KR20160008954A - Diamins, polyamicacids or the dirivatives, liquid crystal aligning agents, liquid crystal alignment films, and liquid crystal display devices - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent comprising a polyamic acid or a derivative thereof obtained by reacting at least one of diamines represented by formula (1) with a tetracarboxylic acid dianhydride, a liquid crystal alignment film formed using the liquid crystal aligning agent, Then, the liquid crystal display element has this liquid crystal alignment film. The liquid crystal display of the present invention has a characteristic that the display quality is not degraded even when exposed to strong light for a long period of time. When the liquid crystal aligning agent of the present invention is used, the performance of such a liquid crystal display element can be realized even at a high temperature Thereby giving a liquid crystal alignment film.

In formula (1), R ¹ is hydrogen or methyl, and R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a polyamic acid and a derivative thereof, a liquid crystal aligning agent containing the polyamic acid and a derivative thereof, and a liquid crystal display element using the diamine represented by the formula (1) as a raw material.

A liquid crystal display device which is commercialized today and is generally circulated is a display device using a nematic liquid crystal. A TN (twisted nematic) mode and a STN (super twisted nematic) mode are well known as a display method of a nematic liquid crystal display element. In recent years, in order to improve narrowness of the viewing angle, which is one of the problems of these modes, a TN type liquid crystal display device using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode using a combination of vertical and projection structures, In-Plane Switching (IPS) mode and FFS (Fringe Field Switching) mode have been proposed and practically used (see Patent Documents 1 to 3).

The development of the liquid crystal display device technology is achieved not only by improving these driving methods and device structures, but also by improving the constituent members used in the devices. Of the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment layer is one of important materials related to the display quality, and it has become important to improve the performance of the alignment layer as the quality of the liquid crystal display element is improved.

Currently, the liquid crystal alignment film mainly used is a polyimide-based liquid crystal alignment film formed by applying a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent to a substrate and then forming the film by means of heating or the like. Generally, a liquid crystal display element is used in which a polyimide-based liquid crystal alignment film produced by this film is subjected to alignment treatment. Some orientation processes are known, and industrially, a rubbing method which is simple and capable of high-speed large-area processing is widely used as an orientation process. The rubbing process is a process of rubbing the surface of the liquid crystal alignment film in one direction by using a fabric obtained by planting fibers such as nylon, rayon, and polyester, thereby making it possible to obtain a uniform orientation of the liquid crystal molecules.

The application of the liquid crystal display element is variously applied to a personal computer monitor, a liquid crystal television, a mobile phone, a display portion of a smart phone, and a liquid crystal projector. In recent years, in consideration of improvement in display quality and outdoor use, there is also a use in which the luminance of a backlight serving as a light source is made higher than that in the prior art, and a liquid crystal display element which does not deteriorate display quality even when exposed to strong light for a long period of time is required .

In order to cope with such a demand, various studies have been made on liquid crystal alignment films. For example, diamines having a structure of hindadine or a structure of hindad phenol are incorporated in a raw material to introduce the same structure into a polyimide chain (See Patent Document 4), or a method of adding an antioxidant having a structure of hindered amine or a structure of hindered phenol to a liquid crystal aligning agent (see Patent Document 5). However, even if these techniques are used, there is a problem that the desired performance is not exhibited depending on the difference in the manufacturing process of the liquid crystal display element, particularly the firing temperature in the process of forming the liquid crystal alignment film on the substrate.

In order to suppress the occurrence of " baking " in the vertically aligned liquid crystal display element, attempts have been made to introduce a hindered amine structure into the side chain portion of the side chain type diamine (see Patent Document 6) This technique is not suitable for the IPS or FFS mode which is the transverse electric field mode because the pretilt angle of the liquid crystal molecules is expressed.

Japanese Unexamined Patent Application Publication No. 6-194646 Japanese Patent Application Laid-Open No. 2001-117083 Japanese Unexamined Patent Application Publication No. 6-160878 Japanese Patent Application Laid-Open No. 2010-244015 Japanese Laid-Open Patent Publication No. 2012-194537 International publication 2008/078629

It is an object of the present invention to provide a liquid crystal display device which does not deteriorate the display quality even when exposed to strong light for a long period of time and also can select a high firing temperature in a process of manufacturing a liquid crystal display device, And to provide a liquid crystal display element exhibiting a desired performance. A liquid crystal alignment agent capable of providing such a display element, and further, a liquid crystal alignment film.

As a result of intensive investigations, the inventors of the present invention have found that the use of the compound of the formula (1) enables stable display without being influenced by the difference in firing temperature of the above-described liquid crystal display element, A liquid crystal aligning agent and an alignment film capable of providing a liquid crystal display element whose quality is not deteriorated have been completed. Particularly, the effects of the present invention are more exerted in the IPS mode and the FFS mode.

The present invention is as follows.

[1] A polyamic acid or a derivative thereof obtained by reacting at least one of diamines represented by the formula (1) with at least one tetracarboxylic acid dianhydride.

In the formula ^(1), R 1 is hydrogen or methyl; and,

R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.

[2] Diamine represented by the formula (1) The polyamic acid or derivative thereof according to [1], wherein at least one of the diamines represented by the formula (1-1) is present.

In the formula (1-1), R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.

[3] Diamine represented by the formula (1) The polyamic acid or derivative thereof according to [1], wherein the diamine has at least one of the diamines represented by the formula (1-2).

In the formula (1-2), R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.

[4] The polyamic acid according to [2], wherein the diamine represented by the formula (1) is at least one selected from the group of the compounds represented by the formulas (1-1-1) to (1-1-28) derivative.

[5] The diamine represented by formula (1) is at least one selected from the group of compounds represented by formulas (1-2-1) to (1-2-28), the polyamic acid according to [3] derivative.

[6] A compound according to any one of [1] to [5], which is obtained by reacting at least one diamine represented by the formula (1) and at least one mixture of other diamines with at least one tetracarboxylic acid dianhydride The polyamic acid or derivatives thereof described.

[7] The method according to any one of [1] to [6], wherein the tetracarboxylic acid dianhydride is at least one selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII) A polyamic acid or a derivative thereof according to item 1.

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;

In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF _{3) 2} - and;

In the formulas (AN-II) to (AN-IV), Y is independently selected from the group of the following trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, Hydrogen may be substituted with methyl, ethyl or phenyl, the bonding hand attached to the ring may be connected to any carbon constituting the ring, and the two bonding hands may be connected to the same carbon;

In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me is methyl, Ph is phenyl,

In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1.

[8] A process for producing a tetracarboxylic acid dianhydride, wherein the tetracarboxylic acid dianhydride has the following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13) (AN-4-17), (AN-4-21), (AN-4-29), and (AN-3-2) AN-10-2, AN-11-3, AN-16-2, AN-11-2, and AN- 3], and the formula (AN-16-4). [7] The polyamic acid or derivative thereof according to [7].

In the formulas (AN-1-2) and (AN-4-17), m is an integer of 1 to 12.

(DI-1) to (DIH-3), and (DI-31) to (DI-35) [6] The polyamic acid or derivative thereof according to [6], wherein the polyamic acid is at least one selected from the group consisting of

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen may be replaced by -OH;

Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONH-, -CONCH 3 -, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m '- -O- (CH ₂ ) _{m '} -O-, -N (CH ₃ ) - (CH ₂ ) _k -N (CH ₃ ) -, - (OC ₂ H ₄ ) _{m' CH 2 -C (CF 3) 2} -CH 2 -O-, -O-CO- (CH 2) m '-CO-O-, -CO-O- (CH 2) m' -O-CO-, _{- (CH 2) m '-NH-} (CH 2) m' -, -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ') k -NH - and _{(NH-C 3 H 6)} n -CO-, or -S- (CH _{2) m '-S-} and, m' are independently an integer of 1 ~ 12, -, -CO- C 3 H 6 k is an integer of 1 to 5, and n is 1 or 2;

In the formula (DI-4), s is independently an integer of 0 to 2;

In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, or an alkylene of 1 to 10 carbon atoms;

Formula (DI-2) ~ formula (DI-7) in cyclohexane at least one hydrogen of the ring and a benzene ring is -F, -Cl, C 1 -C 3 alkyl, -OCH _3, -OH, -CF in _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, phenyl, phenyl and benzyl may be substituted with, besides formula (DI-4) at least one hydrogen has the following formula (DI-4- of the benzene ring in the may be substituted with one of the groups selected from the group of groups a) to (DI-4-e);

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;

A group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary and the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ²² And a position of the engagement portion is not limited;

In formula (DI-11), r is 0 or 1;

In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;

In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego;

In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms , Alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;

In formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, r is 0 or 1;

In the formulas (DI-13) to (DI-16), the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or -C (CF _{3) 2} - and;

In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring wherein at least one hydrogen of the ring may be substituted by methyl, ethyl, or phenyl;

In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the ring may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -;

In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonding to the ring is at any position;

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, m' is an integer of 1 to 12, and R ²⁵ is a group having an alkyl, phenyl, steroid skeleton having 3 to 30 carbon atoms, (DI-31-a) wherein at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be replaced by -O-, -CH = CH- or -C≡ optionally substituted by a C- and a hydrogen of the phenyl is _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms , The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring,

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups and independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one -CH ₂ - -O-, -COO-, -OCO-, -CONH-, -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene- Diyl or anthracene-9,10-diyl, and at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ may be substituted with -F or -CH ₃ , s , t and u are independently an integer of 0 to 2, the sum of them is 1 to 5, and when s, t or u is 2, the two bonding groups in each parenthesis may be the same or different, and two The rings may be the same or different,

R ²⁶ is hydrogen, -F, -OH, C 1 -C 30 alkyl, C 1 -C 30 fluorine-substituted alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2, or -OCF of 1 to 30 carbon atoms in the ₃ , And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b)

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms;

One hydrogen of the benzene ring in the formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl,

In the formulas (DI-32) and (DI-33), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, G ³² is a single bond or alkylene having 1 to 3 carbon atoms,

R ³¹ is hydrogen or alkyl of 1 to 20 carbon atoms, at least one -CH ₂ in the alkyl - is optionally substituted by -O-, -CH = CH- or -C≡C-, R ³² is C 6 - And R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1, and the benzene ring And -NH ₂ bonded to each other represents an arbitrary bonding position in the ring.

(DI-4-1), (DI-4-2), (DI-4-2), and (DI-5-15), (DI-5-13), (DI-5-12) DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI- 1). 6. The polyamic acid or derivative thereof according to [6], wherein the polyamic acid or its derivative is at least one selected from the group consisting of:

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is an integer of 1 to 12;

In the formula (DI-5-30), k is an integer of 1 to 5;

In formula (DI-7-3), n is 1 or 2.

[11] A liquid crystal aligning agent containing the polyamic acid or the derivative thereof according to any one of [1] to [10].

[12] A liquid crystal aligning agent comprising the polyamic acid or derivative thereof according to any one of [1] to [10] and a polymer other than the polyamic acid or its derivative.

[13] A process for producing a compound [11], which further comprises at least one member selected from the group consisting of an alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound and an epoxy compound ] Or the liquid crystal aligning agent according to [12].

[14] A liquid crystal aligning agent for a transverse electric field type liquid crystal display element according to any one of [11] to [13].

[15] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [11] to [14].

[16] A liquid crystal display element comprising the liquid crystal alignment film according to [15].

[17] A diamine represented by the formula (1-2).

In the formula (1-2), R ² is a hydrogen, -OH, alkoxy of 1 to 6 carbon atoms alkyl, or C 1 to 6.

A liquid crystal alignment film formed of a liquid crystal aligning agent containing a polyamic acid or a derivative thereof using the diamine represented by the formula (1) of the present invention as a raw material is excellent in reliability. In addition, it is possible to exhibit a constant performance regardless of the difference in the manufacturing process. The liquid crystal display element provided with this liquid crystal alignment film does not deteriorate the display quality even when it is used for a long time. Further, when it is intended to impart other properties such as reducing the afterimage and improving the printing property on the substrate, it is possible to provide a liquid crystal display element having desired characteristics by blending other polymers or using additives in combination.

In the diamine represented by the formula (1), R ¹ is hydrogen or methyl, and R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms. The substitution position of the two amino groups in the benzene ring is not particularly limited. However, in order to obtain a liquid crystal aligning agent that aligns the liquid crystal molecules better, it is preferable that the substitution position of the amide group is 3, 5 position or 2, 5 position Do.

The diamine represented by the formula (1) is classified into a diamine represented by the formula (1-1) in which R ¹ is hydrogen and a diamine represented by the formula (1-2) in which R ¹ is methyl.

In the formulas (1-1) and (1-2), R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms.

When a liquid crystal aligning agent having a higher solubility in a solvent is desired, it is preferable to use a diamine of the formula (1-1). When a more reliable liquid crystal alignment film is desired, it is preferable to use a compound in which R ² is hydrogen or -OH in formulas (1-1) and (1-2).

Specific examples of the diamine represented by the formula (1-1) are the compounds represented by the following formulas (1-1-1) to (1-1-28).

Specific examples of the diamine represented by the formula (1-2) are the compounds represented by the following formulas (1-2-1) to (1-2-28).

The diamine represented by the formulas (1-1-1) to (1-1-4), the formulas (1-2-1) and (1-2-2) is used as the polymer constituting the liquid crystal aligning agent of the present invention. By using it as one of the raw materials, the liquid crystal alignment film having high liquid crystal alignability can be obtained without lowering the display quality even when used for a long time.

