers such as dialkyl dialkyl and dipropylene glycol monomethyl ether and these acetates.

Among these, particularly preferred solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

Although the density | concentration of the polymer component containing the said polyamic acid in a liquid crystal aligning agent in this invention is not specifically limited, 0.1-40 weight% is preferable. When apply | coating the said liquid crystal aligning agent to a board | substrate, the operation which dilutes the polymer component contained for film thickness adjustment with a solvent beforehand may be needed. At this time, it is preferable that the density | concentration of the said polymer component is 40 weight% or less from a viewpoint of adjusting the viscosity of a liquid crystal aligning agent to the viscosity suitable for mixing a solvent with respect to a liquid crystal aligning agent easily.

Moreover, the density | concentration of the said polymer component in a liquid crystal aligning agent may be adjusted with the coating method of a liquid crystal aligning agent. When the coating method of a liquid crystal aligning agent is spin coating or the printing method, in order to maintain film thickness favorably, the density | concentration of the said polymer component is usually made into 10 weight% or less frequently. In other coating methods, for example, the dipping method and the inkjet method, the concentration may be lowered. On the other hand, when the density | concentration of the said polymer component is 0.1 weight% or more, the film thickness of the liquid crystal aligning film obtained will become easy to be optimal. Therefore, the density | concentration of the said polymer component is 0.1 weight% or more, Preferably it is 0.5 to 10 weight% in normal spin coating method, the printing method, etc. However, depending on the coating method of a liquid crystal aligning agent, you may use in lower concentration.

And when using for preparation of a liquid crystal aligning film, the viscosity of the liquid crystal aligning agent of this invention can be determined according to the means or method of forming the film of this liquid crystal aligning agent. For example, when forming the film of a liquid crystal aligning agent using a printing machine, it is preferable that it is 5 mPa * s or more from a viewpoint of obtaining sufficient film thickness, and it is preferable that it is 100 mPa * s or less from a viewpoint which suppresses printing nonuniformity, More Preferably it is 10-80 mPa * s. When apply | coating a liquid crystal aligning agent and forming a film of a liquid crystal aligning agent by spin coating, it is preferable that it is 5-200 mPa * s from a similar viewpoint, More preferably, it is 10-100 mPa * s. The viscosity of a liquid crystal aligning agent can be made small by curing with dilution and stirring with a solvent.

The liquid crystal aligning film of this invention is a film | membrane in which the coating film of the liquid crystal aligning agent of this invention mentioned above is heated. The liquid crystal aligning film of this invention can be obtained according to the normal method which produces a liquid crystal aligning film from a liquid crystal aligning agent, For example, the liquid crystal aligning film of this invention heats the process of forming the coating film of the liquid crystal aligning agent of this invention, and this is heated. It can obtain by the process of baking. About the liquid crystal aligning film of this invention, you may rub the film obtained by the said baking process as needed.

The said coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to manufacture of a normal liquid crystal aligning film. Examples of the substrate include glass substrates in which electrodes such as ITO (Indium Tin Oxide) electrodes, color filters, and the like may be provided.

As a method of apply | coating a liquid crystal aligning agent to a board | substrate, the spin coating method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. These methods can be similarly applied in the present invention.

Firing of the coating film can be performed under conditions necessary for the dehydration and ring-closure reaction of the polyamic acid. As the baking of the coating film, 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 can be similarly applied in the present invention. Generally, it is preferable to carry out for 1 minute-3 hours at the temperature of about 150-300 degreeC.

The said rubbing process can be performed similarly to the rubbing process for orientation processing of a normal liquid crystal aligning film, and should just be a condition which can obtain sufficient retardation in the liquid crystal aligning film of this invention. Particularly preferable conditions are 0.2 to 0.8 mm of hair pressing amount, stage movement speed 5 to 250 mm / sec, and roller rotation speed 500 to 2,000 rpm. As an orientation processing method of a liquid crystal aligning film, the photo-alignment method, the transfer method, etc. other than the rubbing method are generally known. In the range from which the effect of this invention is acquired, you may use together this other orientation processing method in the said rubbing process.

