KR20160046704A - Liquid crystal aligning agents containing polyamic acid or the derivative, liquid crystal alignment layers and liquid crystal display devices - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent containing at least one polymer (a) selected from polyamic acid obtained by reaction of tetracarboxylic acid dianhydride with diamine, and derivatives thereof, wherein the tetracarboxylic acid dianhydride comprises at least one tetracarboxylic acid dianhydride represented by chemical formula (1) and at least one tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure, and the diamine comprises at least one diamine having a photoreactive structure. It is possible to form a liquid crystal aligning layer inhibited from peeling or cutting by using the liquid crystal aligning agent according to the present invention. In addition, a liquid crystal display device having the liquid crystal aligning layer shows no degradation of display quality even when exposed to strong light for a long time, and causes no non-uniformity or latent image. In chemical formula (1), m is an integer of 1-10.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element comprising a polyamic acid or a derivative thereof, a liquid crystal alignment layer,

The present invention relates to a liquid crystal aligning agent containing a polyamic acid or a derivative thereof obtained by using a specific tetracarboxylic dianhydride, a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film. The term "liquid crystal aligning agent" in the present invention means a polymer-containing composition used for forming a liquid crystal alignment film.

Various display devices such as a PC monitor, a liquid crystal TV, a viewfinder of a video camera, a projection type display, and optoelectronic devices such as an optical printer head, a light Fourier transform device, and a light valve are commercially available today A display device using a nematic liquid crystal is a mainstream liquid crystal display device. As a display method of a nematic liquid crystal display device, TN (Twisted Nematic) mode and STN (Super Twisted Nematic) mode are well known. In recent years, in order to solve the problem of narrow 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 a vertical orientation and a projection structure, (In-Plane Switching) mode and FFS (Fringe Field Switching) mode of a transverse electric field system have been proposed and put into practical use.

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

The liquid crystal alignment film is formed using a liquid crystal aligning agent. At present, a liquid crystal aligning agent mainly used is a solution (varnish) in which a polyamic acid or a soluble polyimide is dissolved in an organic solvent. This solution is applied to a substrate, and then the film is formed by means such as heating to form a polyimide-based liquid crystal alignment film.

As an alignment treatment method for regularly arranging liquid crystal molecules on the surface of a liquid crystal alignment film, a rubbing method which is simple and capable of high-speed processing of a large area is widely used. The rubbing process is a process in which the surface of the liquid crystal alignment film is rubbed in one direction using a cloth obtained by planting fibers such as nylon, rayon, and polyester, whereby it is possible to obtain a uniform orientation of the liquid crystal molecules . However, in the rubbing treatment, there are problems such as dust generation caused by scraping off the liquid crystal alignment film, damage on the liquid crystal alignment film, deterioration in display quality, and occurrence of static electricity. An orientation treatment method has been actively developed.

What is attracting attention as an orientation treatment method instead of the rubbing method is an optical alignment treatment method in which light is irradiated to perform orientation treatment. Many optical alignment methods, such as photolysis, photoisomerization, photo-dimerization, and photo-crosslinking, have been proposed for the photo-alignment treatment (see, for example, Non-Patent Document 1 and Patent Documents 1 and 2). Since the photo alignment method has a higher alignment uniformity than the rubbing method and is also a non-contact alignment treatment method, it is possible to reduce the cause of occurrence of defective display of liquid crystal display elements such as oscillation and static electricity without damaging the film There are advantages. However, the rubbing method has low anchoring energy and low orientation. This causes a decrease in the response speed of the liquid crystal molecules or baking, and therefore improvement has been demanded.

In order to overcome the problems of such a photo-alignment treatment method, there has been proposed a material which amplifies anisotropy of a film by using polyimide having liquid crystallinity and heat-treating the material at the time of film formation (for example, Patent Document 3, 4). However, a photo alignment layer to which such a technique is applied tends to cause peeling and scraping of the film at the time of panel production, and the resulting foreign matter lowers the display quality of the panel.

Japanese Patent Application Laid-Open No. 9-297313 Japanese Patent Laid-Open No. 10-251646 Japanese Patent Laid-Open No. 2010-049230 Japanese Patent Laid-Open No. 2010-197999

Liquid Crystal, Vol. 3, No. 4, 262, 1999

The object of the present invention is to provide a liquid crystal display device capable of providing a liquid crystal display element which does not cause display quality degradation even after exposure to strong light for a long period of time and which does not cause so-called unevenness or afterimage, solves the problems of film peeling, And to provide a liquid crystal aligning agent capable of forming such a liquid crystal alignment film.

The inventors of the present invention used a liquid crystal aligning agent containing a polyamic acid or a derivative thereof synthesized as a raw material of a tetracarboxylic dianhydride represented by the following formula (1) and a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure It is possible to obtain a liquid crystal alignment film in which the film hardness is improved and the above-mentioned foreign matter is not generated, thereby completing the present invention.

The present invention is constituted by the following items.

[1] A liquid crystal aligning agent containing at least one polymer (a) selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic dianhydride and a diamine,

Wherein the tetracarboxylic dianhydride contains at least one tetracarboxylic dianhydride represented by the following formula (1) and at least one selected from tetracarboxylic dianhydrides having an alicyclic structure or aliphatic structure,

Wherein the diamine contains at least one diamine having a photoreactive structure.

In the above formula (1), m is an integer of 1 to 10.

[2] The liquid crystal aligning agent according to [1], wherein the tetracarboxylic dianhydride of the formula (1) is a tetracarboxylic dianhydride represented by the following formula (1-8).

[3] The liquid crystal alignment described in [1] or [2], wherein the tetracarboxylic dianhydride having an alicyclic or aliphatic structure is at least one selected from the compounds represented by the following formulas (3) to (9) My.

At least one of the hydrogen in the above formula may be substituted with -CH _3, -CH ₂ CH ₃ or phenyl.

[4] The liquid crystal aligning agent according to [1] or [2], wherein the tetracarboxylic dianhydride having an alicyclic structure or aliphatic structure is at least one selected from the compounds represented by the following formula (3-1).

In the formula (3-1), R is independently hydrogen, -CH _3, -CH ₂ CH ₃ or phenyl.

[5] The liquid crystal aligning agent according to [1] or [2], wherein the tetracarboxylic dianhydride having an alicyclic structure is 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride.

[6] The liquid crystal aligning agent according to any one of [1] to [5], wherein the diamine having a photoreactive structure is 4,4'-diamino azo benzene.

[7] The resin composition according to any one of [1] to [6], wherein the diamine further contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D- Liquid crystal aligning agent.

In the formulas (D-2) and (D-4), X and Y are a single bond, -O-, -NH-, -S-, or alkylene having 1 to 6 carbon atoms;

At least one hydrogen in the benzene ring may be substituted with -CH ₃ ;

In the formula (D-4), a is an integer of 1 to 8; And,

In the formula (D-5), Ra is alkyl having 1 to 3 carbon atoms.

[8] The resin composition according to any one of [1] to [5], further comprising at least one polymer (b) selected from polyamic acid and derivatives thereof obtained by reacting a tetracarboxylic dianhydride having no photoreactive structure and a diamine having no photoreactive structure. [5] The liquid crystal aligning agent according to any one of [1] to [5].

[9] The liquid crystal aligning agent according to [8], wherein the tetracarboxylic dianhydride used in the synthesis of the polymer (b) contains at least one selected from the following formulas (3) to (13).

At least one of the hydrogen in the above formula may be substituted with -CH _3, -CH ₂ CH ₃ or phenyl.

[10] The polymer according to [8] or [9], wherein the diamine used in the synthesis of the polymer (b) contains at least one selected from the following formulas (D-1) to Liquid crystal aligning agent.