By using the diamine represented by the formulas (1-2-1) to (1-2-6) as one of the raw materials of the polymer constituting the liquid crystal aligning agent of the present invention, other diamines other than the diamine represented by the formula (1) Even when diamines are used in combination, gelation can be suppressed during polymer synthesis. It is thought that this is because the hydrogen in the amide group is substituted with the methyl group, and the intermolecular interaction due to the hydrogen bond disappears.

≪ Synthesis method of diamine represented by formula (1) >

The diamine represented by the formula (1) can be synthesized by the following route.

<Compound in which the substitution position of the amino group is the 3,5-position and R ¹ is hydrogen>

3,5-dinitrobenzoyl chloride and commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative are reacted in the presence of a base such as triethylamine and then hydrogen The diamine of formula (1) wherein the substitution position of the amino group is 3,5-position and R ¹ is hydrogen is obtained.

<The substitution position of the amino group and the 3,5-position, R ¹ is methyl A compound>

A commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative is reacted with methyl iodide to obtain a 4-methylamino-2,2,6,6-tetramethylpiperidine derivative. The subsequent reaction and the substitution position of the group 3, 5-position, and the substitution position of the group 3, 5-position by R ¹ is conducted according to the synthesis of a hydrogen, R ¹ in the formula (1) is methyl Diamine &lt; / RTI &gt;

<Compound in which the substitution position of the amino group is 2,5-position and R ¹ is hydrogen>

The commercially available 2-bromo-5-nitrobenzoic acid is reacted with thionyl chloride to give 2-bromo-5-nitrobenzoyl chloride. The obtained 2-bromo-5-nitrobenzoyl chloride and commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative are reacted in the presence of a base such as triethylamine to obtain an amide form. Bromide of the amide form is obtained by substituting benzophenone imine using Buchwald reaction. By converting the benzophenone imine portion with an acid such as hydrochloric acid with an amino group, and subsequently subjected to reduction of the nitro group under palladium-carbon catalyst to a hydrogen atmosphere, and the substitution position of the amino group of 2,5-position, R ¹ is hydrogen A diamine represented by formula (1) is obtained.

<Compound in which the substitution position of the amino group is 2,5-position and R ¹ is methyl>

A commercially available 4-amino-2,2,6,6-tetramethylpiperidine derivative is reacted with methyl iodide to obtain a 4-methylamino-2,2,6,6-tetramethylpiperidine derivative. The subsequent reaction and the substitution position of the amino group of 2,5-position, and the substitution position of the amino group carried by R ¹ is 2,5-position according to the synthesis of a hydrogen, R ¹ in the formula (1) is methyl Diamine &lt; / RTI &gt;

The polyamic acid and its derivatives of the present invention will be described.

The polyamic acid and its derivatives of the present invention are reaction products of tetracarboxylic acid dianhydrides and diamines including diamines represented by formula (1). The derivative of the polyamic acid is a component dissolved in a solvent when it is a liquid crystal aligning agent which will be described later and contains a solvent. When the liquid crystal aligning agent is used as a liquid crystal alignment film, a derivative capable of forming a liquid crystal alignment film containing polyimide as a main component to be. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, polyamic acid amides, and the like, and more specifically, 1) polyamides obtained by subjecting all amino groups of polyamic acid to dehydration ring- 2) partial polyimide partially dehydrated ring closure reaction, 3) polyamic acid ester converted into carboxyl ester of polyamic acid, 4) part of acid dianhydride contained in tetracarboxylic acid dianhydride compound, A polyamic acid-polyamide copolymer obtained by reacting a polyamic acid-polyamide copolymer by substitution with a carboxylic acid, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to dehydration ring closure reaction. The polyamic acid and the derivative thereof may be one kind of compound or two or more kinds. The polyamic acid and the derivative thereof may be any compound having a structure of the reaction product of a tetracarboxylic acid dianhydride and a diamine, and may be produced by reacting a tetracarboxylic acid dianhydride with a diamine The product may also be contained.

The tetracarboxylic acid dianhydride used for producing the polyamic acid and the derivative thereof of the present invention will be described.

The tetracarboxylic acid dianhydride used in the present invention can be selected without limitation from known tetracarboxylic acid dianhydrides. Such a tetracarboxylic acid dianhydride is an aromatic (including a complex aromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic (alicyclic) anhydride in which a dicarboxylic acid anhydride is not directly bonded to the aromatic ring And a heterocyclic ring system).

Suitable examples of such tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides represented by the formulas (AN-I) to (AN-VII) from the viewpoints of ease of raw material availability, ease of polymer polymerization, 2 anhydride.

In the formula (AN-I), (AN -IV) and (AN-V), X represents a single bond or -CH ₂ independently is. In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF ₃ ) ₂ -. In the formulas (AN-II) to (AN-IV), Y is independently selected from the group consisting of the following trivalent groups, the bonding hand is connected to any carbon, and at least one hydrogen May be substituted with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, May be substituted with methyl, ethyl or phenyl and the bonding hands attached to the ring may be connected to any carbon constituting the ring and two bonding hands may be connected to the same carbon. In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl and Ph represents phenyl. In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

And more specifically, tetracarboxylic acid dianhydrides represented by the following formulas (AN-1) to (AN-16-14).

[Tetracarboxylic acid dianhydride represented by the formula (AN-1)] [

In formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or -CH ₂ -. G ¹² is independently any one of the following trivalent groups:

When G ¹² is &gt; CH-, the hydrogen of &gt; CH- may be substituted with -CH ₃ . When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And R ¹¹ is hydrogen or -CH _3.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-1) include the compounds represented by the following formulas.

In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.

[Tetracarboxylic acid dianhydride represented by the formula (AN-2)

In formula (AN-2), R ¹² is independently hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-2) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-3)

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-3) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-4)

In formula (AN-4), G ¹³ is a single bond, - (CH ₂ ) _m -, -O-, -S-, -C (CH ₃ ) ₂ -, -SO ₂ -, -CO-, C (CF ₃ ) ₂ -, or a bivalent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Ring A ¹¹ is, each independently, a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of the ring A ¹¹ .

In the formula (G13-1), G ^13a and ^13b G is a bivalent group represented by a single bond, -O- or -NHCO-, each independently. Phenylene is preferably 1,4-phenylene and 1,3-phenylene.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-4) include the compounds represented by the following formulas.

In the formula (AN-4-17), m is an integer of 1 to 12.

[Tetracarboxylic acid dianhydride represented by the formula (AN-5)] [

In formula (AN-5), R ¹¹ is hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom constituting the benzene ring indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-6)] [

In the formula (AN-6), X ¹¹ is independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH = CH-. n is 1 or 2;

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-6) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-7)] [

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-7) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-8)

In formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-8) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-9)] [

In formula (AN-9), r is each independently 0 or 1.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-9) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-10-1) and the formula (AN-10-2)

[Tetracarboxylic acid dianhydride represented by the formula (AN-11)] [

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-11) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-12)

In the formula (AN-12), each of the rings A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-12) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-13)] [

In the formula (AN-13), X ¹³ represents alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-13) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-14)

In the formula ^(AN-14), G 14 are independently -O-, -COO- or -OCO-, r is independently 0 or 1;

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-14) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-15)] [

In the formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-15) include the compounds represented by the following formulas.

As the tetracarboxylic acid dianhydride other than the above, the following compounds may be mentioned.

A suitable material for improving the properties of the acid dianhydride will be described. (AN-1), (AN-3) and (AN-4) are preferable, and the compounds represented by formulas (AN-1-2), (AN- (AN-4-19), (AN-4-27) and (AN-4-29) = 4 or 8, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable.

(AN-1-1), (AN-1-2), (AN-2-1), and (AN-3) among the acid dianhydrides in the case where the improvement of the transmittance of the liquid crystal display element is emphasized. AN-4-17, AN-4-30, AN-5-1, AN-7-2, AN-10, And (AN-16-4). Among them, in the formula (AN-1-2), m is preferably 4 or 8, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable.

(AN-1-1), (AN-1-2), (AN-2-1), and (AN-3) among the above acid anhydrides in order to improve the VHR of the liquid crystal display element. -1, AN-4-17, AN-4-30, AN-7-2, AN-10, AN- (AN-1-2), m is preferably 4 or 8, and in the formula (AN-4-17), m is preferably 4 or 8, m = 8 is particularly preferable.

It is effective as one of the methods for preventing baking to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. (AN-1-13), (AN-3-2), (AN-4-21), (AN-4-29), and AN-11-3) is preferable.

The diamines and dihydrazides used for producing the polyamic acid and derivatives thereof of the present invention will be described. In the production of the polyamic acid or its derivative of the present invention, it can be selected without limitation from known diamines and dihydrazides.

The diamine can be divided into two types according to its structure. Namely, when a skeleton connecting two amino groups is regarded as a main chain, it is a diamine which does not have a branching group from the main chain, that is, a diamine having a side chain and a side chain. This side wrench is a unit having an effect of increasing the pre-tilt angle. A side chain having such an effect needs to have a carbon number of 3 or more. Specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and a group having a steroid skeleton. A group having at least one ring and having a ring at the terminal thereof has any one of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as substituents. In the following description, the diamine having such a side chain is sometimes referred to as a side chain diamine. The diamine having no such side chain is sometimes referred to as a side chain type diamine.

By suitably separating the non-side chain diamine and the side chain diamine, it is possible to cope with the pretilt angle required for each. The side chain type diamine is preferably used in combination so as not to impair the characteristics of the present invention. In addition, it is preferable to select and use the side chain type diamine and the side chain type diamine in order to improve the vertical alignment property, the voltage maintaining ratio, the baking property and the orientation property to the liquid crystal.

The non-chain type diamine will be described. Examples of diamines which do not have known side chains include diamines of the following formulas (DI-1) to (DI-16).

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen of the phenylene may be substituted with -OH. Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONCH 3 -, -CONH-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m -, _{-O- (CH 2) m -O-,} -N (CH 3) - (CH 2) k -N (CH 3) -, - (OC 2 H 4) m -O-, -O-CH 2 - _{C (CF 3) 2 -CH 2} -O-, -O-CO- (CH 2) m -CO-O-, -CO-O- (CH 2) m -O-CO-, - (CH 2) _{m -NH- (CH 2) m -} , -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH-, -CO-C 3 H _{6 - (NH-C 3 H} 6) _n is -CO-, or -S- (CH _{2) m} -S-, and m is independently an integer of 1 ~ 12, k is an integer of 1 ~ 5, n Is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, or an alkylene having 1 to 10 carbon atoms. Formula (DI-2) ~ formula (DI-7) cyclohexane ring and benzene, at least one hydrogen is -F, -Cl, alkyl, -OCH _3, -OH, -CF of 1 to 3 carbon atoms in the ring _{3, -CO 2 H, -CONH 2, -NHC} 6 H 5, phenyl, phenyl and benzyl may be substituted with, besides formula (DI-4) in cyclohexane to at least one hydrogen of a benzene ring and a cyclic (DI in May be substituted with one group selected from the group of groups represented by formulas (4-a) to (DI-4-e). A group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary. The bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² .

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ .

In formula (DI-11), r is 0 or 1. In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at an arbitrary position.

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10; In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 to be. In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, And is an integer of 0 to 4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is any position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) may be mentioned as the diamines having no side chains of the formulas (DI-1) to (DI-16).

Examples of the diamine represented by the formula (DI-1) are shown below.

In the formulas (DI-1-7) and (DI-1-8), k is independently an integer of 1 to 3.

Examples of diamines represented by the formulas (DI-2) to (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

Examples of diamines represented by the formula (DI-5) are shown below.

In the formula (DI-5-1), m is an integer of 1 to 12.

In the formulas (DI-5-12) and (DI-5-13), m is an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In the formulas (DI-5-35) to (DI-5-37) and formula (DI-5-39), m is an integer of 1 to 12, DI-5-39), k is an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.

Examples of diamines represented by the formula (DI-6) are shown below.

Examples of diamines represented by the formula (DI-7) are shown below.

In the formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

Examples of diamines represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of diamines represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of diamines represented by the formula (DI-12) are shown below.

Examples of diamines represented by the formula (DI-13) are shown below.

Examples of diamines represented by the formula (DI-14) are shown below.

Examples of the diamine represented by the formula (DI-15) are shown below.

Examples of diamines represented by the formula (DI-16) are shown below.

We will explain Dehydrazide. Dihydroidazides having no known side chain include the following formulas (DIH-1) to (DIH-3).

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or - (CF ₃ ) ₂ -.

In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of this group may be substituted by methyl, ethyl, or phenyl. In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of this group may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -. In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is arbitrary.

Examples of the formulas (DIH-1) to (DIH-3) are shown below.

In the formula (DIH-1-2), m is an integer of 1 to 12.

Such non-chain type diamines and dihydroads have the effect of improving the electric characteristics such as lowering the ion density of the liquid crystal display element. When a non-chain type diamine and / or a dihydrazide is used as a diamine used for producing a polyamic acid or a derivative thereof used in the liquid crystal aligning agent of the present invention, the proportion of the diamine and the dihydrazide in the total amount of the diamine and the dihydrazide Is preferably 0 to 90 mol%, more preferably 0 to 50 mol%.