The liquid crystal aligning film of this invention is obtained preferably by the method of including the other process other than the above-mentioned process further. As such another process, the process of drying the said coating film, the process of washing the film before and behind a rubbing process with a washing | cleaning liquid, etc. are mentioned.

As for the drying process, the method of heat-processing in oven or infrared furnace, the method of heat-processing on a hotplate, etc. are generally known similarly to the said baking process. These methods can be similarly applied to the drying step. It is preferable to perform a drying process at the temperature within the range which can evaporate a solvent, and it is more preferable to carry out at a comparatively low temperature with respect to the temperature in the said baking process.

As a washing | cleaning method by the washing | cleaning liquid of the liquid crystal aligning film before and behind an orientation treatment, brushing, jet spray, steam washing | cleaning, ultrasonic washing | cleaning, etc. are mentioned. These methods may be performed independently or may be used together. Pure water or various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone can be used as the washing liquid. However, it is not limited to these. Of course, these washing | cleaning liquids are refine | purified sufficiently and the thing with few impurities is used. Such a cleaning method can be applied also to the said washing process in formation of the liquid crystal aligning film of this invention.

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal aligning film of this invention can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer.

The liquid crystal display device of the present invention includes a pair of substrates and liquid crystal molecules, and a liquid crystal layer formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and the liquid crystal molecules are aligned in a predetermined direction. It has a liquid crystal aligning film of this invention to make.

The glass substrate mentioned above can be used for the liquid crystal aligning film of this invention for a board | substrate, and the ITO electrode formed in the glass substrate as mentioned above with the liquid crystal aligning film of this invention can be used for an electrode. The liquid crystal layer is formed of a liquid crystal composition sealed between substrates with the liquid crystal alignment film surface inward.

There is no restriction | limiting in particular in the liquid crystal composition to be used, Various liquid crystal compositions which have positive or negative dielectric anisotropy can be used. Preferable liquid crystal compositions having positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Publication No. Hei 5-501735, Japanese Patent Application Publication No. Hei 8-157826, Japanese Patent Application Laid-open No. Hei 8-231960, Japanese Patent Application Laid-open No. Hei 9-241644 (EP885272A1 specification), Japanese Patent Application Publication No. Hei 9-302346 (EP806466A1 specification) and Japanese Patent Application Publication No. Hei Japanese Patent Application Publication No. Hei 9-235552, Japanese Patent Application Publication No. Hei 9-255956, Japanese Patent Application Publication No. Hei 9-241643 (EP885271A1 specification), Japanese Patent Application Publication No. Hei 10-204016 (EP844229A1 specification), Japanese Patent Application Publication No. Hei 10-204436, Japanese Patent Application Publication No. Hei 10-231482, Japanese Patent Application Publication No. 2000-087040,The liquid crystal composition disclosed by Unexamined-Japanese-Patent No. 2001-48822 etc. is mentioned.

Preferred liquid crystal compositions having negative dielectric anisotropy include Japanese Patent Application Laid-open No. 57-114532, Japanese Patent Application Laid-open No. 2-4725, Japanese Patent Application Laid-open No. Hei 4-224885, and Japanese Patent Application Publication Japanese Patent Application Publication No. Hei 8-104869, Japanese Patent Application Publication No. Hei 10-168076, Japanese Patent Application Publication No. Hei 10-168453, Japanese Patent Application Publication No. 10-236989, Japanese Patent Application Laid-Open No. 10-236990, Japanese Patent Application Laid-open No. 10-236992, Japanese Patent Application Laid-open No. 10-236993, Japanese Patent Application Publication No. 10-23 236994, Japanese Patent Application Publication No. Hei 10-237000, Japanese Patent Application Publication No. Hei 10-237004, Japanese Patent Application Publication No. Hei 10-237024, Japanese Patent Application Publication No. Hei 10-237035 Gazette, Japanese Patent Application Publication No. Hei 10-237075, Japanese Patent Application Publication No. Hei 10-237076, Japanese Patent Application Publication No. Hei 10-237448 (EP967261A1 specification), Japanese Patent Application Publication No. Hei 10-287874 Japanese Patent Application Publication No. Hei 10-287875, Japanese Patent Application Publication No. Hei 10-291945, Japanese Patent Application Publication No. Hei 11-029581, Japanese Patent Application Publication No. Hei 11-080049, A liquid crystal composition disclosed in Japanese Patent Application Laid-Open No. 2000-256307, Japanese Patent Application Laid-Open No. 2001-019965, Japanese Patent Application Laid-Open No. 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657, etc. Can be mentioned.