In the formulas (D-2) and (D-4), X and Y are a single bond, -O-, -NH-, -S-, or alkylene having 1 to 6 carbon atoms;

At least one hydrogen in the benzene ring may be substituted with -CH ₃ ;

In the formula (D-4), a is an integer of 1 to 8; And,

In the formula (D-5), Ra is alkyl having 1 to 3 carbon atoms.

[11] The liquid crystal aligning agent according to any one of [1] to [10], which further comprises at least one selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound and a silane coupling agent. .

[12] The positive resist composition according to any one of [1] to [6], wherein the silane coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- A compound comprising 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, , Wherein the liquid crystal aligning agent is at least one selected from the group consisting of the following liquid crystal aligning agents.

[13] The liquid crystal aligning agent according to any one of [1] to [12], which contains at least one solvent selected from an alcohol, an ether and a ketone.

[14] The liquid crystal aligning agent according to any one of [1] to [13], which contains at least one solvent selected from alkylene glycol alkyl ether derivatives, dialkylene glycol dialkyl ether derivatives and propylene glycol derivatives.

[15] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [1] to [14].

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

A liquid crystal aligning agent containing a tetracarboxylic dianhydride represented by the formula (1) of the present invention and a polymer obtained from a raw material containing a tetracarboxylic dianhydride having an alicyclic or aliphatic structure and a compound having a photoreactive structure The liquid crystal alignment film formed by applying and firing has excellent film hardness and good liquid crystal alignability. Further, the liquid crystal display element having the liquid crystal alignment film of the present invention has good display performance and good electrical characteristics. The liquid crystal aligning agent prepared by blending the polymer with another polymer exhibits the same effect.

The polymer (a) is a polymer obtained by reacting a tetracarboxylic dianhydride represented by the formula (1) with a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, and a raw material having a photoreactive structure. The raw material compound used in the synthesis of the polymer will be specifically described.

Specific examples of the tetracarboxylic dianhydrides represented by the formula (1) are represented by the following formulas (1-1) to (1-10).

The linearity of the alkylene moiety is important in order to improve the orientation of the liquid crystal. Preferred compounds are compounds represented by the following formulas (1-4), (1-6), (1-8), or (1-10).

Among them, a compound represented by the following formula (1-8) is more preferable since it exhibits the largest orientation property.

Specific examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure are represented by the following formulas (3) to (9).

At least one of the hydrogen in the above formula may be substituted with -CH _3, -CH ₂ CH ₃ or phenyl.

Among them, the tetracarboxylic dianhydride represented by the formula (3) is particularly preferable, in which the effect of improving the electrical characteristics is remarkable.

More specifically, the tetracarboxylic dianhydride represented by the formula (3) can be represented by the following formula (3-1).

In the formula (3-1), R is independently hydrogen, -CH _3, -CH ₂ CH ₃ or phenyl.

Specific examples of the tetracarboxylic dianhydride represented by the formula (3-1) include the compounds represented by the following formulas (3-1-1) to (3-1-7).

In order to make the polymer (a) have a photoreactive structure, it is preferable to use a diamine having a photoreactive structure or a tetracarboxylic dianhydride having a photoreactive structure as a raw material. A diamine having a photoreactive structure and a tetracarboxylic dianhydride having a photoreactive structure may be used in combination. Preferable examples of the monomer having these photoreactive structures are the compounds represented by the following formulas (I-1) to (I-4).

Among them, a compound represented by the formula (I-3) is more preferable since it exhibits a large anisotropy when an orientation film is formed.

The copolymerization ratio of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure to the tetracarboxylic dianhydride represented by the formula (1) is 10% by weight to 90% by weight, and from the viewpoint of the orientation of the liquid crystal molecules, To 60% by weight. From the viewpoint of improving electrical properties and film hardness, the copolymerization ratio is more preferably 20 wt% to 50 wt%.

(D-1), (D-2-1) to (D-2-9) shown below in addition to the diamines represented by the above formulas (I- ), The diamine represented by the formula (D-3), the compound represented by the formula (D-4-1) to the compound represented by the formula (D-4-72) Or may be copolymerized.

Next, the polymer (b) to be used by blending with the polymer (a) will be described in detail. Polymer (b) is a polymer synthesized using tetracarboxylic dianhydride or diamine having no photoreactive structure. There is no particular limitation on the tetracarboxylic dianhydride used in the synthesis of the polymer (b), but specific examples of the tetracarboxylic dianhydride preferably used are the compounds represented by the following formulas (3) to (13).

At least one of the hydrogen in the above formula may be substituted with -CH _3, -CH ₂ CH ₃ or phenyl.

(D-1), (D-2-1) to (D-2-9) are not particularly limited as far as the diamine used in the synthesis of the polymer (b) (D-3), Formula (D-4-1) to Formula (D-4-72), and Formula (D-5-1) to Formula (D-5-3).

The composition ratio (weight ratio) when the polymer (b) is blended and used in the polymer (a) is in the range of 1/9 to 9/1 of the polymer (a) / polymer (A) / polymer (b) = 2/8 to 5/5, in view of the electrical characteristics, and the polymer (a) / polymer Is more preferable.

Other than the above, tetracarboxylic dianhydrides and diamines can be used as long as they do not affect the electrical properties and orientation.

The tetracarboxylic dianhydride other than the above used for producing the polyamic acid and derivatives thereof of the present invention will be described. The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydrides include aromatic (including a complex aromatic ring system) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, and aliphatic (heterocyclic) systems in which a dicarboxylic anhydride is not directly bonded to an aromatic ring And the like).

Specifically, tetracarboxylic dianhydrides represented by the following formulas (AN-1) and (AN-3) to (AN-16-14) can be given.

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

In formula (AN-1), G ¹¹ is a single bond, alkylene of 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 the group shown below.

And, R ¹¹ is hydrogen or -CH _3.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include 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 dianhydride represented by the formula (AN-3)] [

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

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

[Tetracarboxylic 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 ring A ¹¹ .

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

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

[Tetracarboxylic 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 dianhydride represented by the formula (AN-6) include the compounds represented by the following formulas.

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

In formula (AN-7), X ¹¹ is a single bond.

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

[Tetracarboxylic 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 the ring A ¹² is a cyclohexane ring or a cyclohexene ring.

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

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

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

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

[Tetracarboxylic dianhydride represented by the formula (AN-10-2)] [

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

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

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

[Tetracarboxylic 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 dianhydride represented by the formula (AN-12) include the compounds represented by the following formulas.

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

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

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

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

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

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

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

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

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

As the tetracarboxylic dianhydride other than the above, the following compounds are exemplified.

Preferred materials for improving the properties of the acid dianhydride are described below. (AN-1), (AN-3), and (AN-4) are preferable, and the compounds represented by formulas (AN-1-2) Particularly preferred are the compounds represented by formulas (AN-1-13), (AN-3-2), (AN-4-17) and (AN-4-29) 1-2), it is preferable that m = 4 or 8. 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-2-1) in the above acid anhydrides when it is important to improve the transmittance of the liquid crystal display element. AN-4-17, AN-4-30, AN-5-1, AN-7-2, AN-10, (AN-16-3) and formula (AN-16-4) are preferable. Among them, in formula (AN-1-2), m is preferably 4 or 8, 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-2-1) among the above acid anhydrides in order to improve the VHR of the liquid crystal display element. (AN-4-17), AN-4-30, AN-7-2, AN-10, AN-16-3, The compound represented by the formula (AN-16-4) is preferable, and 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.

It is effective 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 a compound represented by the formula (AN-11-3) are preferable.