The side chain type diamine will be described. As the side chain group of the side chain type diamine, the following groups may be mentioned.

As the side chain, it is preferable to firstly substitute alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyl Examples of the substituent include an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group, and an alkoxy group. The alkyl, alkenyl and alkynyl groups in these groups are all three or more carbon atoms. However, in the case of alkyloxyalkyl, the number of carbon atoms in the whole group may be 3 or more. These groups may be linear or branched.

Subsequently, it is preferable that the ring at the terminal is substituted with at least one substituent selected from the group consisting of phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy , Phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl of 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexyl (Cyclohexyl) phenyloxy, bis (cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) , And cyclohexyl bis (phenyl) oxycarbonyl, and the like.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group of two or more rings composed of a benzene ring and a cyclohexane ring, wherein the bonding group is independently a single bond, -O-, -COO -, -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, and the ring at the terminal is substituted with alkyl having 1 or more carbon atoms, fluorine-substituted alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms And a ring grouping group. It is effective as a prayer side instrument with a steroid skeleton.

Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, and m' is an integer of 1 to 12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH ₂ - and -CH ₂ CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be substituted with -O-, -CH = CH-, or -C≡C-. Hydrogen of the phenyl is _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, or may be substituted by alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group &quot; R ²⁵ -G ²⁶ - &quot; is taken as 1 position, it is preferable that the two bonding positions are 3 position and 5 position or 2 position and 5 position.

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups and independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one -CH ₂ - -O-, -COO-, -OCO-, -CONH- or -CH = CH-. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, , 5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or an anthracene-9,10-diyl, ring B ^21, B loop ^{22, 23} and ring B In ring B ²⁴ , at least one hydrogen may be replaced by -F or -CH ₃ , s, t and u are independently integers from 0 to 2, the sum of these being 1 to 5, s, t or When u is 2, the two couplers in each parenthesis may be the same or different and the two rings may be the same or different. R ²⁶ is hydrogen, -F, -OH, C 1 -C 30 alkyl, C 1 -C 30 fluorine-substituted alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2, or -OCF of 1 to 30 carbon atoms in the ₃ And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are alkyl having 1 to 30 carbon atoms and alkoxy having 1 to 30 carbon atoms.

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl. A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. Formula (DI-32) 2 group of from the "- phenylene -G ³⁰ -O-" is one of a bond to the 3 position of the steroid nucleus, and the other one is preferably bonded to the 6-position of the steroid nucleus . Equation 2 groups in (DI-33) "- phenylene -G ³⁰ -O-" binding site on the benzene ring is, for the engaged position of the steroid nucleus, preferably in the meta-position or para-position, respectively . In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or alkylene having 1 to 3 carbon atoms. R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH═CH-, or -C≡C-. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring represents any bonding position in the ring, it is preferable that the bonding position of G ³¹ is independently a meta position or a para position with respect to the bonding position of G ³¹ .

Specific examples of the side chain type diamine are illustrated below. Examples of the diamines having side chains of the formulas (DI-31) to (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3).

Examples of the compound represented by the formula (DI-31) are shown below.

In the formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms, Lt; / RTI &gt; R ³⁵ is alkyl of 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms, preferably alkyl of 3 to 25 carbon atoms or alkoxy of 3 to 25 carbon atoms.

In the formulas (DI-31-12) to (DI-31-17), R ³⁶ is alkyl of 4 to 30 carbon atoms, preferably alkyl of 6 to 25 carbon atoms. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably 8 to 25 carbon atoms.

In the formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl of 1 to 20 carbon atoms or alkoxy of 1 to 20 carbon atoms, preferably alkyl of 3 to 20 carbon atoms, Lt; / RTI &gt; R ³⁹ is hydrogen, -F, a C 1 -C 30 alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF of 1 to 30 carbon atoms of _3, preferably an alkyl, or with a carbon number of 3 to 25 Alkoxy of 3 to 25 carbon atoms. And G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

Examples of the compound represented by the formula (DI-34) are shown below.

In formula (DI-34-1) ~ formula (DI-34-12), R ⁴⁰ is hydrogen or alkyl of 1 to 20 carbon atoms, preferably hydrogen or alkyl of 1 to 10 carbon atoms, and R ⁴¹ is hydrogen Or alkyl having 1 to 12 carbon atoms.

Examples of the compound represented by the formula (DI-35) are shown below.

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is alkyl having 6 to 30 carbon atoms and R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms.

(DI-1-1) to (DI-16-1), DIH-1-1 to DIH-3-6, and DI- -1) to (DI-35-3) may also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

In the formulas (DI-36-1) to (DI-36-8), each of R ⁴² independently represents an alkyl group having 3 to 30 carbon atoms.

In formula (DI-36-9) to formula (DI-36-11), e is an integer of 2 to 10, and in formula (DI-36-12), R ⁴³ is each independently hydrogen, -NHBoc and -N (Boc) _2, at least one of R ⁴³ is -NHBoc or -N (Boc) _2, in formula (DI-36-13), R ⁴⁴ is -NHBoc or -N (Boc) _2, and , And m is an integer of 1 to 12. Wherein Boc is a t-butoxycarbonyl group.

(DI-1-3), the formula (DI-5-1), the formula (DI-5-5), and the dihydroxy compound represented by the formula (DI-5-12), the formula (DI-5-12), the formula (DI-5-13) (DI-5-1), m = 2, 4, or 6 is preferable, and m = 4 (DI-5-12), m = 2 to 6 is preferable, m = 5 is particularly preferable, and in the formula (DI-5-13), m = 1 or 2 , And m = 1 is particularly preferable.

(DI-3-1), the formula (DI-2-1), the formula (DI-5-1) and the formula (DI-2-1) among the above diamines and dihydrazides, , Diamines represented by the formulas (DI-5-5), (DI-5-24) and (DI-7-3) are preferred and diamines represented by (DI-2-1) are particularly preferable. In the formula (DI-5-1), it is preferable that m = 2, 4 or 6, m = 4 is particularly preferable, m = 2 or 3 and n = 1 or 2 is preferable, and m = 1 is particularly preferable.

(DI-2-1), formula (DI-4-1) and formula (DI-4-2) among the diamines and dihydrazides described above are of importance in improving the VHR of the liquid crystal display element. (DI-5-28), the formula (DI-5-30), and the formula (DI- Diamine represented by the formula (DI-2-1), the formula (DI-5-1) and the formula (DI-13-1) is particularly preferable. Among them, in the formula (DI-5-1), m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

It is effective as one of the methods for preventing baking to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-2) (DI-5-1), DI-5-12, DI-5-13, DI-5-28 and DI-16-1 Diamine represented by the formula (DI-4-1), the formula (DI-5-1) and the formula (DI-5-13) is particularly preferable. Among them, in the formula (DI-5-1), m is preferably 2, 4 or 6, m is particularly preferably 4, and m is preferably 2 to 6 in the formula (DI-5-12) And m = 5 is particularly preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

In each of the diamines, a part of the diamine may be substituted with a monoamine in the range that the ratio of the monoamine to the diamine is 40 mol% or less. Such substitution can cause termination of the polymerization reaction at the time of producing the polyamic acid, and it is possible to inhibit further progress of the polymerization reaction. Therefore, by such substitution, it is possible to easily control the molecular weight of the obtained polymer (polyamic acid or its derivative), and to improve the coating property of the liquid crystal aligning agent without impairing the effect of the present invention have. The diamine substituted with a monoamine may be used in one kind or in two or more types unless the effect of the present invention is impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, Octadecylamine, and n-eicosylamine.

The polyamic acid or derivative thereof of the present invention may further contain a monoisocyanate compound in its monomer. By incorporating the monoisocyanate compound into the monomer, the terminal of the resulting polyamic acid or its derivative is modified and the molecular weight is controlled. By using the polyamic acid of the terminal modification type or a derivative thereof, for example, the coating property of the liquid crystal aligning agent can be improved without hindering the effect of the present invention. The content of the monoisocyanate compound in the monomer is preferably from 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic acid dianhydride in the monomer from the viewpoint of the above. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid and the derivative thereof of the present invention are obtained by reacting a mixture of the acid anhydride and a diamine in a solvent. In this synthesis reaction, special conditions other than the selection of the raw materials are not required, and the conditions for conventional synthesis of polyamic acid can be applied as they are. The solvent to be used will be described later.

The liquid crystal aligning agent of the present invention may further contain components other than the polyamic acid or the derivative thereof. The other ingredients may be one kind or two kinds or more. As other components, for example, other polymers and compounds described later can be mentioned.

The liquid crystal aligning agent of the present invention may further contain other polymers other than the polyamic acid or derivatives thereof of the present invention. The other polymer is a polymer other than a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing the diamine of the present invention and is obtained by reacting a diamine not containing a diamine of the formula (1) Polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (styrene-phenylmaleimide) derivative, poly (Meth) acrylate, and the like. One kind may be used, or two or more kinds may be used. Of these, other polyamic acid or derivatives thereof and polysiloxane are preferable, and other polyamic acids or derivatives thereof are more preferable.

In the alignment agent in which the polyamic acid or its derivative of the present invention is blended with other polyamic acid or its derivative, the structure and the molecular weight of each polymer are controlled, and the resultant is applied to the substrate as described later and subjected to preliminary drying , The polyamic acid or its derivative component [A] of the present invention can be separated into the upper layer and the other polyamic acid or its derivative component [B] can be separated into the lower layer. This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. It can be confirmed that the confirmation of the layer separation is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component in the surface energy of the formed alignment film.

The tetracarboxylic acid dianhydride used for synthesizing other polyamic acid or its derivative is a tetracarboxylic acid dianhydride used for synthesizing a polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention The tetracarboxylic acid dianhydride may be selected from the known tetracarboxylic dianhydrides without limitation and the same ones as those exemplified above may be mentioned.

Among them, when it is important to improve the layer separability in the acid dianhydride, the formula (AN-3-2), the formula (AN-1-13) and the formula (AN-4-30) desirable.

(AN-1-1), (AN-1-2), (AN-2-1), and (AN-2-1) among the above-mentioned acid dianhydrides in the case where it is important to improve the transmittance of the liquid crystal display element. AN-3-1), AN-4-17, AN-4-30, AN-5-1, AN-7-2, AN-10-1 ), (AN-10-2), (AN-16-3) and (AN-16-4) = 4 or 8, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is particularly preferable.

(AN-1-2), (AN-2-1), (AN-7-2), and (AN-7-2) among the acid dianhydrides in the case of emphasizing the improvement of the VHR of the liquid crystal display element. (AN-10-1), (AN-10-2), (AN-16-3) and (AN-16-4) ), It is preferable that m = 4 or 8.

It is effective as one of the methods for preventing baking to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. (AN-1-13), (AN-3-2), (AN-4-21), and (AN-4-29) among the above acid anhydrides, , And a compound represented by the formula (AN-11-3) are preferable.

The tetracarboxylic acid dianhydride used for synthesizing the other polyamic acid or its derivative preferably contains 10 mol% or more of the aromatic tetracarboxylic acid dianhydride relative to the total tetracarboxylic acid dianhydride, More preferably 30 mol% or more.

The diamines and dihydroidazides used for synthesizing other polyamic acids or their derivatives include other diamines which can be used for synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention, The same thing as the one can be cited.

When it is desired to further improve the layer separability, that is, the orientation of the liquid crystal, it is preferable to use a compound represented by the formula (DI-4-1), formula (DI-4-2) Diamines and dihydrides represented by the formulas (DI-4-10), (DI-5-1), (DI-5-9), (DI-5-28) Among them, in the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is particularly preferable.

(DI-2-1), (DI-2-1), (DI-5-1), and (DI-5-1) among the diamines and dihydrazides described above, DI-7-3), and the diamine represented by the formula (DI-2-1) is particularly preferable. In the formula (DI-5-1), m = 1, 2, or 4 is preferable, m = 1 or 2 is particularly preferable, n = 1 or 2 is preferable, and m = 1 is particularly preferable.

(DI-2-1), formula (DI-4-1) and formula (DI-4-2) among the diamines and dihydrazides described above are of importance in improving the VHR of the liquid crystal display element. , The diamine represented by the formula (DI-4-15), the formula (DI-5-1), the formula (DI-5-28), the formula (DI- 5-30) And diamines represented by the formulas (DI-2-1), (DI-5-1) and (DI-13-1) are particularly preferable. Among them, in formula (DI-5-1), m = 1 or 2 is particularly preferable, and in formula (DI-5-30), k = 2 is particularly preferable.

It is effective as one of the methods for preventing baking to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film. (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-2) 5-15), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-1), and (DI-5-1), and the diamine represented by the formula (DI- 5-12) are particularly preferable. Among them, m is preferably 1 or 2 in formula (DI-5-1), m is preferably 2 to 6, particularly preferably m = 5 in formula (DI-5-12) In the formula (DI-5-13), m = 1 or 2 is preferable, m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

The diamine used for synthesizing the other polyamic acid or its derivative is preferably one containing 30 mol% or more, and more preferably 50 mol% or more, of the aromatic diamine with respect to the total diamine.

The other polyamic acid or its derivative can be synthesized in accordance with the method described below as a method for synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention.

The proportion of the [A] component relative to the total amount of the polyamic acid or its derivative (component (A)) of the present invention and the other polyamic acid or derivative thereof (component [B]) is preferably 10% by weight to 100% By weight, more preferably 20% by weight to 100% by weight.