There is no problem even if one or more optically active compounds are added to the liquid crystal composition having the dielectric anisotropy being positive or negative.

The liquid crystal display element of this invention can form the liquid crystal display element for various electric field systems. In such a liquid crystal display device for an electric field system, a liquid crystal display device for a transverse electric field system in which the electrode applies a voltage to the liquid crystal layer in a horizontal direction with respect to the surface of the substrate, or in a direction perpendicular to the surface of the substrate. The liquid crystal display element for the vertical electric field system in which the said electrode applies a voltage to the said liquid crystal layer is mentioned.

The liquid crystal display element for the transverse electric field system does not have to express a relatively large pretilt angle. Therefore, the liquid crystal aligning film formed from the liquid crystal aligning agent containing the non-branched polyamic acid obtained using non-branched diamine is used suitably for the liquid crystal display element for a transverse electric field system.

The liquid crystal display device for the longitudinal field system requires the expression of a relatively large pretilt angle. Therefore, the liquid crystal aligning film formed from the liquid crystal aligning agent containing the side chain type diamine or the side chain type polyamic acid obtained using the diamine mixture containing this is used suitably for the liquid crystal display element for electric field systems.

Thus, the liquid crystal aligning film produced using the liquid crystal aligning agent of this invention as a raw material can be applied to the liquid crystal display element of various display drive systems by selecting the polymer which is the raw material suitably.

The liquid crystal display element of this invention may further have elements other than the component mentioned above. As such other components, components commonly used in liquid crystal display elements such as polarizing plates (polarizing films), wavelength plates, light scattering films, and driving circuits may be mounted on the liquid crystal display elements of the present invention.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

The compound used in the Example is as follows.

Tetracarboxylic dianhydride

Carboxylic acid (1): pyromellitic dianhydride

Carboxylic Acid (19): 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride

<Diamine>

Diamine (VI-7): 1,4-bis (4-aminophenyl) -1,4-diazacyclo hexane

Diamine (V-1): 4,4'-diaminodiphenylmethane

Diamine (V-7): 1,2-bis (4-aminophenyl) ethane

Diamine (XII-4-1): 1,1-bis [4- (4-aminophenoxy) phenyl- (4-trans- (4-n-pentylcyclohexyl) cyclohexane

Diamine (XII-2-1): 1,1-bis [4- (4-aminophenylmethyl) phenyl]-(4-n-heptylcyclohexane

Diamine (N-1): 1,4-bis (4-aminophenoxy) naphthalene

Diamine (V-36): N, N'-bis (4-aminophenyl) -N, N'-dimethylethylenediamine

<Solvent>

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

1. Synthesis of Polyamic Acid

Synthesis Example 1

In a 100 mL four-necked flask equipped with a thermometer, agitator, raw material inlet and nitrogen gas inlet, 2.242 g of diamine (VI-7), 1.072 g of diamine (N-1) and 0.569 of diamine (XII-2-1) g and 80.0 g of dehydrated NMP were added and stirred and dissolved under a dry nitrogen stream. Next, 0.683 g of carboxylic acid (1) and 1.434 g of carboxylic acid (19) were added and reacted for 30 hours in a room temperature environment. When reaction temperature rises during reaction, reaction temperature was suppressed to about 70 degreeC or less, and it was made to react. 14.0 g of BC was added to the obtained solution to obtain a polyamic acid solution having a concentration of 6% by weight. Let this polyamic acid be PA1. The weight average molecular weight of PA1 was 40,100.