The diamines used for preparing the polyamic acid and derivatives thereof of the present invention will be described. The diamine is represented by the group consisting of the following formulas (DI-1) to Formula (DI-16), Formulas (DIH-1) to Formulas (DIH-3) and Formulas (DI- And the like. (D-2) and (D-5) to the formula (DI-5), the formula (D-3) ) Is included in equation (DI-13), and equation (D-4) is included in equation (DI-7), respectively.

In the formula (DI-1), G ²⁰ is -CH ₂ -, and 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-, -CONH-, -CONCH 3 -, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m '- _{, -O- (CH 2) m '} -O-, -N (Ra) - (CH 2) k -N (Ra) -, - (O-C2H4) 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 -CO-, or -S- (CH _{2) m 'is} -S-, m' are independently an integer of 1~12, Ra carbon atoms 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, cyclo hexane ring and the benzene ring of which at least one hydrogen, -F, -Cl, alkylene, having a carbon number of 1~3 -OCH _3, -OH, a _{-CF 3, -CO 2 H, -CONH} 2, -NHC 6 H 5, phenyl, phenyl may be substituted with benzyl, and the formula (DI-4) to, at least one hydrogen of the benzene ring in the formula ( May be substituted with one group selected from the group of groups represented by the formulas DI-4-a to Formula (DI-4-e). 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 and the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ²² It is an arbitrary position excluding the bonding position.

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 an arbitrary position.

In formula (DI-12), R ²¹ and R ²² are independently alkyl of 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene of 1 to 6 carbon atoms, phenylene or alkyl- w is an integer of 1 to 10; In formula (DI-13), R ²³ is independently an alkyl having 1 to 5 carbon atoms, an alkoxy having 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, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, having a carbon number of 2 to 6 alkenyl , Alkynyl having 1 to 6 carbon atoms, and q is independently an integer of 0 to 4. In formula (DI-15), ring C is a monocyclic ring containing a hetero atom. 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. In the formulas (DI-13) to (DI-16), 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 formula (DIH-1), G ²⁵ represents a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ - - (CF ₃ ) ₂ -. In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one of these rings may be substituted with methyl, ethyl, or phenyl. In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, and at least one of these rings 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 an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) include diamines having no side chain 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 of each other, an integer of 1 to 3.

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

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

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

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

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

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

[92]

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

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

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

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

We will explain Dehydrazide. Examples of the dihydrazides having no known side chains include those represented by the following formulas (DIH-1) to (DIH-3).

In formula (DIH-1), G ²⁵ represents a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ - - (CF ₃ ) ₂ -. In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one of these groups may be substituted with 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 of these groups 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 an arbitrary position.

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-branched-chain diamines and hydrazides have the effect of improving the electrical characteristics, such as lowering the ion density of the liquid crystal display element. When a non-branched-chain diamine and / or hydrazide is used as the diamine used for producing the polyamic acid or its derivative 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 / Is preferably 0 to 90 mol%, more preferably 0 to 50 mol%.

The side chain type diamine will be explained. As the side chain group of the side chain type diamine, the following groups are exemplified.

The side chain group is preferably a group selected from the group consisting of alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy , Alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl, alkenyl and alkynyl in these groups are all three or more carbon atoms. However, in alkyloxyalkyl, the number of carbon atoms in the whole group may be 3 or more. These groups may be linear or branched.

Subsequently, the ring may be substituted with at least one substituent selected from the group consisting of phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy, and phenylcarbonyl, provided that the ring at the terminal is substituted with alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms. Cyclohexyloxyphenyl, cyclohexylphenylalkyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, cyclohexylphenyl, (Cyclohexyl) phenyloxy, bis (cyclohexyl) oxy carbonyl, bis (cyclohexyl) phenyloxycarbonyl, And cyclohexylbis (phenyl) oxycarbonyl, and the like.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or 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 terminal ring 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 An aggregator is an example. Is effective as an airway side chain group having a steroid skeleton.

Examples of the diamine having a side chain include the 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. 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, may be substituted with alkyl or alkoxy having a carbon number of 3 to 30 carbon atoms of 3 to 30. 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.

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 one or more -CH ₂ - -O-, -COO-, -OCO-, -CONH-, -CH = CH-. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 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 ²² ring, ring B and ²³ In ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , s, t and u are independently integers of 0 to 2, the sum of them is 1 to 5, and 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, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF 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). Preferable examples of R ²⁶ are alkyl having 1 to 30 carbon atoms and alkoxy having 1 to 30 carbon atoms.

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 represents a single bond independently, -CO- or -CH ₂ -, and, R ²⁹ is hydrogen or -CH ₃ independently, 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 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 any 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, 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 indicates arbitrary bonding position in the ring, but it is preferably 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 of 1 to 30 carbon atoms or alkoxy of 1 to 30 carbon atoms, preferably alkyl of 5 to 25 carbon atoms or alkyl Lt; / RTI > 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 an alkyl having 6 to 30 carbon atoms, preferably an alkyl having 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 > R ³⁹ is hydrogen, -F, alkyl of 1 to 30 carbon atoms, an alkoxy _{group, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ group of 1 to 30 carbon atoms, and preferably having a carbon number of 3 to 25 alkyl, or 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.

Formula (DI-34-1) ~ expression in (DI-34-12), R ⁴⁰ is hydrogen or alkyl, preferably hydrogen or alkyl of 1 to 10 carbon atoms having 1 to 20 carbon atoms, and, R ⁴¹ is Hydrogen or alkyl of 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.

As the diamine in the present invention, the diamines represented by the formulas (DI-1-1) to (DI-16-1), the formulas (DIH-1-1) to (DIH- ) To a diamine other than the diamine represented by the formula (DI-35-3). 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 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 or an -N (Boc) _2, at least one of R ⁴³ is ₂ -NHBoc or -N (Boc), in the 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 tert-butoxycarbonyl group.

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

(DI-3-1), formula (DI-2-1), formula (DI-5-1) and formula (DI-3-1) among the diamines and dihydrazides described above, The diamine represented by the formula (DI-2-1) is particularly preferable, and the diamine represented by the formula (DI-5-1) Do. In the formula (DI-5-1), it is preferable that m = 2, 4 or 6, m = 4 is particularly preferable, m = 2 or 3, 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 in order to improve the VHR of the liquid crystal display element, Diamine represented by the formula (DI-4-10), the formula (DI-4-15), 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 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 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), the formula (DI-4-2), the formula (DI-4-10) and the formula (DI-4-2) among the diamines and dihydrazides described above, -15), the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), the formula (DI-5-28) Diamines represented by the formulas (DI-4-1), (DI-5-1) and (DI-5-13) are particularly preferable. 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 are 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 of the proportion of the monoamine to the diamine being 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, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and for example, the effect of the present invention is not impaired and the coating property of the liquid crystal aligning agent can be improved . The diamine substituted with a monoamine may be one type or 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 comprise a monoisocyanate compound in its monomer. By incorporating the monoisocyanate compound into the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified to control the molecular weight. By using the terminal-modified polyamic acid or its derivative, for example, the effect of the present invention is not impaired and the application properties of the liquid crystal aligning agent can be improved. 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 derivatives 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 conditions for usual polyamic acid synthesis 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 a component other than the polyamic acid or the derivative thereof. The other components may be one kind or two or more kinds. Other components include, for example, other polymers and compounds described below.

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. As the other polymer, a polyamic acid or a derivative (hereinafter referred to as "other polyamic acid or a derivative thereof") obtained by reacting a tetracarboxylic dianhydride not containing a tetracarboxylic dianhydride of the formula (1), a polyester , Polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. It may be one or two or more. 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 a derivative thereof, the structure and the molecular weight of each polymer are controlled, and the preliminary drying is performed , 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 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. Confirmation of layer separation can be confirmed by that the surface energy of the formed alignment film is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component.