As the polysiloxane, there may be mentioned, for example, Japanese Patent Application Laid-Open Nos. 2009-036966, 2010-185001, 2011-102963, Japanese Laid-Open Patent Publication No. 2011-253175, Japanese Laid-Open Patent Publication No. 2012-159825, , International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International &Lt; RTI ID = 0.0 &gt; 2012/165354, &lt; / RTI &gt;

&Lt; Alkenyl-substituted nadimide compound &

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The alkenyl-substituted nadimide compound may be used alone or in combination of two or more. The content of the alkenyl-substituted nadimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight based on the polyamic acid or the derivative thereof for the above purpose desirable.

The nadimide compound will be specifically described below.

The alkenyl-substituted nadimide compound is preferably a compound capable of dissolving in the solvent for dissolving the polyamic acid or the derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadimide compound include compounds represented by the following formula (NA).

In formula (NA), L ¹ and L ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons or benzyl, n is 1 or 2;

In the formula (NA), when n = 1 il, W is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, having a carbon number of 5-8 of the cycloalkyl, aryl, benzyl having a carbon number of 6 ~ 12, -Z ¹ of - (O) _r - (Z ² O) _k -Z ³ -H wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, r is 0 or 1, and k (Z ⁴ ) _r -BZ ⁵ -H wherein Z ⁴ and Z ⁵ are each independently an alkylene group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, alkylene and, B is phenylene, and, r is a group, -BTBH (wherein, B is a phenylene group, and, T is _{-CH 2 -, -C (CH 3} ) represented by a 0 or a 1) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or a group in which one to three hydrogens of these groups are substituted with -OH.

In this case, preferred W is an alkyl having 1 to 8 carbon atoms, an alkenyl having 3 to 4 carbon atoms, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbon atoms, phenyloxyphenyl, phenylmethylphenyl, And a group in which one or two hydrogens of these groups are substituted with -OH.

In the formula (NA), when n = 2, W is an alkylene having 2 to 20 carbon atoms, a cycloalkylene having 5 to 8 carbon atoms, an arylene having 6 to 12 carbon atoms, -Z ¹ -O- (Z ² O ) _k -Z ³ -. (wherein, Z Z ¹ ~ ^3, and the definition of k are as defined above) represents a group, -Z ⁴ -BZ ⁵ - (wherein, Z ^4, Z ⁵ and B are defined in the -B- (OB) _r -T- (BO) _r -B- wherein B is phenylene, T is alkylene having 1 to 3 carbon atoms, -O- or -O-, -SO ₂ -, and the definition of r is as defined above), or a group in which one to three hydrogens of these groups are substituted with -OH.

In this case, preferable W is an alkylene group having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, -C ₃ H ₆ -O- (Z ² -O) _n -OC ₃ H ₆ - , Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2, -BTB- (wherein B is phenylene and T is -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (wherein B is phenylene), and a group in which one or two hydrogen of these groups is substituted with -OH to be.

Such an alkenyl-substituted nadimide compound is obtained by synthesizing an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C for 0.5 to 20 hours as described in, for example, Japanese Patent Publication No. 2729565 A compound or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadimide compound include the following compounds.

2,1-hept-5-ene-2,3-dicarboxyimide, N-methyl-allylbicyclo [2.2.1] 2.2.1] hept-5-ene-2,3-dicarboxyimide, N-methyl-methallylmethylbicyclo [2.2.1] hept- , 3-dicarboxyimide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

2.2.1] hept-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo [2.2.1] hepto-5- N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-allyl- 2,1-hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-methallylbicyclo [2.2.1] N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept- , 3-dicarboxyimide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo [2.2.1] Ene-2,3-dicarboxyimide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo [2.2.1] hepto- Benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-benzyl-allylmethylbicyclo [2.2.1] hept- 2,3-dicarboxyimide, N- (2-hydroxyethyl) - allylbicyclo [2.2.1] hept-5- 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl) -malilylbicyclo [2.2.1] hept- , 3-dicarboxyimide,

(2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-hydroxycyclohexyl) (Methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

(4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- 2,1-hept-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) methallylbicyclo [2.2.1] hept- - (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] (P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hepto-5- Ethyl} - methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- [2- {2- (2- hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] -2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] 2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -malilylicyclo [2.2.1] hept- Dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {4- (Methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {4- Phenyl} -methallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, and their oligomers,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Bis {3 '- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2- Bis [3 '- (methallylbicyclo [2.2.1] hept-5-en-2-yl) , 3-dicarboxyimide) propoxy} ethane, bis [2 '- (3' - (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} , Bis [2 '- {3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} butane, 1,4-bis {3 ' - ene-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- Xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

Bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2- Phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- Phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- 2,1-hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone,

Bis [4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hepto- -2,3-dicarboxyimide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane, 1,5-bis { 3'- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane, 1,4- ] Hept-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

Di-hydroxy-benzene, N, N'-p- (2- (4-hydroxyphenyl) N'-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Methylcyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylylene- bis (allylbicyclo [2.2.1] N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-di Carboxyimide), N, N'-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Phenoxy} phenyl] propane, bis {4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -2- - (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -2-hydroxyphenyl} methane, bis {3- Phenyl] ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) - Phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane, N , N ', N "-tri (ethylene methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) isocyanurate, and oligomers thereof.

The alkenyl-substituted nadimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene-phenylene group.

Among the alkenyl-substituted nadimide compounds, preferable compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, Phenoxy} phenyl] propane, 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5- (methallylbicyclo [2.2.1] hept- -2,3-dicarboxyimide) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane.

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- Phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- 2,1-hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 Phenyl] sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} Sulfone.

More preferred alkenyl substituted nadimide compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide).

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- Xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide).

Bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2- Phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane .

Particularly preferred alkenyl-substituted nadimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl } Methane, N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) represented by the formula (NA- -3), and N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide).

<Compound Having Radically Polymerizable Unsaturated Double Bond>

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The compound having a radically polymerizable unsaturated double bond may be a single compound or two or more compounds. The compound having a radically polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. The content of the compound having a radical polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight based on the weight of the polyamic acid or the derivative thereof for the above- %.

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is preferably such that the ion density of the liquid crystal display element is reduced, the time-dependent increase in the ion density is suppressed, , The compound having a radical polymerizable unsaturated double bond / alkenyl-substituted nadimide compound is preferably in a weight ratio of 0.1 to 10, more preferably 0.5 to 5.

The compound having a radically polymerizable unsaturated double bond will be specifically described below.

Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid derivatives such as (meth) acrylic acid ester, (meth) acrylamide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic esters include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include ethylenebisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200 manufactured by Toa Synthetic Chemical Industry Co., Ltd., KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684 manufactured by Osaka Organic Chemical Industry Co., Ltd., V260, V312 and V335HP manufactured by Kyowa Chemical Industry Co., Ltd., and Light Acrylate BA -4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of trifunctional or more polyfunctional (meth) acrylic acid esters include 4,4'-methylene bis (N, N-dihydroxyethylene acrylate aniline), Aro, a product of Toagosei Chemical Industry Co., KAYARADDPCA-20, KAYARADDPCA-20 manufactured by NIPPON KAYAKU CO., LTD., Which are products of Nikon M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M- 30, KAYARADDPCA-60, KAYARADDPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-propyl acrylamide, N-propyl methacrylamide, N-cyclopropyl acrylamide, Tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethylacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-methylacrylamide, N, N-diethylacrylamide, N-methyl-N-propyl acrylamide, N-methyl- N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacryloyl Amide, N-phenylmethacrylamide, N-butyl methacrylamide, N- (iso- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethyl methacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, (Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebis methacrylamide .

Among the above-mentioned (meth) acrylic acid derivatives, N, N'-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate and 4,4'-methylenebis - dihydroxyethylene acrylate aniline) is particularly preferred.

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by K-I Hasegawa Co., Ltd. and BMI-1000, BMI-3000, BMI-4000 and BMI-5000 manufactured by Daika Chemical Industry Co., And BMI-7000.

&Lt;

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound in order to stabilize the electric characteristics of the liquid crystal display element for a long term. The oxazine compound may be a single compound or two or more compounds. The content of the oxazine compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and still more preferably from 1 to 20% by weight, based on the weight of the polyamic acid or the derivative thereof .

The oxazine photochemical compound will be specifically described below.

The oxazine compound is soluble in a solvent which dissolves the polyamic acid or its derivative. In addition, an oxazine compound having ring-opening polymerization property is preferable.

The number of the oxazine structures in the oxazine photographic compound is not particularly limited.

Various structures are known in the structure of the jade photograph. In the present invention, the structure of the oxazine is not particularly limited, but the structure of the oxazine having an aromatic group containing a condensed polycyclic aromatic group, such as benzoxazine or naphthoxy, .

Examples of the oxazine compound include the compounds represented by the following formulas (OX-1) to (OX-6). In the following formulas, the bond indicated toward the center of the ring indicates that it is bonded to any carbon which constitutes a ring and is capable of bonding with a substituent.

In the formula (OX-1) ~ formula ^(OX-3), L 3 and L ⁴ are in an organic group of 1 to 30 carbon atoms, formula (OX-1) ~ formula ^{(OX-6), L 5} ~ L ⁸ is in a hydrocarbon group having 1 to 6 carbon atoms or hydrogen, formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ represents a single bond, -O-, -S- _{, -SS-, -SO 2 -, -CO-} , -CONH-, -NHCO-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) v -, -O - (CH ₂ ) _v -O-, -S- (CH ₂ ) _v -S-, wherein v is an integer of 1 to 6, and in formula (OX-5) and formula (OX- ² is a single bond independently, -O-, -S-, -CO-, -C (CH 3) 2 -, -C (CF 3) 2 - or an alkylene group having a carbon number of 1 to 3, in the Q ² of the benzene ring, hydrogen bonded to the naphthalene ring is optionally independently be substituted with _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2.

The oxazine photographic compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

As the oxazine compound represented by the formula (OX-1), for example, the following oxazine compounds can be mentioned.

In the formula (OX-1-2), L ³ is preferably an alkyl having 1 to 30 carbon atoms, more preferably an alkyl having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably alkyl of 1 to 30 carbon atoms, more preferably alkyl of 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-3) include an oxazine compound represented by the following formula (OX-3-I).

Wherein L ³ and L ⁴ are each an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, Q ¹ is a single bond, - _{CH 2 -, -C (CH 3} ) 2 -, -CO-, -O-, -SO 2 -, -C (CH 3) 2 -, or -C (CF _{3) 2} - a. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

In the formulas, L ³ and L ⁴ are preferably alkyl of 1 to 30 carbon atoms, more preferably alkyl of 1 to 20 carbon atoms.

As the oxazine compound represented by the formula (OX-4), for example, the following oxazine compounds can be mentioned.

As the oxazine compound represented by the formula (OX-5), for example, the following oxazine compounds can be mentioned.

As the oxazine photographic compound represented by the formula (OX-6), for example, the following oxazine photographic compounds may be mentioned.

Among them, more preferred are compounds of the formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX- 3-5) ), Formula (OX-3-9), Formula (OX-4-1) to Formula (OX-4-6), Formula (OX-5-3) OX-6-2) to (OX-6-4).

The oxazine compound can be produced by the same method as described in International Publication Nos. 2004/009708, 11-12258 and 2004-352670.

An oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine and an aldehyde (see WO 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting a primary amine with formaldehyde by a slow addition method and then adding a compound having a naphthol-based hydroxyl group to react it (see WO 2004/009708 .).

The oxazine compound represented by the formula (OX-3) is obtained by reacting 1 mole of a phenol compound, at least 2 moles of an aldehyde and 1 mole of a primary amine per one phenolic hydroxyl group in an organic solvent, In the presence of a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see WO 2004/009708 and JP-A 11-12258).

The oxazine compounds represented by the formulas (OX-4) to (OX-6) can be prepared by reacting a plurality of benzene rings such as 4,4'-diaminodiphenylmethane with an aldehyde having an organic group bonding them, , And phenol in dehydration condensation reaction in n-butyl alcohol at a temperature of 90 占 폚 or higher (see JP-A-2004-352670).

<Oxazoline compound>

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element in the long term. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight based on the polyamic acid or the derivative thereof for the above purposes. Alternatively, the content of the oxazoline compound is preferably from 0.1 to 40% by weight based on the weight of the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.

The oxazoline compound may have only one oxazoline structure or two or more oxazoline structures in one compound. The oxazoline compound may have at least one oxazoline structure in one compound, but preferably has two or more oxazoline compounds. The oxazoline compound may be a polymer having an oxazoline structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or may be a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxazoline structure. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or may be a copolymer of two or more monomers having an oxazoline structure in the side chain and a monomer having no oxazoline structure Or may be a copolymer.

The oxazoline structure is preferably a structure existing in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure and the carbonyl group of the polyamic acid can react with each other.

Examples of the oxazoline compound include 2,2'-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxa Benzyl-2-oxazoline, 2,6-bis (iso-propyl-2-oxazoline) Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl- (2-oxazoline), 2,2'-methylenebis (4-tert-butyl-2-oxazoline) and 2,2'-methylenebis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having an oxazolyl such as Epocross (trade name, manufactured by Nippon Kogyo Co., Ltd.) are also exemplified. Among them, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.