The weight average molecular weight of the polyamic acid is diluted with the obtained polyamic acid in a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100): weight ratio) so that the polyamic acid concentration becomes about 1% by weight, and the 2695 Separation Module 2414 time difference Using the refractometer (made by Waters), the said mixed solution was measured by GPC method as a developing agent, and it calculated | required by polystyrene conversion. The column was HSPgel RT MB-M (manufactured by Waters) and measured at a column temperature of 40 ° C. under a flow rate of 0.35 mL / min.

Synthesis Examples 2 to 7

As shown in Table 1, except having changed tetracarboxylic dianhydride and diamine, the polyamic-acid solution (PA2)-(PA7) was prepared according to the synthesis example 1.

Including the synthesis example 1, the result is put together in Table 1.

TABLE 1

<2. Fabrication of Liquid Crystal Display Devices>

Example 1

The polyamic-acid solution (PA1) of 6 weight% of concentration synthesize | combined by the synthesis example 1 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4 weight% to make the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced as follows.

<Manufacturing Method of Liquid Crystal Display Device>

The liquid crystal aligning agent was apply | coated to the glass substrate with two ITO electrodes by spin coating, and the film | membrane with a film thickness of 70 nm was formed. After coating and heating at 80 degreeC for about 5 minutes, it heat-processed at 210 degreeC for 20 minutes, and formed the liquid crystal aligning film. Next, the surface of the board | substrate with which the liquid crystal aligning film was formed was rubbed with the rubbing apparatus, and the orientation process was performed. Then, the liquid crystal aligning film was ultrasonically cleaned in ultrapure water for 5 minutes, and it dried at 120 degreeC in oven for 30 minutes.

After spread | dispersing a 7 micrometers gap material on one glass substrate, the surface in which the liquid crystal aligning film was formed, and facing it so that a rubbing direction may become antiparallel is sealed, it is sealed with an epoxy hardening | curing agent, and the gap is 7 micrometers antiparallel cell. Produced. The liquid crystal composition shown below was injected to the said cell, and the injection hole was sealed with the photocuring agent. Subsequently, heat processing were performed for 30 minutes at 110 degreeC, and the liquid crystal display element was produced.

<Liquid crystal composition>

Example 2

The polyamic-acid solution (PA2) of 6 weight% of concentration synthesize | combined by the synthesis example 2 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), the whole was diluted to 4 weight%, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

Example 3

The polyamic-acid solution (PA3) of 6weight% of concentration synthesize | combined by the synthesis example 3 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4 weight% to make the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

Comparative Example 1

The polyamic-acid solution (PA4) of 6 weight% of concentration synthesize | combined by the synthesis example 4 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), the whole was diluted to 4 weight%, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

Comparative Example 2

The polyamic-acid solution (PA5) of 6 weight% of concentration synthesize | combined by the synthesis example 5 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4 weight% to make the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

Comparative Example 3

The polyamic-acid solution (PA6) of 6weight% of concentration synthesize | combined by the synthesis example 6, the mixed solvent of NMP / BC = 1/1 (weight ratio) was added, the whole was diluted to 4 weight%, and it was set as the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

[Comparative Example 4]

The polyamic-acid solution (PA7) of 6 weight% of concentration synthesize | combined by the synthesis example 7 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4 weight% to make the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

3. Evaluation of Electrical Characteristics

About the liquid crystal display element produced in Examples 1-3 and Comparative Examples 1-4, the measurement of voltage retention and the measurement of long-term reliability were performed as follows.

(1) Measurement of voltage holding ratio

The voltage holding ratio was measured using a liquid crystal property evaluation apparatus 6254 manufactured by Toyo Technica. Measurement conditions were gate width: 60 microseconds, frequency: 3 Hz, wave height: +/- 1V, and measurement temperature was 60 degreeC. The higher this value, the better the electrical characteristics.

The results are shown in Table 2.

(2) Measurement of retention characteristics of voltage holding ratio

About the produced liquid crystal display element, voltage retention [%] was calculated | required over time, and the retention characteristic was evaluated. In the test method for the retention characteristics, a method of leaving the liquid crystal display element in an atmosphere having a temperature of 100 ° C., withdrawing it over time and measuring the voltage holding ratio [%] was adopted. As the decrease in the voltage holding ratio is small (for example, the reduction ratio by the following formula is less than 10%), it can be said that the holding characteristic of the voltage holding ratio is good, and the long-term reliability of the electrical characteristics is good.