As the polysiloxane, there can be mentioned, for example, Japanese Patent Publication Nos. 2009-036966, 2010-185001, 2011-102963, Japanese Patent Laid-Open No. 2011-253175, Japanese Laid-Open Patent Application 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 Publication 2012/165354, and the like.

≪

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound in order to stabilize the electrical characteristics of the liquid crystal display element for a long period of time. The photographic compound may be a single compound or two or more compounds. The content of the oxazine 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, desirable.

The oxazine compound will be described in detail below.

The oxazine compound is preferably an oxazine compound having solubility in a solvent for dissolving polyamic acid or a derivative thereof and having ring-opening polymerizability.

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 examples of the structure of the oxazine having an aromatic group containing a condensed polycyclic aromatic group, such as benzoxazine and naphthoquinone, .

Examples of the oxazine compound include 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 the ring is bonded to any carbon capable of bonding with a substituent.

Formula (OX-1) ~ expression in ^(OX-3), L 3 and L ⁴ is an organic group of 1 to 30 carbon atoms, in the formula (OX-1) ~ formula ^{(OX-6), L 5} ~ L ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, formula (OX-3), in the 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 are independently a single bond, -O-, -S-, -CO-, -C (CH 3) 2 -, -C (CF 3) 2 - or an alkylene with a carbon number of 1 to 3, and Q ² in the benzene ring, hydrogen bonded to the naphthalene ring may be independently 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, there are the following oxazine compounds.

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.

As the oxazine compound represented by the formula (OX-2), for example, there are 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.

As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be used.

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. As the oxazine compound represented by the formula (OX-3-I), for example, there are 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.

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

As the oxazine compound represented by the formula (OX-5), for example, there are the following oxazine compounds.

As the oxazine compound represented by the formula (OX-6), for example, there are the following oxazine compounds.

(OX-2-1), Formula (OX-3-1), Formula (OX-3-3), Formula (OX- 3-5) (OX-5), the formula (OX-5-4), the formula (OX-3-9) (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.

The 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 method of slow addition and then reacting with a compound having a naphthol-based hydroxyl group (WO 2004/009708 Reference).

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

The oxazine compound represented by the formula (OX-4) to formula (OX-6) can be produced 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 Japanese Patent Application Laid-Open No. 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 electrical characteristics of the liquid crystal display element for a long period of time. 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, desirable. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the amount of the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline, considering the above-mentioned object.

The oxazoline compound will be specifically described below.

The oxazoline compound may have one oxazoline structure or two or more oxazoline structures in one compound. The oxazoline compound may have one oxazoline structure in one compound, but it is preferable to have 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 the side chain, or may be a copolymer of a monomer having an oxazoline structure in the 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 a copolymer.

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

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-oxazolyl ) Benzene, 2,2-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl- 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 oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai 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 electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be a single compound or two or more compounds. The content of the epoxy compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, further preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof, Do.

Hereinafter, the epoxy compound will be specifically described.

As the epoxy compound, various compounds having one or more epoxy rings in the molecule can be exemplified. 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 ox Epoxycyclohexyl) ethyl triethoxy silane, 2- (3,4-epoxycyclohexyl) ethyl triethoxy silane, 2- Silane, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, Aniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

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-bis [4- -Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name: Techmore 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-m (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 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 (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (Meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (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. 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-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmor VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Particularly preferred.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, 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, There are footprint 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 A glycidyl ether compound has, 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, there is a glycidyl amide type epoxy compound.

As the chain type aliphatic epoxy compound, there is, for example, a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

As the cyclic aliphatic epoxy compound, for example, there is a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Examples of the bisphenol A type epoxy compound include epoxy resins such as 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 Chemical Co., Ltd.), and the like.

Examples of the bisphenol F type epoxy compounds include jER806, jER807, jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epitoto YDF-170, Eptoto YDF-175S, 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 compound include an epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include SANTOTO ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), Ricare resin HBE-100 (trade name, -252 (trade name, manufactured by Nagase Chemtex Co., Ltd.).

As the hydrogenated bisphenol type epoxy compound, there is, for example, an epoxy compound 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 epoxy compounds include: jER152, jER154 (all trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Toto Chemical), DEN431 and DEN438 EPPN-201, and EPPN-202 (both trade names, manufactured by Nippon Gakkai Co., Ltd.).

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, EOCN-1025, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Gakkai Co., Ltd.) .

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), and NC-7000 ).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (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 (both trade names, manufactured by Nippon Yakuza Co., Ltd.), DPPN- (Manufactured by Mitsui Chemicals), 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 (following formula EP-8), diethylene glycol diglycidyl ether (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, , New Japan Ewha ), 1,3,5,6-tetraglycidyl-2,4-hexanediol (the following formula EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycol Denacol EX-311, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all trade names, manufactured by Nagase ChemteX Corporation) have.

As the polysulfide-type diglycidyl ether compound, for example, FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Thiokol Co., Ltd.) are available.

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 have.

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: &Lt; / RTI &gt;

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

Examples of the polyglycidylamine compound 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-xylenediamine (TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., -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) cyclohexane P-35), 1,4-bis (N, N-diglycidylamino) cyclohexane (the following formula EP-36), 1,3- Bis (N, N-diglycidylaminomethyl) benzene (formula EP-38), 2,6-bis N, N ', N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula EP-40), 2, (N, N, N ', N'-tetraglycidyl) -4,4'-diaminophenyl (formula EP-41) 4,4'-diaminodiphenyl ether (following formula EP-42), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene -43), 2,4,4'-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44), tris ), Methane (the following formula EP-45), 3,4,3 ', 4'-tetrakis (N, N-diglycidylamino) biphenyl 4,4'-tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), A compound represented by the formula EP-48, and a compound represented by the following formula: EP-49.

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

(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate and the like can be given as examples of the monomers other than the oxiranyl-containing monomers in the copolymer of the oxiranyl- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (Meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N- Phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) (EP-50), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) , And glycidyl isocyanurate type epoxy resin.

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

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- , 3'-epoxycyclopentane ether (following formula EP-54), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2: CY-177, and CY-179 (all of which are represented by the following formula: EP-55), diepoxy limonene (Celloxide 3000 (trade name, manufactured by Daicel) , Available from The Ciba-Geigy Chemical Corp. (available from Huntsman Japan Co., Ltd.), EHPD-3150 (trade name, manufactured by Daicel Co.), and cyclic aliphatic epoxy resins.

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'-dia Aminodiphenylmethane, trade name "Techmore 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.

Further, for example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than a polyamic acid and a derivative thereof, and a low-molecular compound, and can be selected depending on the purpose.

For example, as the polymer compound, there is 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 electrical 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 low-molecular compound 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 charge prevention, (3) A silane coupling agent or a titanium-based coupling agent, and (4) an imidization catalyst when the 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-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- There is a silyl ethoxy) -1-propylamine, and N, N'- bis [3- (trimethoxysilyl) propyl] ethylenediamine. Preferred silane coupling agents are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane.

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline, and hydroxy substituted aniline; Substituted substituted isoquinoline, substituted isoquinoline, substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, and the like can be used. Examples of the substituted pyrrolidine derivative include pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, Of cyclic amines. Wherein the imidation catalyst is at least one selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline desirable.

The addition amount of the silane coupling agent is usually 0 to 30% by weight, preferably 0.1 to 15% by weight, based on the total weight of the polyamic acid or its derivative.

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

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

The polyamic acid or 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 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 derivative thereof 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 a gel permeation chromatography (GPC) method.