<Epoxy Compound>

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element in the long term. The epoxy compound may be one kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and still more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof for the above purposes.

Hereinafter, the epoxy compound will be specifically described.

Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclo (3,4-epoxycyclohexyl) ethyl trimethoxysilane, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxy Epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, epibromohydrin, N, N-diglycidyl aniline, and 3- [2- (perfluorohexyl) ethoxy] - epoxy propane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether , 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- 3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name "Techmoa VG3101L", manufactured by Mitsui Chemicals).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl Methane, and 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of other monomers copolymerizable with the monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl Butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Ethyl (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide .

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Specific examples of preferred copolymers of monomers having an epoxy ring and other monomers include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer , Benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3- Ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

Among these examples, N, N, N ', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N , N'-tetraglycidyl-4,4'-diaminodiphenyl methane, trade name "Techmoa VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate , N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferable.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, Epoxy compounds, and cyclic aliphatic epoxy compounds. The epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

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

Examples of the glycidyl ether include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol-A type epoxy compounds, hydrogenated bisphenol-F type epoxy compounds, A bisphenol-A epoxy compound, a bisphenol-S epoxy compound, a hydrogenated bisphenol-type epoxy compound, a brominated bisphenol-A type epoxy compound, a brominated bisphenol-F type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, , Brominated cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, naphthalene skeleton containing epoxy compounds, aromatic polyglycidyl ether compounds, dicyclopentadiene phenol type epoxy compounds, alicyclic diglycidyl ether compounds, aliphatic Polyglycidyl ether compounds, polysulfide Type diglycidyl there may be mentioned ether compound, and biphenol type epoxy compound.

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

Examples of glycidyl amines include polyglycidyl amine compounds and glycidyl amine type epoxy resins.

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

As the glycidyl amide, for example, a glycidyl amide type epoxy compound can be mentioned.

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

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

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007 and jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation) DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all trade names, manufactured by DIC) (Trade name, manufactured by Mitsui Chemicals, Inc.) can be mentioned.

Examples of the bisphenol F type epoxy compounds include jER806, jER807, and jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epitoto YDF-170, Eptoto YDF-175S and Eptoto YDF- DER-354 (trade name, manufactured by Dow Chemical Company), Epiclon 830, and Epiclon 835 (all trade names, manufactured by DIC Corporation).

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

As the hydrogenated bisphenol-A type epoxy compound, there can be mentioned, for example, Santotto ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), Ricare resin HBE-100 (trade name, manufactured by Shin- -252 (trade name, manufactured by Nagase Chemtex Co., Ltd.).

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

Examples of the brominated bisphenol-A type epoxy compound include jER5050, jER5051 (all trade names, manufactured by Mitsubishi Chemical Corporation), Ecototo YDB-360 and Ecototo YDB-400 (all trade names, DER-530, DER-538 (all trade names, manufactured by The Dow Chemical Company), Epiclon 152, and Epiclone 153 (all trade names, manufactured by DIC Corporation).

Examples of the phenol novolak type epoxy compound include jER152, jER154 (all trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Toto Hossei Co., Ltd.), DEN431 and DEN438 EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) can be mentioned.

Examples of the cresol novolak epoxy compounds include epoxy resins such as jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701 and YDCN-702 (all trade names, manufactured by Toto Chemical Industry Co., Ltd.), Epiclon N-665, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) were charged into a reactor equipped with a stirrer, .

Examples of the bisphenol A novolac epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation) and Epiclon N-880 (trade name, manufactured by DIC Corporation).

Examples of the naphthalene skeleton-containing epoxy compound include Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade name, ).

Examples of the aromatic polyglycidyl ether compounds include hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether ( Bis [4 - ([2,3-epoxypropoxy] phenyl) -2- [4- [ ] Ethyl] phenyl] propane (the following formula EP-4), tris (4-glycidyloxyphenyl) methane (the following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation) DPPN-501H, DPPN-501H, and NC6000 (all trade names, manufactured by Nippon Yakitori Co., Ltd.), DPPN- (Manufactured by Mitsui Chemicals, Inc.), a compound represented by the following formula EP-6, and a compound represented by the following formula: EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company) and Epiclon HP-7200 (trade name, manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexanedimethanol diglycidyl ether compound and ricerazine DME-100 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether (following formula EP-10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromonopentyl Denacol EX-910, Denacol EX-830, Denacol EX-911, Denacol EX-920, Denacol EX-931, (Trade name, manufactured by Nagase Chemtex Co., Ltd.), DD-503 (trade name, manufactured by ADEKA), Rica resin W-100 (trade name, , Shin Nippon 1,3,5,6-tetraglycidyl-2,4-hexanediol (the following formula: EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylol Denacol EX-311, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all trade names, available from Nagase Chemtex Co., Ltd.) ).

Examples of polysulfide diglycidyl ether compounds include FLDP-50 and FLDP-60 (all trade names, manufactured by Toray Industries, Inc.).

Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P and NC-3000S (all trade names, .

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following formula EP-17), diglycidyl phthalate (the following formula EP-18), bis (2-methyloxiranylmethyl) phthalate A compound represented by the following formula: EP-21, a compound represented by the following formula: EP-22, and a compound represented by the following formula: .

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epiclon 200, Epiclon 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711 , And Denacol EX-721 (both trade names, manufactured by Nagase Chemtex Co., Ltd.).

Examples of the polyglycidylamine compounds include N, N-diglycidyl aniline (formula EP-24), N, N-diglycidyl-o-toluidine (formula EP- , N-diglycidyl-m-toluidine (following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline , N, N, O-triglycidyl-p-aminophenol (formula EP-29), aminopropyltrimethoxysilane (formula EP- N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (the following formula EP-31), N , N, N ', N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33) ) Cyclohexane (the following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohex (N, N-diglycidylamino) cyclohexane (the following formula EP-36), 1,3-bis (N, N-diglycidylamino) Benzene (the following formula EP-37), 1,4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2,6- ) N, N, N ', N'-tetraglycidyl-4,4'-diaminodicyclohexyl methane (formula EP-40) N, N ', N', N'-tetramethylbiphenyl (formula EP-41), 2,2'-dimethyl- -Tetraglycidyl-4,4'-diaminodiphenyl ether (EP-42), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (Represented by the following formula EP-43), 2,4,4'-tris (N, N-diglycidylamino) diphenyl ether (N, N-diglycidylamino) biphenyl (formula EP-46), 3,4, 4,3'4'-tetrakis , 3 ', 4'-tetrakis (N, N-diglycidylamino) diphenyl Ter (EP-47 shown below), a compound represented by the following formula EP-48, and a compound represented by the following formula: EP-49.

The homopolymer of the oxiranyl-containing monomer includes, for example, polyglycidyl methacrylate. Examples of the copolymer of the monomer having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-gly Methyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl ) Methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

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

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

Examples of the glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) 5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione (EP- ), And glycidyl isocyanurate type epoxy resin.

Examples of the chain type aliphatic epoxy compounds include epoxidized polybutadiene and Epolide PB3600 (trade name, manufactured by Daicel Co.).

Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celloxide 2021 (manufactured by Daicel), EP -52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (the following formula EP- Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2: 8', 3'-epoxycyclopentane ether (following formula EP-54), epsilon -caprolactone- , 9-diepoxy limonene (Celloxide 3000 (trade name, manufactured by Daicel), the following formula EP-55), a compound represented by the following formula EP-56, CY-175, CY-177 and CY- EHPD-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.), and a cyclic aliphatic epoxy resin (trade name) manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan) .

The epoxy compound is preferably at least one of a polyglycidylamine compound, a bisphenol A novolak type epoxy compound, a cresol novolak type epoxy compound and a cyclic aliphatic epoxy compound, and more preferably at least one of N, N, N ', N'- (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, trade name "Techmoa VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer , N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type epoxy compound, and cresol novolak type epoxy compound.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include polymer compounds other than polyamic acid and derivatives thereof, and low molecular weight compounds, each of which can be selected depending on the purpose.

For example, the polymer compound may be a polymer compound soluble in an organic solvent. The addition of such a polymer compound to the liquid crystal aligning agent of the present invention is preferable from the viewpoint of controlling the electric characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

Examples of the above-mentioned low-molecular compounds include: 1) a surfactant for this purpose when it is desired to improve the coating property, 2) an antistatic agent when it is necessary to improve the antistatic property, and 3) A silane coupling agent or a titanium coupling agent; and 4) an imidization catalyst when imidization proceeds at a low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N '-Bis [3- (trimethoxysilyl) propyl] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; aliphatic amines such as N, N-dimethylaniline, N, N-diethylaniline, Aromatic substituted amines such as pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, And cyclic amines such as hydroxy substituted imidazole. The imidation catalyst is preferably at least one member selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline Do.

The addition amount of the silane coupling agent is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or the derivative thereof.

The addition amount of the imidation catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents relative to the carbonyl group of the polyamic acid or its derivative.

The amount of the other additives to be added varies depending on the use, but is usually 0 to 100% by weight and preferably 0.1 to 50% by weight based on the total weight of the polyamic acid or its derivative.

The polyamic acid or a derivative thereof of the present invention can be produced in the same manner as the known polyamic acid or derivative thereof used for forming a film of polyimide. The total amount of the tetracarboxylic acid dianhydride is preferably approximately equivalent to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The molecular weight of the polyamic acid or its derivative of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement by gel permeation chromatography (GPC).

The polyamic acid or its derivative of the present invention can be confirmed by analyzing a solid component obtained by precipitating with a large amount of a poor solvent by IR and NMR. Further, the monomer used can be identified by analyzing an extract of the decomposition product of the polyamic acid or its derivative with an organic solvent by an aqueous solution of a strong alkali such as KOH or NaOH by GC, HPLC or GC-MS.

In addition, for example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoints of application of the liquid crystal aligning agent and adjustment of the concentration of the polyamic acid or its derivative. The solvent can be applied without limitation if it is a solvent capable of dissolving a polymer component. The solvent widely includes solvents conventionally used in the production process or use of polymer components such as polyamic acid and soluble polyimide, and may be appropriately selected depending on the purpose of use. The solvent may be one kind or two or more kinds of mixed solvents.

Examples of the solvent include a hydrophilic solvent for the polyamic acid or a derivative thereof, and other solvents for improving the applicability.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for the polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N And lactones such as dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and? -Butyrolactone.

Examples of other solvents for the purpose of improving the coating property include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, and ethylene glycol monobutyl ether, diethylene glycol mono Diethylene glycol monoalkyl ether such as ethyl ether, ethylene glycol monoalkyl or phenylacetate, propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether, diethyl malonate and the like Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, and ester compounds such as acetates thereof.

Among them, the solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, dimethylimidazolidinone,? -Butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Methyl ether, and dipropylene glycol monomethyl ether are particularly preferable.

The concentration of the polyamic acid in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When this alignment agent is applied to the substrate, it may be necessary to dilute the polyamic acid contained in advance with a solvent in order to adjust the film thickness.

The solid content concentration in the alignment agent of the present invention is not particularly limited, and the optimum value may be selected in accordance with the following various coating methods. The amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the varnish, in order to suppress unevenness and pinholes at the time of coating.

The viscosity of the liquid crystal aligning agent of the present invention varies depending on the method of application, the concentration of the polyamic acid or its derivative, the type of the polyamic acid or derivative thereof, and the type and ratio of the solvent. For example, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s) in the case of application by a printing machine. If it is smaller than 5 mPa · s, it is difficult to obtain a sufficient film thickness. If it exceeds 100 mPa · s, printing unevenness may become large. In the case of coating by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method and measured (measured temperature: 25 ° C) using, for example, a rotational viscometer (TVE-20L type manufactured by Toray Industries).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the above-mentioned liquid crystal aligning agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a conventional method for producing a liquid crystal alignment film with a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal aligning agent of the present invention, a step of heating and drying, and a step of heating and firing. In the liquid crystal alignment film of the present invention, anisotropy may be imparted to the liquid crystal alignment film by rubbing the film obtained through the heating and drying process and the heating and firing process as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating film process, the heating and drying process, or after the heating and baking process. It may also be used as a liquid crystal alignment film for VA which has not undergone rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element in the same manner as in the production of a conventional liquid crystal alignment film. Examples of the substrate include glass substrates on which electrodes such as indium tin oxide (ITO), IZO (In ₂ O ₃ -ZnO), and IGZO (In-Ga-ZnO ₄ ) electrodes and color filters may be formed.

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

The heating and drying process is generally known as a heating process in an oven or an infrared room, a heating process on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within a range in which evaporation of the solvent is possible, and more preferably at a relatively low temperature relative to the temperature in the heat-firing step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C.

The heating and firing process may be carried out under the conditions necessary for the polyamic acid or its derivative to exhibit dehydration and ring-closing reaction. The firing of the coating film is generally known as a heating method in an oven or an infrared lamp, a method of heating on a hot plate, and the like. These methods are equally applicable to the present invention. In general, the reaction is preferably carried out at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, and even more preferably 150 to 250 ° C.

In the method for forming a liquid crystal alignment film of the present invention, a well-known forming method such as a rubbing method or a photo alignment method is preferably used as means for giving anisotropy to the alignment film in order to orient the liquid crystal in one direction with respect to the horizontal and / Can be used.

The liquid crystal alignment film of the present invention using the rubbing method may be formed by a process of applying the liquid crystal aligning agent of the present invention to a substrate, a step of heating and drying the substrate coated with the alignment agent, a step of heating and firing the film, As shown in FIG.