Reduction ratio (%) = (voltage retention rate-(voltage retention rate after 500 hours) / initial voltage retention rate of initial (0 hours) * 100

Data after 300 hours and after 500 hours is shown in Table 2.

TABLE 2

As shown in Table 2, when manufacturing a polyamic acid using the raw material diamine containing diamine (N), in the liquid crystal display element which used the liquid crystal aligning film containing this polymer as a liquid crystal aligning film, time-lapse of a voltage holding ratio Significantly improved the effect of suppressing the reduction.

Claims (21)

A composition containing at least one polymer selected from the group consisting of polyamic acids and derivatives thereof, the polymer comprising at least one of diamines represented by formula (N) or at least one of diamines represented by formula (N) The liquid crystal aligning agent which is a polyamic acid or its derivative (s) obtained by making the mixture with at least 1 of other diamine which is diamine which is not represented by Formula (N) react with tetracarboxylic dianhydride:

Wherein A ¹ is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, hydroxy, trifluoromethyl, fluorine, chlorine or bromine; m is independently an integer of 0 to 3; A ² is independently —O—, —NH—, —N (CH ₃ ) —, or —S —; The bonding position of the two amino groups to the benzene ring is any position except for the bonding positions of A ¹ and A ² . The liquid crystal aligning agent of Claim 1 whose all the bonding positions of the two amino groups in Formula (N) are para positions with respect to A <^2> . The diamine according to claim 1, wherein the diamine is formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and A liquid crystal aligning agent, which is a mixture of at least one diamine or di (ed) diamine selected from the group of compounds represented by formula (N-16) and other diamines:

In the above formula, Me means methyl. 4. The liquid crystal aligning agent according to claim 3, wherein the diamine is at least one of diamines represented by formulas (N-1) and (N-3) or a mixture of two or more diamines with other diamines. 5. The diamine is a mixture of at least one of the diamines represented by the formula (N) with other diamines, and the other diamines are represented by the formulas (VIII) and (X) to (XIII). Liquid crystal aligning agent which is at least 1 of the diamine which has a side chain group chosen from a diamine group:

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Optional -CH ₂ -in alkyl of 30 may be substituted with -O-, -CH = CH- or -C≡C-:

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxy alkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene:

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms, and R ⁷ and R ⁸ are each Independently alkyl or phenyl having 1 to 20 carbon atoms and A ⁶ is independently a single bond, -CO- or -CH _2- :

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1) The diamine according to claim 3, wherein the diamine is formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), formula (N-15) and It is a mixture of at least 1 diamine selected from the compound group represented by Formula (N-16), and other diamine, and other diamine is Formula (VIII-2), Formula (VIII-4)-Formula (VIII-) 6) The liquid crystal aligning agent which is at least 1 of the diamine which has a side chain group chosen from diamine represented by Formula (XII-2), Formula (XII-4), and Formula (XII-6).

In these formulae, R ²³ , R ²⁹ and R ³⁰ are each alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, respectively. The diamine according to claim 1 is a mixture which also contains a diamine having no side chain group, wherein the diamine having no side chain group is selected from the group of compounds represented by formulas (I) to (VII) and formula (XV). At least 1 liquid crystal aligning agent:

In these formulas, X is C2-C12 linear alkylene; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms, t is an integer from 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl. The diamine which does not have a side chain group, Formula (IV-1), Formula (IV-2), Formula (IV-15)-Formula (IV-17), Formula (V-1)-Formula (V) -12), in the diamine represented by formula (V-33), formula (V-35) to formula (V-37), formula (VI-7), formula (VII-2) and formula (XV-1). At least one liquid crystal aligning agent.