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

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

As the solvent, there can be mentioned both of the polyamic acid or its derivative and other solvent for improving the coating property.

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

It is preferable to use at least one solvent selected from the group consisting of other solvents, particularly, alcohol, ether and ketone for the purpose of improving the coating property.

Examples of the alcohol include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether , 1-butoxy-2-propanol, 2- (2-methoxypropoxy) propanol, ethyl lactate, methyl lactate, propyl lactate and butyl lactate.

Examples of the ether include alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether; Ether: dialkylene glycol monoalkyl ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, propylene Glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates such as acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate: propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether ether propionate And propylene glycol monoalkyl ether propionate such as propylene glycol monobutyl ether propionate, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and methyl 3-methoxypropionate .

Among them, the solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, gemethylimidazolidinone,? -Butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene Particularly preferred are glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether and 1-butoxy-2-propanol.

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 is sometimes necessary to dilute the contained polyamic acid with a solvent in advance in order to adjust the film thickness.

The concentration of the solid content 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. In general, it 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 in coating and pinhole.

The viscosity of the liquid crystal aligning agent of the present invention differs 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, in the case of application by a printing machine, it is 5 to 100 mPa · s (more preferably, 10 to 80 mPa · s). If it is smaller than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and when 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 measuring method and measured (measured temperature: 25 ° C) using, for example, a rotational viscometer (TVE-20L manufactured by Toki Industry Co., Ltd.).

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 usual method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained through 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 heat drying step and the heat firing step as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating process, the heating and drying process, or after the heating and firing process. It can also be used as a VA liquid crystal alignment film which does not undergo 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 normal liquid crystal alignment film. Examples of the substrate include glass substrates on which electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ -ZnO), and IGZO (In-Ga-ZnO ₄ ) electrodes and color filters may be provided.

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 also 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 performed 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 in the range of 30 ° C to 150 ° C and preferably in the range of 50 ° C to 120 ° C.

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

The method of forming the liquid crystal alignment film of the present invention by the photo alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo alignment method can be formed by applying anisotropy to the coated film by irradiating linearly polarized light or unpolarized light of radiation after heating and drying the coated film and then heating and firing the film. Alternatively, the coating film can be formed by heating and drying, heating and baking, and then irradiating linearly polarized light or unpolarized light of radiation. From the standpoint of the orientation property, it is preferable that the irradiation step of the radiation is performed before the heating and firing step.

Further, in order to enhance the liquid crystal alignment capability of the liquid crystal alignment film, linearly polarized light or unpolarized light of the radiation may be irradiated while heating the coating film. The irradiation of the radiation may be performed in a step of heating and drying the coating film or a step of heating and firing, or may be carried out between the heating and drying step and the heating and firing step. The heating and drying temperature in the above step is in the range of 30 ° C to 150 ° C and preferably in the range of 50 ° C to 120 ° C. The heating and firing temperature in the above step is in the range of 30 to 300 캜, and preferably in the range of 50 to 250 캜.

As the radiation, for example, ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having 300 to 400 nm are preferable. In addition, linearly polarized light or unpolarized light can be used. These lights are not particularly limited as far as they can impart a liquid crystal aligning ability to the above-mentioned coating film. However, in order to exhibit a strong alignment restricting force against a liquid crystal, linearly polarized light is preferable.

The liquid crystal alignment film of the present invention can exhibit a high liquid crystal aligning ability even with light irradiation with low energy. Dose of the linearly polarized light in the irradiation step is in preferably 0.05~20 J / cm ^2, more preferably 0.5~10 J / cm ^2. The wavelength of the linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The angle of irradiation with respect to the film surface of the linearly polarized light is not particularly limited, but when it is desired to exhibit a strong alignment restraining force against the liquid crystal, it is preferable that the film is as perpendicular as possible to the film surface from the viewpoint of shortening the orientation treatment time. Further, the liquid crystal alignment film of the present invention can orient the liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

In the case where the pretilt angle is intended to be expressed, light to be irradiated to the film may be linearly polarized light or unpolarized light as described above. When the pretilt angle is to be developed, the amount of light to be irradiated on the film is preferably 0.05 to 20 J / cm ² , more preferably 0.5 to 10 J / cm ² , and the wavelength is preferably 250 to 400 nm , And particularly preferably from 300 to 380 nm. When the pretilt angle is intended to be developed, the angle of irradiation with respect to the film surface of the light irradiated to the film is not particularly limited, but it is preferably 30 to 60 degrees from the viewpoint of shortening the orientation treatment time.

Examples of the light source used in the step of irradiating linearly polarized light or unpolarized light of radiation include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep UV lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, and a microwave excitation non-electrode lamp.

The liquid crystal alignment film of the present invention can also impart anisotropy by the rubbing method. The liquid crystal alignment film of the present invention using the rubbing method can be produced by a process comprising the steps of applying the liquid crystal aligning agent of the present invention to a substrate, heating and drying the substrate coated with the aligning agent, heating and firing the film, And can be formed through a process.

The rubbing treatment can be carried out in the same manner as in the rubbing treatment for the alignment treatment of an ordinary liquid crystal alignment film, and it is required that sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. The preferable conditions are the amount of moisture input (hair pressing amount) 0.2 to 0.8 mm, the stage moving speed 5 to 250 mm / sec, and the roller rotation speed 500 to 2,000 rpm.

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

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. As the cleaning liquid, pure water or 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, and ketones such as acetone and methyl ethyl ketone can be used However, the present invention is not limited thereto. Needless to say, these cleaning liquids are sufficiently purified so that a small amount of impurities are used. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

Annealing treatment by heat or light may be used before or after the heating and firing process, before or after the rubbing process, or before or after irradiation with polarized or unpolarized light, in order to enhance the liquid crystal alignment capability of the liquid crystal alignment film of the present invention. In the annealing treatment, the annealing temperature is 30 to 180 캜, preferably 50 to 150 캜, and the time is preferably 1 to 2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The amount of light to be irradiated 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 system 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 Japanese Laid-Open Patent Publication No. 2005-275364. It can also be evaluated by a method using ellipsometry as shown in the following examples. Specifically, the birefringence phase difference value of the liquid crystal alignment film can be measured by the spectroscopic ellipsometer. The birefringence phase difference value of the film becomes larger in proportion to the degree of orientation of the polymer main chain. That is, having a large birefringence retardation value has a large degree of orientation, and when used as a liquid crystal alignment film, it is considered that 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 preferably used for a liquid crystal display device of a transverse electric field system. In the case of use in a liquid crystal display device of a transverse electric field system, 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 optical compensation materials and all other liquid crystal materials in addition to the orientation of liquid crystal compositions for liquid crystal displays. Further, since the alignment film of the present invention has a large anisotropy, it can be used solely for optical compensation materials.

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 opposing surfaces of the pair of substrates; In a liquid crystal display element having an alignment film and a liquid crystal layer formed between the pair of substrates, 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. Such electrodes include, for example, a vapor-deposited film of ITO or metal. The electrode may be formed on the entire surface of one side of the substrate, or may be formed in a patterned desired shape, for example. The desired shape of the electrode is, for example, a comb-shaped or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. For example, in the case of an IPS type liquid crystal display element, electrodes are arranged on one side of the pair of substrates, and in the case of other liquid crystal display elements, Electrodes are disposed on both sides of the pair of substrates. And the liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in a form in which the liquid crystal composition is sandwiched by the pair of substrates on which the liquid crystal alignment film is formed and the surfaces thereof face each other. 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 positive (+) or negative (-) dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy are disclosed in JP 3086228, JP 2635435, JP 5-501735, JP 08-157826, JP 8-231960, JP-A 9-241644 (EP 88272A1) Japanese Patent Application Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Application Laid-Open No. 8-199168 (EP722998A1), Japanese Patent Application Laid-Open Nos. 9-235552, 9-255956, 9-241643 (EP885271A1) A liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. 10-204016 (EP844229A1), JP-A No. 10-204436, JP-A No. 10-231482, JP-A No. 2000-087040, .