The rubbing treatment can be carried out in the same manner as in the rubbing treatment for the alignment treatment of a liquid crystal alignment film in general, but only in the condition that satisfactory retardation can be obtained in the liquid crystal alignment film of the present invention. The preferable conditions are a hair pressing amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm / sec, and a roller rotation speed of 500 to 2,000 rpm.

The liquid crystal alignment film of the present invention is suitably obtained by a method including a process other than the process described above. For example, in the liquid crystal alignment film of the present invention, a step of cleaning the film after baking or irradiation with radiation is not essential, but a cleaning step can be provided for other processes.

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning, and the like. These methods may be carried out alone or in combination. Examples of the cleaning liquid include pure water, various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone But the present invention is not limited thereto. Needless to say, these cleaning liquids are used with a sufficiently small amount of purified impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment capability of the liquid crystal alignment film of the present invention, annealing treatment by heat or light can be used before, after, and after the heat firing step, before or after the rubbing step, or before or after irradiation with polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30 to 180 占 폚, preferably 50 to 150 占 폚, and the time is preferably 1 minute to 2 hours. Examples of the annealing light used in the annealing process include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3 to 10 J / cm 2.

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring apparatus such as a step difference meter or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having anisotropy particularly in a large orientation. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364 or the like. It is also possible to evaluate by the method using ellipsometry as shown in the following examples. In detail, the retardation value of the liquid crystal alignment film can be measured by the spectroscopic ellipsometer. The retardation value of the film becomes larger in proportion to the degree of orientation of the polymer main chain. That is, it is considered that having a large retardation value has a large degree of orientation, and when used as a liquid crystal alignment film, an alignment film having a larger anisotropy has a large alignment restraining force for the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a liquid crystal display device of a transverse electric field system. When the liquid crystal display device is used in a transverse electric field type liquid crystal display device, the lower the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state, and the contrast is improved. The Pt angle is preferably 0.1 DEG or less.

The liquid crystal alignment film of the present invention can be used for alignment control of an optical compensator or any other liquid crystal material in addition to the alignment of a liquid crystal composition for a liquid crystal display. Further, since the alignment film of the present invention has large anisotropy, it can be used solely for optical compensation material applications.

The liquid crystal display element of the present invention will be described in detail.

The present invention provides a liquid crystal display device comprising a pair of substrates arranged to face each other, an electrode formed on one or both sides of the surface on which the pair of substrates face each other, and a liquid crystal alignment film And a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is an alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include a vapor-deposited film of ITO or a metal. The electrodes may be formed on the entire surface of one surface of the substrate, or may be formed into a desired shape that is patterned, for example. The desired shape of the electrode is, for example, a comb-like or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both of the substrates. For example, in the case of an IPS type liquid crystal display element, electrodes are disposed on one side of the pair of substrates, and in the case of other liquid crystal display elements, the pair of electrodes The electrodes are disposed on both sides of the substrate. And the liquid crystal alignment film is formed on the substrate or the electrode.

And the liquid crystal layer is formed in a form in which the liquid crystal composition is sandwiched by the pair of substrates opposed to each other with the liquid crystal alignment film formed thereon. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, which forms an appropriate gap between the pair of substrates can be used as needed.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy may be used. Preferred liquid crystal compositions whose dielectric anisotropy is fixed are disclosed in Japanese Patent Publication Nos. 3086228, 2635435, 5-501735, 8-157826, 8-231960, JP-A 9-241644 (EP885272A1), JP-A-9-302346 (EP806466A1), JP-A 8-199168 (EP722998A1), JP-A 9-235552, JP- Japanese Patent Application Laid-Open Nos. 9-241643 (EP885271A1), 10-204016 (EP844229A1), 10-204436, 10-231482, 2000-087040, And a liquid crystal composition disclosed in JP-A-2001-48822.

There is no problem that one or more optically active compounds are added to a liquid crystal composition having a dielectric anisotropy of positive or negative.

The liquid crystal composition having a negative dielectric anisotropy will be described. As a liquid crystal composition having negative dielectric anisotropy, for example, a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component can be mentioned.

Wherein R ^1a and R ^2a are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine , Ring A ² and ring B ² are independently selected from the group consisting of 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl or 7,8-difluorochroman- , Wherein at least one of ring A ² and ring B ² is selected from the group consisting of 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4- Di-fluoro-chromene-2,6-diyl, and Z ¹ is independently a single bond, - (CH ₂ ) ₂ -, - CH ₂ O-, -COO-, or -CF ₂ O-, j is 1, 2, or 3 And when j is 2 or 3, any two rings A ² may be the same or different and any two Z ^{1 s} may be the same or different.

Preferred rings A ² and B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl in order to increase the dielectric anisotropy, respectively, and 1,4- Hexylene.

A preferred Z ¹ is -CH ₂ O- in order to increase the dielectric anisotropy and is a single bond to lower the viscosity.

The preferred j is 1 to lower the lower limit temperature and 2 to raise the upper limit temperature.

Specific examples of the liquid crystal compound of the above formula (NL-1) include the compounds represented by the following formulas (NL-1-1) to (NL-1-32).

Wherein R ^1a and R ^2a are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine , Ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene, and Z ¹¹ and Z ¹² are independently a single bond , - (CH ₂ ) ₂ -, -CH ₂ O- or -COO-.

Preferred R &lt; ^{1a &gt;} and R &lt; ² &gt; are alkyl having 1 to 12 carbon atoms or alkoxy having 1 to 12 carbon atoms for increasing the absolute value of dielectric anisotropy so as to increase stability against ultraviolet rays or heat.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyl is ethyl, propyl, butyl, pentyl, or heptyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. To lower the viscosity, the more preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, , 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for lowering viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. In order to lower the viscosity, the trans is preferred for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl. In the case of alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferable. In these alkenyl groups, straight-chain alkenyl groups are preferred over branches.

Preferred examples of the alkenyl in which at least one hydrogen is substituted with fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3- 5,5-difluoro-4-pentenyl, and 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for lowering the viscosity.

Preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene for lowering the viscosity.

Preferred Z ¹¹ and Z ¹² are -CH ₂ O- in order to increase the dielectric anisotropy and are single bonds to lower the viscosity.

The compound (NL-1-1), (NL-1-4), (NL-1-7), or (NL- 1-32).

As preferred examples of the liquid crystal composition having negative dielectric anisotropy, JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, Japanese Patent Application Laid-Open Nos. 8-104869, 10-168076, 10-168453, 10-236989, 10-236990, 10 -236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, Japanese Patent Application Laid-Open Nos. 10-237035, 10-237075, 10-237076, 10-237448 (EP967261A1), 10-287874, 10-287874 10-287875, JP-A-10-291945, JP-A- Japanese Unexamined Patent Publication No. 11-029581, Japanese Unexamined Patent Application Publication No. 11-080049, Japanese Unexamined Patent Publication No. 2000-256307, Japanese Unexamined Patent Application Publication No. 2001-019965, Japanese Unexamined Patent Application Publication No. 2001-072626, Japanese Unexamined Patent Application Publication No. 2001-192657, 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Laid-Open Patent Publication No. 2010-537010, Japanese Laid-Open Patent Publication No. 2012-077201, Japanese Laid-Open Patent Publication No. 2009-084362 and the like.

For example, the liquid crystal composition used in the device of the present invention may further contain an additive, for example, from the viewpoint of improving the orientation. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, polymerization inhibitors and the like.

The most preferred structure of the photopolymerizable monomer or oligomer for the purpose of improving the alignment property of the liquid crystal includes the structures of (PM-1-1) to (PM-1-6).

The photopolymerizable monomer or oligomer is preferably 0.01% by weight or more in order to exhibit the effect of determining the direction of the liquid crystal after polymerization. In order to make the orientation effect of the polymer after polymerization to be appropriate, or to avoid elution of the unreacted monomer or oligomer into the liquid crystal after ultraviolet irradiation, it is preferably 30% by weight or less.

An optically active compound is mixed into the composition for the purpose of imparting a twist angle to the helical structure of the liquid crystal. Examples of such compounds are compounds (PAC-1-1) to (PAC-1-4).

The preferred ratio of the optically active phosphorus compound is 5% by weight or less. A more preferable range is from 0.01 wt% to 2 wt%.

An antioxidant is mixed with the liquid crystal composition in order to prevent a decrease in resistivity due to heating in the air or to maintain a large voltage holding ratio at room temperature as well as at a high temperature after the device is used for a long time.

A preferred example of the antioxidant is a compound (AO-1) wherein w is an integer of 1 to 10, and the like. In the compound (AO-1), a preferable w is 1, 3, 5, 7, or 9. More preferred w is 1 or 7. The compound (AO-1) wherein w is 1 is effective in preventing a decrease in resistivity due to heating in the atmosphere because of its high volatility. The compound (AO-1) with w = 7 is effective for maintaining a large voltage holding ratio at room temperature as well as at a high temperature after long use of the device because of low volatility. A preferable proportion of the antioxidant is not less than 50 ppm so as not to lower the upper limit temperature or to raise the lower limit temperature. A more preferable range is from 100 ppm to 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as amines with steric hindrance are also desirable. A preferable proportion of these absorbents and stabilizers is not less than 50 ppm in order to obtain the effect and not more than 10000 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferable range is from 100 ppm to 10000 ppm.

A dichroic dye such as an azo dye, an anthraquinone dye or the like is mixed into the composition in order to be suitable for a device in the GH (Guest host) mode. A preferable proportion of the pigment is in the range of 0.01 wt% to 10 wt%.

In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are mixed into the composition. A preferable proportion of the antifoaming agent is 1 ppm or more in order to obtain the effect, and is 1000 ppm or less in order to prevent defective display. A more preferable range is from 1 ppm to 500 ppm.

Polymerizable compounds may be incorporated into the compositions to make them suitable for devices in the PSA (polymer sustained alignment) mode. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. A particularly preferred example is a derivative of acrylate or methacrylate. Examples of such compounds are compounds (PM-2-1) to (PM-2-9). A preferable proportion of the polymerizable compound is about 0.05% by weight or more for obtaining the effect, and is about 10% by weight or less for preventing defective display. A more preferred range is from about 0.1 wt% to about 2 wt%.

Wherein R ^3a , R ^4a , R ^5a and R ^6a are independently acryloyl or methacryloyl, R ^7a and R ^8a are independently hydrogen, halogen, or alkyl of 1 to 10 carbon atoms, and Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ - may be substituted by -O- or -CH═CH-, s , t, and u are each independently 0, 1, or 2.

A polymerization initiator can be mixed as a substance necessary for easily generating a radical or an ion and initiating a chain polymerization reaction. Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan K. K.), which are photo polymerization initiators, are suitable for radical polymerization. The polymerizable compound preferably contains the photopolymerization initiator in the range of 0.1 wt% to 5 wt%. Particularly preferably, the photopolymerization initiator is contained in an amount of 1 wt% to 3 wt%.

In the radical polymerization system, the polymerization inhibitor can be mixed with a radical initiator or a radical generated from the monomer to rapidly change into a stable radical or a neutral compound, and as a result, the polymerization inhibitor can be mixed for the purpose of stopping the polymerization reaction. Polymerization inhibitors are classified into several groups. One of them is a self-stable radical such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine and the like, and the other is easily converted into a stable radical by reacting with a radical present in the polymerization system. Amino, polyhydroxy compounds, and the like. Representative examples of the latter include hydroquinone, dimethoxybenzene and the like. A preferable proportion of the polymerization inhibitor is 5 ppm or more in order to obtain the effect, and is 1000 ppm or less in order to prevent defective display. A more preferable range is from 5 ppm to 500 ppm.

By using a liquid crystal composition having negative dielectric anisotropy in the liquid crystal display element of the present invention, it is possible to provide a liquid crystal display element having excellent afterimage characteristics and good alignment stability.

Example

Hereinafter, the present invention will be described by way of examples. The evaluation methods and compounds used in the examples are as follows.

<Evaluation method>

1. Weight average molecular weight (Mw)

The weight average molecular weight of the polyamic acid was determined by the GPC method using a 2695 separation module · 2414 differential refractometer (manufactured by Waters) and calculating by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) such that the concentration of polyamic acid was about 2% by weight. The column was subjected to measurement under the conditions of a column temperature of 50 캜 and a flow rate of 0.40 ml / min using HSPgel RT MB-M (manufactured by Waters) as the developing solution. Standard polystyrene was TSK standard polystyrene manufactured by Tosoh Corporation.

2. Pre-tilt angle measurement

And measured according to a crystal rotation method.

3. Voltage maintenance rate

And the method described in &quot; Mizushima et al., Proceedings of the 14th Liquid Crystal Display Discussion p78 (1988) &quot;. The measurement was performed by applying a square wave of ± 5 V to the cell. The measurement was carried out at 60 占 폚. This value is an index indicating how much the applied voltage is maintained after the frame period. If this value is 100%, it indicates that all the charges are maintained. In a cell mounted with a positive type liquid crystal, it is 99.5% or more, and in a cell loaded with a negative type liquid crystal, 97.5% or more, a liquid crystal display device having good display quality is obtained.