The at least 1 of the diamine of Claim 1 in which a polymer has a side chain group chosen from at least 1 of the diamine represented by Formula (N), and the diamine group represented by Formula (VIII) and Formula (X)-(XIII). At least one of diamines having a side chain group selected from a mixture with a dog or a diamine represented by formula (N) and a diamine group represented by formulas (VIII) and (X) to (XIII) and formula (I) Polyamic acid or derivatives thereof obtained by reacting a mixture of at least one of diamines having no side chain group selected from the diamine groups represented by formulas (VII) and (XV) with tetracarboxylic dianhydride, and the side chain group A mixture of at least one of diamines or at least one of diamines having no side chain group and at least one of diamines represented by formula (N) with tetracarboxylic dianhydride; The liquid crystal aligning agent which is a mixture with the polyamic acid obtained by making it react, or its derivative (s):

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Any of —CH ₂ — in alkyl of 30 may be substituted with —O—, —CH═CH— or —C≡C—:

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene:

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms, and R ⁷ and R ⁸ are each independently having 1 to C carbon atoms. 20 alkyl or phenyl and A ⁶ is independently a single bond, -CO- or -CH _2- :

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1:

In formulas (I) to (VII) and (XV), X is straight chain alkylene having 2 to 12 carbon atoms; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH3)-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ —, —O— (CH ₂ ) _t —O—, —S—, —SS—, —SO ₂ —, —S— (CH ₂ ) _t —S— or straight chain alkylene having 1 to 12 carbon atoms, t Is an integer of 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl. The polymer according to claim 1, wherein at least one of the diamines having no side chain group selected from the diamine group represented by at least one of the diamines represented by the formula (N) and the formulas (I) to (VII) and the formula (XV). At least one of a polyamic acid or derivative thereof obtained by reacting a mixture with one with tetracarboxylic dianhydride and a diamine having a side chain group selected from the group of diamines represented by formulas (VIII) and (X) to (XIII) Or a mixture of a polyamic acid or a derivative thereof obtained by reacting a mixture of at least one of the diamines having this side chain group with at least one of the diamines not having the side chain group with tetracarboxylic dianhydride.

Wherein A ³ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O-, or alkylene having 1 to 6 carbon atoms And optionally -CH ₂ -in this alkylene may be substituted with -O-, -CH = CH- or -C≡C-; R ¹ is a group having a steroid skeleton, alkyl having 3 to 30 carbon atoms, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms as a substituent, or a group represented by formula (IX). Optional -CH ₂ -in alkyl of 30 may be substituted with -O-, -CH = CH- or -C≡C-:

Here, A ⁴ and A ⁵ are independently a single bond, -O-, -COO-, -OCO-, -CONH-, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 3 carbon atoms, or 1 carbon atom. Alkyleneoxy of -3; Ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; R ² and R ³ are independently fluorine or methyl, f and g are independently 0, 1 or 2; c, d and e are each independently an integer of 0 to 3, and the sum thereof is 1 or more; R ⁴ is alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, or alkoxyalkyl having 2 to 30 carbons, and in these alkyls, alkoxy and alkoxyalkyl, arbitrary hydrogen may be substituted with fluorine, and -CH ₂ -may be substituted with difluoromethylene:

In formulas (X) and (XI), R ⁵ is independently hydrogen or methyl, R ⁶ is hydrogen or alkyl or alkenyl having 1 to 20 carbon atoms, and R ⁷ and R ⁸ are each independently having 1 to C carbon atoms. 20 alkyl or phenyl and A ⁶ is independently a single bond, -CO- or -CH _2- .)

In formulas (XII) and (XIII), R ⁹ is alkyl having 1 to 30 carbon atoms, and any -CH ₂ -of this alkyl is -O-, -CH = CH- or -C≡C-. May be substituted; R ¹⁰ is alkyl having ⁶ to ²² carbon atoms; R ¹¹ is alkyl having 1 to 22 carbons; A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms; A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms; Ring T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1:

In formulas (I) to (VII) and (XV), X is straight chain alkylene having 2 to 12 carbon atoms; Y is independently a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O- (CH ₂ ) _t -O-, -S-, -SS-, -SO _2- , -S- (CH ₂ ) _t -S- or straight chain alkylene having 1 to 12 carbon atoms; t is an integer from 1 to 12; Z ¹ and Z ² are hydrogen, but when Y is -NH-, -N (CH ₃ )-, -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- May form a single bond; Ring D is phenylene or 1,4-diazacyclohexylene; R ³³ and R ³⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms; A ³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms; m is an integer from 1 to 10; Cyclohexane ring or benzene ring is any of hydrogen, may be substituted with fluorine, _{methyl, -OH, -COOH, -SO 3 H} , -PO 3 H 2, benzyl or hydroxybenzyl. The diamine represented by the formula (N) is a compound represented by formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), The diamine represented by a formula (N-15) or a formula (N-16), and the diamine which has a side chain group is a formula (VIII-2), a formula (VIII-4)-a formula (VIII-6), and a formula (XII- 2), the diamine represented by Formula (XII-4) or Formula (XII-6), and the diamine which does not have a side chain group is Formula (IV-1), Formula (IV-2), Formula (IV-15)- Formula (IV-17), Formula (V-1) to Formula (V-12), Formula (V-33), Formula (V-35) to Formula (V-37), Formula (VI-7), Formula Liquid crystal aligning agent which is diamine represented by (VII-2) or Formula (XV-1).

In these formulas, Me means methyl:

In these formulae, R ²³ , R ²⁹ and R ³⁰ are each alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, respectively.

The diamine represented by the formula (N) is a compound represented by formula (N-1) to formula (N-5), formula (N-7), formula (N-8), formula (N-13), The diamine represented by a formula (N-15) or a formula (N-16), and the diamine which has a side chain group is a formula (VIII-2), a formula (VIII-4)-a formula (VIII-6), and a formula (XII- 2), the diamine represented by Formula (XII-4) or Formula (XII-6), and the diamine which does not have a side chain group is Formula (IV-1), Formula (IV-2), Formula (IV-15)- Formula (IV-17), Formula (V-1) to Formula (V-12), Formula (V-33), Formula (V-35) to Formula (V-37), Formula (VI-7), Formula Liquid crystal aligning agent which is a diamine represented by (VII-2) or Formula (XV-1):

In these formulas, Me means methyl:

In these formulae, R ²³ , R ²⁹ and R ³⁰ are each alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, respectively.

The liquid crystal aligning agent of Claim 1 whose tetracarboxylic dianhydride is a mixture of aromatic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride, and tetracarboxylic dianhydride other than aromatic. The compound according to claim 13, wherein the aromatic tetracarboxylic dianhydride is at least selected from the group of compounds represented by formula (1), formula (2), formula (5) to formula (7), formula (11) and formula (14). One liquid crystal aligning agent.

The liquid crystal aligning agent of Claim 14 whose aromatic tetracarboxylic dianhydride is a compound represented by Formula (1). The liquid crystal aligning agent of Claim 13 whose tetracarboxylic dianhydride other than aromatic is alicyclic tetracarboxylic dianhydride and / or aliphatic tetracarboxylic dianhydride. 15. The method according to claim 14, wherein the aromatic tetracarboxylic dianhydride is at least selected from the group of compounds represented by formulas (1), (2), (5) to (7), (11) and (14). One, and tetracarboxylic dianhydride other than aromatic is represented by Formula (19), Formula (23), Formula (25), Formula (35)-Formula (39), Formula (44) and Formula (49). The liquid crystal aligning agent which is at least 1 chosen from a compound group.

The liquid crystal aligning agent of Claim 17 whose aromatic tetracarboxylic dianhydride is a compound represented by Formula (1), and tetracarboxylic dianhydride other than aromatic is a compound represented by Formula (19). The liquid crystal aligning agent of Claim 1 which also contains at least 1 compound chosen from an alkenyl substituted naziimide compound, the compound which has a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. The liquid crystal aligning film formed by heating the coating film of the liquid crystal aligning agent in any one of Claims 1-19. A liquid crystal having a pair of substrates, a liquid crystal layer containing liquid crystal molecules, formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for orienting the liquid crystal molecules in a predetermined direction The display device according to claim 20, wherein the liquid crystal alignment film is a liquid crystal alignment film according to claim 20.