In addition, one or more optically active compounds may be added to the liquid crystal composition having a negative or negative dielectric constant anisotropy.

The liquid crystal composition having negative dielectric anisotropy will now be described. As a liquid crystal composition having a negative dielectric anisotropy, for example, there is 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 a first component.

Wherein R ^1a and R ^2a are independently selected from the group consisting of alkyl having from 1 to 12 carbon atoms, alkoxy having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, or alkenyl having from 2 to 12 carbon atoms substituted with at least one hydrogen atom , 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, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4- Chloro-1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl or 7,8-difluorochroman- Diyl 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- Methyl-1,4-phenylene or 7,8-difluorochroman-2,6-diyl, Z ¹ is independently a single bond, - (CH ₂ ) ₂ - , -CH ₂ O-, -COO-, or -CF ₂ O-, j is 1, 2, or 3, j is 2 or 3 , Any two rings A &lt; ² &gt; may be the same or different, and any two Z &lt; ¹ &gt; s may be the same or different.

Preferred Ring A ² and Ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, respectively, and 1,4 -Cyclohexylene.

Preferred Z ¹ is -CH ₂ O- for increasing the dielectric anisotropy and is a single bond for lowering the viscosity.

The preferred j is 1 to lower the lower limit temperature and 2 to increase 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 selected from the group consisting of alkyl having from 1 to 12 carbon atoms, alkoxy having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, or alkenyl having from 2 to 12 carbon atoms substituted with at least one hydrogen atom , 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 - (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 for enhancing stability against ultraviolet rays or heat, or alkoxy having 1 to 12 carbon atoms for increasing the absolute value of dielectric anisotropy.

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, Decenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for lowering the viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. For the purpose of lowering the viscosity, a trans is preferable 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 alkenyls, straight-chain alkenyl is preferred over branching.

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- , 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 to reduce viscosity.

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

The compound (NL-1-1), the compound (NL-1-4) and the compound (NL-1-7) are preferable as the first component, Or a compound (NL-1-32).

As preferred examples of the liquid crystal composition having negative dielectric anisotropy described above, Japanese Laid-Open Patent Publication Nos. 57-114532, 2-4725, 4-224885, 8-40953, Japanese Patent Laid-Open Nos. 10-106869, 10-168076, 10-168453, 10-236989, 10-236990, 10-236992, 10 -236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075 Japanese Patent Application Laid-Open Nos. 10-237076 and 10-237448 (EP967261A1), Japanese Patent Laid-Open Nos. 10-287874, 10-287875, 10-291945, 029581, JP-A-11-080049, JP-A 2000-256307, JP-A 2001-019965, JP-A 2001-072626, Japanese Laid-Open Patent Publication No. 2001-192657, Japanese Laid-Open Patent Application No. 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Laid-Open Patent Application No. 2010-537010, Japanese Laid-Open Patent Application No. 2012-077201, And liquid crystal compositions disclosed therein.

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

As the most preferable structure of the photopolymerizable monomer or oligomer to be added for the purpose of improving the alignment property of the liquid crystal, the structures of (PM-1-1) to (PM-1-6) are exemplified.

The photopolymerizable monomer or oligomer is preferably 0.01% by weight or more in order to exhibit the effect of determining the oblique direction of the liquid crystal after polymerization. Further, in order to make the orientation effect of the polymer after polymerization appropriate, or after irradiation with ultraviolet rays, it is preferable that the amount is not more than 30% by weight in order to avoid elution of the unreacted monomer or oligomer into the liquid crystal.

An optically active compound is incorporated into the composition for the purpose of inducing a helical structure of the liquid crystal to give a twist angle. Examples of such compounds are compound (PAC-1-1) to compound (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 the lowering of the resistivity due to heating in the atmosphere or after the device is used for a long time and to maintain a large voltage holding ratio at room temperature as well as at a high temperature.

Preferable examples of the antioxidant include 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 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 because the volatility thereof is small. A preferable proportion of the antioxidant is not less than 50 ppm in order to obtain the effect, and not more than 600 ppm in order 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 include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as amines with steric hindrance are also desirable. A preferable ratio in these absorbers and stabilizers is 50 ppm or more in order to obtain the effect, and is not more than 10,000 ppm in order not to lower the upper limit temperature or to increase the lower limit temperature. A more preferable range is from 100 ppm to 10000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, and the like are mixed into the composition in order to suit the devices of 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 1000 ppm or less in order to prevent defective display. A more preferable ratio is in the range of 1 ppm to 500 ppm.

Polymerizable compounds may be incorporated into the compositions to suit the devices of the PSA (polymer sustained aligment) 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 about 10% by weight or less for preventing defective display. A more preferred ratio is in the range of about 0.1 wt% to about 2 wt%.

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

A polymerization initiator can be mixed as a substance required to easily generate a radical or an ion and initiate a chain polymerization reaction. For example, Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan K. K.), which are photopolymerization 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 the range 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 quickly 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 fall into several structural categories. One of them is itself a stable radical such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine and the like, and the other is easily reacted with a radical present in the polymerization system to change into a stable radical , Nitro, nitrite, amino, and polyhydroxy compounds. As the latter representative examples, hydroquinone, dimethoxybenzene and the like can be mentioned. A preferable proportion of the polymerization inhibitor is 5 ppm or more to obtain the effect and 1000 ppm or less to prevent display failure. A more preferable ratio is in the range of 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) so that the polyamic acid concentration became about 2% by weight. The column was subjected to measurement under the conditions of a column temperature of 50 캜 and a flow rate (flow rate) of 0.40 mL / min using HSPgel RT MB-M (manufactured by Waters) as the developing solution. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

2. Pencil Hardness

Followed by the JIS standard "JIS-K-5400, 8.4, Pencil Drawing Hardness Test" method. The result is expressed as the hardness of the pencil core. If the pencil hardness is low, peeling or scraping easily occurs. If the pencil hardness is larger than 2H, an alignment film which does not readily scrape off can be obtained.

3. Foreign matter test

The foreign substance test of the liquid crystal display element described later was performed using FORCE MEASUREMENT, DS2-50N (manufactured by Imada Co., Ltd.). A force of 9.8 N was applied to the produced liquid crystal display element at 60 times / minute for 1 minute. The liquid crystal display element was observed by a microscope, and the presence or absence of a foreign substance was confirmed after pressing.

4. Contrast

The contrast of a liquid crystal device to be described later was evaluated using a luminance meter (YOKOGAWA 3298F). A liquid crystal display element was placed under a polarization microscope under a crossed Nicol state, and the minimum luminance was measured as black luminance. Next, an arbitrary rectangular wave voltage was applied to the device, and the maximum luminance was measured as white luminance. The value of the white luminance / black luminance was taken as a contrast. If the contrast is less than 2500, it is defective. If the contrast is 2500 or more, it is good. If the contrast is 3000 or more, it is the best.

5. AC afterimage measurement

The luminance-voltage characteristic (B-V characteristic) of the liquid crystal display element described later was measured. This is called a luminance-voltage characteristic before the stress application: B (before). Next, an AC voltage of 4.5 V and 60 Hz was applied to the device for 20 minutes, followed by a short circuit for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This is called a luminance-voltage characteristic after the application of the stress: B (after). Based on these values, the luminance change rate? B (%

B (before) / B (before) (formula AC1)

Using the following equation. These measurements were made by referring to the brochure of International Publication No. 2000/43833. The smaller the value of? B (%) at the voltage of 0.75 V is, the more the AC residual image can be suppressed, but it is preferably 3.0% or less.