4. Measurement of the amount of ions in the liquid crystal (ion density)

Was measured using a liquid crystal physical property measuring system Model 6254 manufactured by Toyotechnika Co., Ltd. according to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996). (Electrode area: 1 cm 2) at a voltage of ± 10 V and a temperature of 60 ° C. using a triangular wave having a frequency of 0.01 Hz. If the ion density is high, problems such as baking due to ionic impurities tend to occur. That is, the ion density is a physical property value which is an index for predicting the occurrence of baking. When this value is 40 pC or less, a liquid crystal display element having good display quality is obtained.

&Lt; Tetracarboxylic acid dianhydride &gt;

(AN-1-1): 1,2,3,4-butanetetracarboxylic acid dianhydride

(AN-1-13): Ethylenediamine tetraacetic acid dianhydride

(AN-2-1): 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

(AN-3-2): pyromellitic acid dianhydride

(AN-4-30): N, N'- (1,4-phenylene) bis (1,3-dioxoctahydroisobenzofuran-5-carboxamide)

(AN-7-2): 2,3,5-tricarboxycyclopentylacetic acid dianhydride

(AN-10-1): octahydropentalene-1,3,4,6-tetracarboxylic acid-1,3,4,6-2 anhydride

<Diamine>

(DI-5-1, m = 1): 4,4'-diaminodiphenylmethane

(DI-5-1, m = 4): 4,4'-diaminodiphenylbutane

(DI-5-9): 4,4'-diaminodiphenyl ether

(DI-5-12, m = 3): 1,3-bis (4-aminophenoxy) propane

(DI-5-30, k = 2): N, N'-bis (4-aminophenyl) -N, N'-dimethylethylenediamine

(4 - ((4-aminophenyl) methyl) phenyl) propane (DI-7-3, m = 3, n =

(DI-13-1): 4,4'-N, N'-bis (4-aminophenyl) piperazine

^{(DI-34-6, R 41 =} nC 5 H 11): 4 ', 4' - (4- (2- (4- aminophenyl) ethyl) phenyl) -4-pen tilbi cyclohexane

(DI-31-44): cholesteryl 3,5-diaminobenzoate

<Solvent>

Tetrahydrofuran: THF

N-methyl-2-pyrrolidone: NMP

? -butyrolactone: GBL

Butyl cellosolve (ethylene glycol monobutyl ether): BC

[Synthesis Example 1]

Synthesis of the compound represented by the formula (1-1-1).

<Step 1> Synthesis of amide form

4-amino-2,2,6,6-tetramethylpiperidine (15.0 g, 96.0 mmol) and potassium carbonate (19.9 g, 144.0 mmol) were added to a 300-ml three-necked flask equipped with a thermometer and reflux tube, And 100 ml of tetrahydrofuran (THF) was added. A solution of 3,5-dinitrobenzoyl chloride (24.3 g, 105.6 mmol) dissolved in 100 ml of THF was slowly added thereto while keeping the solution at 5 占 폚 or lower. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 ml of pure water, and the precipitated crystals were collected by filtration and dried at 80 DEG C for 6 hours to obtain the following compound. Yield 32.0 g, yield 95%.

<Step 2> Reduction of nitro group

To the 1 L autoclave reactor was added the compound obtained in the first step (32.0 g, 91.3 mmol) and 5 wt% palladium carbon powder (3.2 g), and 300 ml of tetrahydrofuran was added. The mixture was stirred at 50 DEG C under a hydrogen atmosphere of 0.5 mPa until absorption of hydrogen stopped. After cooling, the palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from ethanol (50 ml) to obtain a compound represented by the formula (1-1-1). Yield 25.0 g, yield 70%.

[Synthesis Example 2]

Synthesis of Compound Represented by Formula (1-1-2).

<Step 1> Synthesis of acid chloride

2-Bromo-5-nitrobenzoic acid (25.0 g, 101.6 mmol) was added to a 300 ml eggplant flask and 100 ml of thionyl chloride was added. The mixture was heated under reflux for 6 hours, and after cooling, thionyl chloride was distilled off under reduced pressure to obtain 2-bromo-5-nitrobenzoyl chloride. Yield 23.5 g, yield 87%.

<Step 2> Synthesis of amide form

Amino-2,2,6,6-tetramethylpiperidine (13.6 g, 87.0 mmol) and potassium carbonate (14.4 g, 104.4 mmol) were added to a 300 ml three-necked flask equipped with a thermometer and reflux tube, And 100 ml of THF was added. A solution prepared by dissolving the compound (23.0 g, 87.0 mmol) obtained in the first step in 100 ml of THF was slowly added thereto while keeping the solution at 5 캜 or lower. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 ml of pure water, and the precipitated crystals were collected by filtration and dried at 80 DEG C for 6 hours to obtain the following compound. Yield 29.0 g, yield 87%.

<Step 3>

(29.0 g, 75.5 mmol), benzophenone imine (15.0 g, 83.0 mmol), and [1,3-bis (2, Pyridyl) palladium (II) dichloride (2.1 g, 3.0 mmol) and t-butoxy potassium (12.7 g, 113.2 mmol, ), And 200 ml of toluene was added. After heating under reflux for 8 hours under nitrogen atmosphere, the insolubles were removed by filtration, and the filtrate was poured into pure water (500 ml) and extracted with ethyl acetate (500 ml). The organic layer was washed three times with pure water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were separated and purified by silica gel column chromatography (eluent: toluene: ethyl acetate = 6: 4) to obtain the following compounds. Yield 22.4 g, yield 62%.

<Step 4> Conversion to an amino group

The compound (22.0 g, 45.3 mmol) obtained in the third step was placed in a 500 ml eggplant flask, and 50 ml of 6 N hydrochloric acid and 200 ml of THF were added thereto. After stirring at room temperature for 12 hours, the solvent was distilled off under reduced pressure. 100 ml of pure water was added to the residue, and a 20% aqueous solution of sodium hydroxide was added thereto with stirring until the pH became &gt; 7, and further stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, and the crystals were washed with pure water to obtain the following compounds. Yield 12.3 g, yield 85%.

<Step 5> Reduction of nitro group

To the 1 L autoclave reactor, the compound (12.0 g, 37.5 mmol) obtained in the fourth step and 5 wt% palladium carbon powder (1.2 g) were added, and 100 ml of THF was added. The mixture was stirred at 50 DEG C under a hydrogen atmosphere of 0.5 mPa until absorption of hydrogen stopped. After cooling, the palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from 20 ml of ethanol to obtain a compound represented by the formula (1-1-2). Yield 9.4 g, yield 86%.

[Synthesis Example 3]

Synthesis of compound represented by formula (C1).

&Lt; Step 1 &gt; Synthesis of ester

4-amino-2,2,6,6-tetramethylpiperidine (15.0 g, 95.4 mmol) and potassium carbonate (19.8 g, 143.1 mmol) were added to a 300 ml three-necked flask equipped with a thermometer and reflux tube, And 100 ml of THF was added. A solution of 3,5-dinitrobenzoyl chloride (24.2 g, 105.0 mmol) dissolved in THF (100 mL) was slowly added thereto while maintaining the solution at 5 占 폚 or lower. Cooling of the reaction solution was stopped, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into 500 ml of pure water, and the precipitated crystals were collected by filtration and dried at 80 DEG C for 6 hours to obtain the following compound. Yield 30.3 g, yield 90%.

<Step 2> Reduction of nitro group

To a 1 L autoclave reactor was added the compound obtained in the first step (30.0 g, 85.4 mmol) and 5 wt% palladium carbon powder (3.0 g), and 300 ml of THF was added. The mixture was stirred at 50 DEG C under a hydrogen atmosphere of 0.5 mPa until absorption of hydrogen stopped. After cooling, the palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from 40 ml of ethanol to obtain a compound represented by the formula (C1). Yield 17.6 g, yield 71%.

[Synthesis Example 4]

Synthesis of the compound represented by formula (C2).

&Lt; First Step &gt;

In a 300 ml three-necked flask equipped with a thermometer and a reflux condenser, 3,5-dinitrobromobenzene (20.0 g, 81.0 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (14.0 g, 89.1 mmol), potassium carbonate (13.4 g, 97.2 mmol) and potassium iodide (1.3 g, 8.1 mmol) were added and 200 ml of N, N-dimethylformamide was added. The reaction solution was poured into 500 ml of pure water after cooling in a nitrogen atmosphere at 80 DEG C for 8 hours. The precipitated crystals were filtered and dried at 80 DEG C for 6 hours to obtain the following compound. Yield 18.9 g, yield 72%.

<Step 2> Reduction of nitro group

To a 1 L autoclave reactor was added the compound obtained in the first step (18.0 g, 55.7 mmol) and 5 wt% palladium carbon powder (1.8 g), and THF (200 mL) was added. The mixture was stirred at 50 DEG C under a hydrogen atmosphere of 0.5 mPa until absorption of hydrogen stopped. After cooling, the palladium carbon powder was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from 30 ml of a mixed solvent of toluene / ethanol = 5/1 to obtain a compound represented by the formula (C2). Yield 11.9 g, yield 81%.

[Example 1] Preparation of varnish

2.5874 g of the compound DI-7-3 (m = 3, n = 1) and 0.610 g of the compound (1-1-1) were placed in a 200 ml eggplant flask equipped with a thermometer, 59.0 g of methyl-2-pyrrolidone (NMP) and 15.0 g of? -Butyrolactone (GBL) were added. (AN-3-1), 0.9152 g of (AN-2-1) and 0.3261 g of (AN-1-13) were put into the autoclave, Lt; / RTI &gt; 20.0 g of butyl cellosolve (BC) was added thereto, and the mixture was heated and stirred at 70 캜 until the viscosity of the solution reached about 35.0 cP to obtain a varnish 1 having a solid content of 6 wt%. The varnish had a weight average molecular weight (Mw) of 68,000.

In accordance with the method described in Example 1, the following varnish having a solid content of 6 wt% was obtained. The composition and the weight average molecular weight (Mw) of the obtained varnish are shown in Table 1. Example 1 is also shown again. [] Represents the respective molar ratios in the tetracarboxylic acid compound group and the diamine compound group.

[Example 35]

&Lt; Preparation of liquid crystal aligning agent, production method of FFS cell, measurement of voltage holding ratio and ion density &

10 g of varnish 1 was weighed in a 50 ml eggplant type flask, 10 g of N-methyl-2-pyrrolidone and 10 g of butyl cellosolve were added thereto, and the mixture was shaken for 2 hours to obtain a liquid crystal alignment The first was obtained.

The coating varnish thus obtained was applied onto an FFS cell glass substrate with a spinner. The application condition was 2300 rpm, 15 seconds. After the coating film was prebaked at 80 캜 for about 5 minutes, baking treatment was performed at 200 캜 for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The resulting polyimide film was subjected to a rubbing treatment by a rubbing treatment apparatus manufactured by Iinuma Gage Co., Ltd., with a hair pressing amount of 0.40 mm for a rubbing cloth (fur length 1.9 mm: rayon), a stage moving speed of 60 mm / sec, Rubbing treatment was performed. The obtained substrate was ultrasonically cleaned in ethanol for 5 minutes, then rinsed with ultrapure water, and then dried in an oven at 120 ° C for 30 minutes. The surfaces on which the alignment films of the two substrates with the alignment film formed on the substrate are formed are opposed to each other so that the rubbing directions are parallel to the respective alignment films and voids for injecting the liquid crystal composition between the opposing alignment films are formed And an empty FFS cell having a cell thickness of 4 탆 was assembled. The following positive-type liquid crystal composition A was vacuum-injected into the produced empty FFS cell, and the injection port was sealed with a photo-curing agent. Subsequently, heat treatment was performed at 110 占 폚 for 30 minutes to produce an FFS liquid crystal display element (FFS cell) 1-1 for evaluating electrical characteristics.

&Lt; Positive type liquid crystal composition A &gt;

Property: NI 100.1 ° C; ?? 5.1;? N 0.093;? 25.6 mPa? S.

The voltage holding ratio of the obtained measuring cell was 99.8% at 5 V 30 Hz and the ion density was 10 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measuring cell after the reliability test was 99.7% and the ion density was 10 pC.

[Examples 36 to 68 and Comparative Examples 5 to 7]

For the varnishes 2 to 34 and varnishes C1 to C3, preparation of liquid crystal aligning agent, preparation of FFS cell, voltage holding ratio and ion density were carried out in accordance with the method described in Example 35. [ The results are shown in Table 2. The results of Example 35 are also shown again.

All of the cells other than the display device having the orientation film made of the alignment agent using the varnish C3 as one of the raw materials were satisfactory results after the initial and reliability tests.

[Examples 69 to 102 and Comparative Examples 8 to 10]

An FFS cell for evaluating electrical characteristics was manufactured in accordance with the method described in Example 35 except that the firing temperature at the time of forming the liquid crystal alignment film was 230 캜 in the production of the FFS cell for evaluation of electric characteristics, Respectively. The results are shown in Table 3.

In Cells 1-2 to 34-2, good results were obtained after both the initial and the reliability. However, in the cells C1-2 to C3-2, the voltage holding ratio and the ion density were initially decreased, and further deterioration was confirmed after the reliability test .

[Examples 103 to 136 and Comparative Examples 11 to 13]

An FFS cell for evaluating electric characteristics was manufactured in accordance with the method described in Example 35 except that the liquid crystal composition to be injected was replaced with the negative type liquid crystal composition B in the positive type liquid crystal composition A and the voltage holding ratio and ion density Respectively. The results are shown in Table 4.

<Negative Liquid Crystal Composition B>

Property: NI 75.7 ° C; ?? -4.1;? N 0.101;? 14.5 mPa? S.

Good results were obtained in all cells related to the example.

[Examples 137 to 170 and Comparative Examples 14 to 16]

An FFS cell for evaluating electrical characteristics was prepared in accordance with the method described in Example 35 except that the liquid crystal composition to be injected was replaced with the negative type liquid crystal composition B in the positive type liquid crystal composition A and the firing temperature at the time of forming the liquid crystal alignment film was set to 230 캜 And the voltage holding ratio and ion density of the cells were measured. The results are shown in Table 5.

In Cells 1-4 to 34-4, both good and reliable results were obtained. However, in Cells C1-4 to C3-4, the voltage holding ratio and the ion density were decreased at the beginning, and further deterioration was confirmed after the reliability test .

From the above examples, it is understood that the liquid crystal display element provided with the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention exhibits a constant performance at all times irrespective of the manufacturing process and maintains a good display quality even after a long time elapses. . &Lt; / RTI &gt;

[Examples 171 to 177] Confirmation of effect in polymer blend type alignment agent

In accordance with the method described in Example 1, the following varnish having a solid content of 6 wt% was obtained. The composition and weight average molecular weight (Mw) of the obtained varnish are shown in Table 6. [] Represents the respective molar ratios in the tetracarboxylic acid compound group and the diamine compound group.

[Example 178] Preparation of polymer blend type alignment agent

0.2 g of varnish 1 and 0.8 g of varnish 39 were weighed and placed in a sample bottle, and NMP / BC = 1/1 (weight ratio) was added to make 1.67 g to obtain Aligner B1.

[Examples 179 to 207]

The polymer blend alignment agents prepared in the same manner are shown in Table 7. Example 178 is also published. The numbers in brackets [] in Table 7 indicate weight%.

[Example 208] Evaluation of electric characteristics of alignment film made of polymer blend type alignment agent

An FFS liquid crystal display element (FFS cell) B1C for evaluating electrical characteristics was produced in accordance with the method described in Example 35 except that the prepared polymer blend alignment agent B1 was used and the firing treatment temperature was changed from 200 占 폚 to 230 占 폚.

The voltage holding ratio of the obtained measuring cell B1C was 99.7% at 5 V 30 Hz and the ion density was 10 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measuring cell after the reliability test was 99.7% and the ion density was 10 pC.

[Examples 209 to 237, Comparative Examples 23 to 28]

For the polymer blend alignment agents B2 to B30 and C1-B to C6-B, the production of the FFS cell, measurement of the voltage holding ratio, ion density and reliability test were carried out in accordance with the method described in Example 208. [ The results are shown in Table 8. The results of Example 208 are also published.

[Example 238]

An FFS for evaluating electric characteristics was prepared in the same manner as in Example 35 except that the prepared polymer blend alignment agent B1 was used and the liquid crystal composition for injecting the firing treatment at 200 ° C to 230 ° C was replaced by the negative liquid crystal composition B A liquid crystal display element (FFS cell) B1C-N was produced.

The voltage holding ratio of the obtained measuring cell B1C-N was 98.0% at 5 V 30 Hz and the ion density was 15 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measurement cell after the reliability test was 97.9%, and the ion density was 15 pC.

[Examples 239 to 267, Comparative Examples 29 to 34]

The polymer blend alignment agents B2 to B30 and C1-B to C6-B were also subjected to the production of the FFS cell, the measurement of the voltage holding ratio, the ion density and the reliability test according to the method described in Example 238. The results are shown in Table 9. The results of Example 238 are also published.

From the above results, it was found that the alignment film made of the liquid crystal aligning agent of the present invention exerts the effects of the invention also in the polymer blend system. Further, the liquid crystals sandwiched between the positive and negative liquid crystals exhibit the effects of the present invention.

[Comparative Example 35]

1.08 g of the varnish 41 synthesized in Example 177 was weighed and 0.18 mg of an amine-based antioxidant (trade name ADEKA, trade name; Adegas Star LA-72) was added thereto and NMP / BC = 1/1 Weight ratio) was added to 1.67 g, and the mixture was shaken at room temperature for 1 hour to obtain orientation agent R3HA.

An FFS liquid crystal display element (FFS cell) R3HAC for evaluating electric characteristics was manufactured in accordance with the method described in Example 35 except that the liquid crystal composition to be injected using the prepared orientation agent R3HA was replaced with the negative type liquid crystal composition B.

The voltage holding ratio of the obtained measurement cell R3HAC was 97.5% at 5 V 30 Hz and the ion density was 20 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measuring cell after the reliability test was 83.2%, and the ion density was 195 pC.

[Comparative Example 36]

An orientation agent R3HB was prepared by the method described in Comparative Example 35 except that the addition amount of adegasta LA-72 was changed to 1.8 mg to prepare an FFS liquid crystal display element R3HBC for electric characteristics.

The voltage holding ratio of the obtained measurement cell R3HBC was 97.8% at 5 V 30 Hz and the ion density was 25 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measuring cell after the reliability test was 91.1% and the ion density was 105 pC. However, in the cell R3HBC, display failure due to the luminescent spot was confirmed at the initial stage. This defective display is thought to be caused when the JF-90 added in the orientation film is segregated on the outermost surface and defective bright point is generated there.

[Comparative Example 37]

An orientation agent R3HC was prepared by the method described in Comparative Example 35 except that the addition amount of adegasta LA-72 was changed to 18.0 mg to prepare an FFS liquid crystal display element R3HCC for electric characteristics.

The voltage holding ratio of the obtained measurement cell R3HCC was 97.6% at 5 V 30 Hz and the ion density was 25 pC. The cell was placed on a backlight tester (Fuji COLOR LED Viewer Pro HR-2, manufactured by Fuji Film Co., Ltd., brightness: 2,700 cd / m 2) for 1,000 hours, and a reliability test was conducted. The voltage holding ratio of the measuring cell after the reliability test was 91.9% and the ion density was 95 pC. However, even in the case of the cell R3HCC, defective display due to the luminescent spot was confirmed at the initial stage.

By using the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal display device which does not deteriorate display quality over a long period of time. This effect is characteristic of the IPS mode and FFS mode liquid crystal display device.

Claims (17)

A polyamic acid or a derivative thereof obtained by reacting at least one of diamines represented by the formula (1) with at least one tetracarboxylic acid dianhydride.

In the formula ^(1), R 1 is hydrogen or methyl; and,
R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms. The method according to claim 1,
Diamine represented by the formula (1): Polyamic acid having at least one diamine represented by the formula (1-1) or a derivative thereof.

In the formula (1-1), R ² is hydrogen, -OH, alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms. The method according to claim 1,
Diamine represented by the formula (1): Polyamic acid having at least one diamine represented by the formula (1-2) or a derivative thereof.

In the formula (1-2), R ² is a hydrogen, -OH, alkoxy of 1 to 6 carbon atoms alkyl, or C 1 to 6. 3. The method of claim 2,
Diamine represented by the formula (1): at least one polyamic acid or derivative thereof selected from the group of compounds represented by the formulas (1-1-1) to (1-1-28).

The method of claim 3,
The diamine represented by the formula (1) is at least one polyamic acid or a derivative thereof selected from the group of compounds represented by the formulas (1-2-1) to (1-2-28).

6. The method according to any one of claims 1 to 5,
A polyamic acid or a derivative thereof obtained by reacting at least one of diamines represented by the formula (1) and at least one mixture of other diamines with at least one tetracarboxylic acid dianhydride. 7. The method according to any one of claims 1 to 6,
At least one polyamic acid or derivative thereof selected from the group of tetracarboxylic acid dianhydrides represented by the following formulas (AN-I) to (AN-VII).

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;
In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF _{3) 2} - and;
In the formulas (AN-II) to (AN-IV), Y is independently selected from the group of the following trivalent groups,

At least one hydrogen of these groups may be replaced by methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, Hydrogen may be substituted with methyl, ethyl or phenyl, the bonding hand attached to the ring may be connected to any carbon constituting the ring, and the two bonding hands may be connected to the same carbon;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me is methyl, Ph is phenyl,
In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1. 8. The method of claim 7,
(AN-1-1), (AN-1-13), (AN-2-1) and (AN-3- 1), AN-3-2, AN-4-5, AN-4-17, AN-4-21, AN-4-29, AN-4-30), AN-5-1, AN-7-2, AN-10, AN-11-3, AN-16-3, And at least one polyamic acid or derivative thereof selected from the formula (AN-16-4).

In the formulas (AN-1-2) and (AN-4-17), m is an integer of 1 to 12. The method according to claim 6,
The other diamine is a group consisting of the following formulas (DI-1) to (DI-16), formulas (DIH-1) to formula (DIH-3), and formulas (DI- At least one polyamic acid or derivative thereof.

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen may be replaced by -OH;
Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONH-, -CONCH 3 -, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m '- -O- (CH ₂ ) _{m '} -O-, -N (CH ₃ ) - (CH ₂ ) _k -N (CH ₃ ) -, - (OC ₂ H ₄ ) _{m' CH 2 -C (CF 3) 2} -CH 2 -O-, -O-CO- (CH 2) m '-CO-O-, -CO-O- (CH 2) m' -O-CO-, _{- (CH 2) m '-NH-} (CH 2) m' -, -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m ') k -NH - and _{(NH-C 3 H 6)} n -CO-, or -S- (CH _{2) m '-S-} and, m' are independently an integer of 1 ~ 12, -, -CO- C 3 H 6 k is an integer of 1 to 5, and n is 1 or 2;
In the formula (DI-4), s is independently an integer of 0 to 2;
In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, or an alkylene of 1 to 10 carbon atoms;
Formula (DI-2) ~ formula (DI-7) in cyclohexane at least one hydrogen of the ring and a benzene ring is -F, -Cl, C 1 -C 3 alkyl, -OCH _3, -OH, -CF in _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, phenyl, phenyl and benzyl may be substituted with, besides formula (DI-4) at least one hydrogen has the following formula (DI-4- of the benzene ring in the may be substituted with one of the groups selected from the group of groups a) to (DI-4-e);

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;
A group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary and the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ²² Is an arbitrary position except for the bonding position;

In formula (DI-11), r is 0 or 1;
In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego;
In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms , Alkynyl having 1 to 6 carbon atoms, q is independently an integer of 0 to 4;
In formula (DI-15), ring C is a monocyclic ring containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, r is 0 or 1;
In the formulas (DI-13) to (DI-16), the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or -C (CF _{3) 2} - and;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring wherein at least one hydrogen of the ring may be substituted by methyl, ethyl, or phenyl;
In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the ring may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonding to the ring is at any position;

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, m' is an integer of 1 to 12, and R ²⁵ is a group having an alkyl, phenyl, steroid skeleton having 3 to 30 carbon atoms, (DI-31-a) wherein at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be replaced by -O-, -CH = CH- or -C≡ optionally substituted by a C- and a hydrogen of the phenyl is _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms , The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring,

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups and independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one -CH ₂ - -O-, -COO-, -OCO-, -CONH-, -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene- Diyl or anthracene-9,10-diyl, and at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ may be substituted with -F or -CH ₃ , s , t and u are independently an integer of 0 to 2, the sum of them is 1 to 5, and when s, t or u is 2, the two bonding groups in each parenthesis may be the same or different, and two The rings may be the same or different,
R ²⁶ is hydrogen, -F, -OH, C 1 -C 30 alkyl, C 1 -C 30 fluorine-substituted alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2, or -OCF of 1 to 30 carbon atoms in the ₃ , And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b)

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms;
One hydrogen of the benzene ring in the formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl,
In the formulas (DI-32) and (DI-33), a group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, G ³² is a single bond or alkylene having 1 to 3 carbon atoms,
R ³¹ is hydrogen or alkyl of 1 to 20 carbon atoms, at least one -CH ₂ in the alkyl - is optionally substituted by -O-, -CH = CH- or -C≡C-, R ³² is C 6 - And R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1, and the benzene ring And -NH ₂ bonded to each other represents an arbitrary bonding position in the ring. The method according to claim 6,
The other diamines are represented by the following formulas (DI-1-3), (DI-2-1), (DI-4-1), (DI- (DI-5-15), the formula (DI-5-13), the formula (DI-5-15) -28), Formula (DI-5-30), Formula (DI-7-3), Formula (DI-13-1), Formula (DI-16-1) At least one polyamic acid or a derivative thereof selected from the group consisting of

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is an integer of 1 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5;
In formula (DI-7-3), n is 1 or 2. 10. A liquid crystal aligning agent containing the polyamic acid according to any one of claims 1 to 10 or a derivative thereof. 10. A liquid crystal aligning agent comprising the polyamic acid or a derivative thereof according to any one of claims 1 to 10 and a polymer other than the polyamic acid or its derivative. 13. The method according to claim 11 or 12,
Wherein the liquid crystal aligning agent further contains at least one member selected from the group consisting of an alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. 14. A liquid crystal aligning agent for a transverse electric field type liquid crystal display element according to any one of claims 11 to 13. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 11 to 14. A liquid crystal display element comprising the liquid crystal alignment film according to claim 15. A diamine represented by the formula (1-2).

In the formula (1-2), R ² is a hydrogen, -OH, alkoxy of 1 to 6 carbon atoms alkyl, or C 1 to 6.