<Tetracarboxylic dianhydride>

(1-8): 1,8-bis (3,4-dicarboxylic acid phenyl) octane dianhydride

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

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

(5): 1,2,4,5-Cyclohexanetetracarboxylic dianhydride

(6): Ethylenediamine tetraacetic acid dianhydride

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

(9): Octahydrophthalene-1,3,4,6-tetracarboxylic acid-1,3,4,6-dianhydride

(10): pyromellitic dianhydride

(11): biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride

(12): 4,4'-Oxydiphthalic anhydride

(13): 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride

(1-6): 1,6-bis (3,4-dicarboxylic acid phenyl) hexane dianhydride

(1-4): 1,4-bis (3,4-dicarboxylic acid phenyl) butane dianhydride

(3-1-5): 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride

<Diamine>

(I-3): 4,4'-diamino azobenzene

(D-1): 1,4-Phenylenediamine

(D-2-1): 4,4'-diaminodiphenylmethane

(D-2-2): 4,4'-diaminodiphenylethane

(D-2-4): 4,4'-diaminodiphenylbutane

(D-2-7): 4,4'-diaminodiphenyl ether

(D-3): 4,4'-N, N'-bis (4-aminophenyl) piperazine

(D-4-3): 1,3-bis (4- (4-aminophenyl) methyl) phenyl) propane

(D-5-1): N, N'-bis (4-aminophenyl) -N, N'- dimethylethylenediamine

<Solvent>

NMP: N-methyl-2-pyrrolidone

DMI: 1,3-dimethyl-2-imidazolidinone

GBL:? -Butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

EDE: diethylene glycol diethyl ether

BP: 1-butoxy-2-propanol

<Additives>

Add.1: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene

Add.2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

Add.3: 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane

Add.4: 3-glycidoxypropyltrimethoxysilane

Positive liquid crystal composition:

Property: NI 100.1 ℃; Δε 5.1; ? N 0.093; η 25.6 mPa · s.

Negative liquid crystal composition:

Property Value: NI 75.7 ℃; Δε -4.1; [Delta] n 0.101; η 14.5 mPa · s.

<Synthesis of polyamic acid>

[Synthesis Example A-1]

3.3066 g of the diamine of the formula (I-3) and 100.0 g of dehydrated NMP were placed in a 200 mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. Then, 3.1658 g of the tetracarboxylic dianhydride of the formula (1-8), 1.5276 g of the tetracarboxylic dianhydride of the formula (3-1-1) and 52.0 g of dehydrated NMP were added and stirring was continued at room temperature for 24 hours . 40.0 g of BC was added to this reaction solution to obtain a polyamic acid solution having a polymer solid content concentration of 4% by weight. This polyamic acid solution is referred to as PA-1. The weight average molecular weight of the polyamic acid contained in PA-1 was 18,300.

[Synthesis Examples A-2 to A-31 and Synthesis Examples B-1 to B-13]

(PA-2) to (PA-31) and (PB-1) having a polymer solid content concentration of 4% by weight in accordance with Synthesis Example 1 except that the tetracarboxylic dianhydride, diamine, To (PB-13). These are shown in Table 1 and Table 2. Synthesis Example A-1 was also shown.

[Table 1]

[Table 1] (Continued)

[Table 2]

<Polymer blending>

[Synthesis Example PC-1]

[A] A polyamic acid solution (PB-1) having a polymer solid content concentration of 4% by weight prepared in Synthesis Example A-1 and a polyamic acid solution (PB-1 ) Were mixed at a mixing ratio by weight ratio [A] / [B] = 3/7. The obtained polyamic acid solution is referred to as PC-1.

[Synthesis Examples PC-2 to PC-38]

A polyamic acid solution selected from polyamic acid solutions (PA-1) to (PA-31) and a polyamic acid solution (PB-1) (PC-1) to (PC-38) were prepared by mixing the polyamic acid solutions (A) and (B) This is shown in Table 3. Synthesis Example PC-1 was also shown.

[Table 3]

[Synthesis Example PD-1]

To the polyamic acid solution (PA-1) having a polymer solid content concentration of 4% by weight, an additive (Add.1) was added at a ratio of 10% by weight per polymer weight. The obtained polyamic acid solution is referred to as PD-1.

[Synthesis Examples PD-2 to PD-28]

Polyamic acid solutions (PD-2) to (PD-28) having a polymer solid content concentration of 4% by weight were prepared in accordance with PD-1 except that the type and amount of the polyamic acid solution and additives were changed. This is shown in Table 4. PD-1 was also described.

[Table 4]

[Example 1]

&Lt; Measurement method of substrate for measurement and pencil hardness measurement >

A polyamic acid solution (PA-1) having a solid polymer concentration of 4% by weight prepared in Synthesis Example 1 was applied as a liquid crystal aligning agent to a glass substrate by a spinner (spin coater (1H-DX2) manufactured by Mikasa Corporation). Incidentally, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including the following examples and comparative examples, so that the orientation film had the following film thickness. After coating, the coating was heated and dried at 70 DEG C for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by Asuzon Co., Ltd.). Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., linearly polarized light of ultraviolet rays was irradiated from the perpendicular direction to the substrate through a polarizing plate. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., Ltd., and the light quantity was measured to be 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. Subsequently, the substrate was subjected to heat treatment at 230 占 폚 for 15 minutes in a clean oven (Espec Co., PVHC-231) to form an alignment film having a thickness of 100 占 10 nm. The pencil hardness of the resulting substrate was measured and found to be 3H.

&Lt; Fabrication method of FFS cell, confirmation of flow orientation, confirmation of foreign matter generation, and measurement of residual image after AC &

The surfaces on which the alignment films of the two substrates on which the alignment films were formed were formed so as to face each other so that the rubbing directions were parallel to the respective alignment films and voids for injecting the positive type liquid crystal compositions were formed between the opposing alignment films, , And an empty FFS cell having a cell thickness of 4 탆 was assembled. The positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, no flow orientation was observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, no generation of foreign matter was observed. Also, the value of the contrast was measured to be 2730, and the after-image of the AC was measured to be 2.6%.

[Examples 2 to 41, Comparative Examples 1 to 9]

A polyamic acid solution used as a liquid crystal aligning agent was changed, a substrate for measurement was prepared by the method according to Example 1, and pencil hardness was measured. Further, FFS cells were fabricated by the method according to Example 1, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The polyamic acid solution used as the liquid crystal aligning agent and the measurement results are shown in Table 5-1. Example 1 was also described.

[Table 5-1]

[Table 5-1] (Continued)

As shown in Table 5-1, the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has a pencil hardness of 2H or more and a high film hardness. Further, it was confirmed that the liquid crystal display element of the present invention does not cause the generation of foreign matter, has a high contrast, and is also suppressed from the AC residual image.

[Examples 42 to 68, Comparative Examples 10 to 13]

A substrate for measurement was prepared in the same manner as in Example 1 except that the polyamic acid solution shown in Table 5-2 was used as a liquid crystal aligning agent and the pencil hardness was measured. The results of the obtained pencil hardness are shown in Table 5-2.

The procedure of Example 1 was repeated except that the negative type liquid crystal composition was vacuum-injected instead of the positive type liquid crystal composition using the polyamic acid solution shown in Table 5-2 as a liquid crystal aligning agent, Thereby producing a display device. The results of the polyamic acid solution used as the liquid crystal aligning agent, the flow orientation confirmation, the foreign matter test, the contrast measurement and the AC residual image measurement are shown in Table 5-2.

[Table 5-2]

As shown in Table 5-2, even when a negative type liquid crystal composition is used, the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has a pencil hardness of 2H or more and a high film hardness. Further, it was confirmed that the liquid crystal display element of the present invention does not cause the generation of foreign matter, has a high contrast, and is also suppressed from the AC residual image.

[Example 69]

A polyamic acid solution (PC-1) having a polymer solid content concentration of 4% by weight prepared by blending was used as a liquid crystal aligning agent, and this liquid crystal aligning agent was applied to a glass substrate by an ink jet application device (DMP-2831 manufactured by Fuji Film Co., Ltd.). Then, the droplet gap and the cartridge application voltage were adjusted so that the liquid crystal alignment film had the following film thicknesses. After coating, the coating was heated and dried at 70 DEG C for 80 seconds on a hot plate (EC hot plate (EC-1200N) manufactured by Asuzon Co., Ltd.). Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., linearly polarized light of ultraviolet rays was irradiated from the perpendicular direction to the substrate through a polarizing plate. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., Ltd., and the light quantity was measured to be 1.0 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. Subsequently, the substrate was subjected to heat treatment at 230 캜 for 15 minutes in a clean oven (Espec Co., PVHC-231) to form a liquid crystal alignment film having a thickness of 100 ± 10 nm. The pencil hardness of the resulting substrate was measured and found to be 3H.

A liquid crystal alignment film is formed on the substrate so that the two liquid crystal alignment films are formed on the two liquid crystal alignment films so that the two liquid crystal alignment films face each other and the polarizing direction of the ultraviolet light irradiated to each liquid crystal film is parallel, And a bonded FFS cell having a cell thickness of 4 탆 was assembled. The positive type liquid crystal composition was vacuum-injected into the fabricated blank FFS cell to produce an FFS liquid crystal display device. When the orientation of the liquid crystal in the obtained liquid crystal display element was confirmed, no flow orientation was observed. Subsequently, when the liquid crystal display element after the foreign matter test was observed with a microscope, no generation of foreign matter was observed. Further, the contrast value was measured to be 3010, and the AC residual image was measured, and the ΔB was 2.0%.

[Examples 70 to 75 and Comparative Examples 14 to 18]

A substrate for measurement was prepared by the method according to Example 69 except that the polyamic acid solution shown in Table 5-3 was used as the liquid crystal aligning agent, and the pencil hardness was measured. Further, an FFS cell was fabricated by the method according to Example 69, and flow orientation confirmation, foreign matter test, contrast measurement and AC afterimage measurement were performed. The measurement results are shown in Table 5-3.

[Table 5-3]

As shown in Table 5-3, even when the liquid crystal aligning agent is printed by the ink jet method, the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has a pencil hardness of 2H or more and a high film hardness. Further, it was confirmed that the liquid crystal display element of the present invention does not cause the generation of foreign matter, has a high contrast, and is also suppressed from the AC residual image.

It was confirmed that the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film exhibiting high film hardness and excellent liquid crystal alignability. It has been confirmed that a liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has excellent characteristics such that foreign substances are not easily generated during operation of the touch panel and high contrast is exhibited and AC afterimage does not easily occur . The liquid crystal aligning agent of the present invention can be suitably applied particularly to a transverse electric field type liquid crystal display element.

Claims (16)

A liquid crystal aligning agent containing at least one polymer (a) selected from polyamic acid and derivatives thereof obtained by reacting tetracarboxylic dianhydride and diamine,
Wherein the tetracarboxylic dianhydride contains at least one tetracarboxylic dianhydride represented by the following formula (1) and at least one selected from tetracarboxylic dianhydrides having an alicyclic structure or aliphatic structure,
Wherein the diamine is a liquid crystal aligning agent containing at least one diamine having a photoreactive structure,

In the above formula (1), m is an integer of 1 to 10. The method according to claim 1,
Wherein the tetracarboxylic dianhydride of the formula (1) is a tetracarboxylic dianhydride represented by the following formula (1-8): Liquid crystal aligning agent:

. 3. The method according to claim 1 or 2,
Wherein the tetracarboxylic dianhydride having an alicyclic or aliphatic structure is at least one selected from the compounds represented by the following formulas (3) to (9), liquid crystal aligning agent:

At least one of the hydrogen atoms in the formulas (3) to (9) may be substituted with -CH ₃ , -CH ₂ CH _3, or phenyl. 3. The method according to claim 1 or 2,
A tetracarboxylic dianhydride having an alicyclic or aliphatic structure is at least one selected from the compounds represented by the following formula (3-1), a liquid crystal aligning agent:

In the formula (3-1), R is being independently hydrogen, -CH _3, -CH ₂ CH ₃ or phenyl. 3. The method according to claim 1 or 2,
Wherein the tetracarboxylic dianhydride having an alicyclic structure is 1,2,3,4-cyclobutane tetracarboxylic dianhydride. 6. The method according to any one of claims 1 to 5,
A liquid crystal aligning agent wherein the diamine having a photoreactive structure is 4,4'-diamino azobenzene. 7. The method according to any one of claims 1 to 6,
Wherein the diamine further contains at least one selected from the group of compounds represented by the following formulas (D-1) to (D-5): Liquid crystal aligning agent:

In the formulas (D-2) and (D-4), X and Y are a single bond, -O-, -NH-, -S-, or an alkylene having 1 to 6 carbon atoms;
At least one hydrogen in the benzene ring may be substituted with -CH ₃ ;
In the formula (D-4), a is an integer of 1 to 8; And,
In the formula (D-5), Ra is alkyl having 1 to 3 carbon atoms. 6. The method according to any one of claims 1 to 5,
(B) selected from polyamic acid and derivatives thereof obtained by reacting tetracarboxylic dianhydride having no photoreactive structure and diamine having no photoreactive structure, and derivatives thereof. 9. The method of claim 8,
The tetracarboxylic dianhydride used in the synthesis of the polymer (b) is a liquid crystal aligning agent containing at least one selected from the following formulas (3) to (13)

At least one of the hydrogens in the formulas (3) to (13) may be substituted with -CH ₃ , -CH ₂ CH _3, or phenyl. 10. The method according to claim 8 or 9,
The liquid crystal aligning agent containing at least one diamine selected from the following formulas (D-1) to (D-5), wherein the diamine used in the synthesis of the polymer (b)

In the formulas (D-2) and (D-4), X and Y are a single bond, -O-, -NH-, -S-, or an alkylene having 1 to 6 carbon atoms;
At least one hydrogen in the benzene ring may be substituted with -CH ₃ ;
In the formula (D-4), a is an integer of 1 to 8; And,
In the formula (D-5), Ra is alkyl having 1 to 3 carbon atoms. 11. The method according to any one of claims 1 to 10,
Wherein the liquid crystal aligning agent further contains at least one member selected from the group consisting of an oxazine compound, an oxazine compound, an epoxy compound, and a silane coupling agent. 12. The method of claim 11,
Wherein the silane coupling agent is at least one selected from the group consisting of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, paraaminophenyltrimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. The group of compounds Wherein the liquid crystal aligning agent is at least one selected from the group consisting of a liquid crystal aligning agent, 13. The method according to any one of claims 1 to 12,
A liquid crystal aligning agent containing at least one solvent selected from alcohols, ethers and ketones. 14. The method according to any one of claims 1 to 13,
A liquid crystal aligning agent containing at least one solvent selected from alkylene glycol alkyl ether derivatives, dialkylene glycol dialkyl ether derivatives and propylene glycol derivatives. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 14. A liquid crystal display element comprising the liquid crystal alignment film according to claim 15.