KR20160021021A - Triazole-containing tetracaboxylic acid dianhydrides, liquid crystal aligning agents, liquid crystal alignment layers, and liquid crystal display devices using the same - Google Patents

Abstract

식(1)에 있어서, X는 트리아졸 환을 적어도 1개 포함하는 2가의 유기기이며;
R¹ 및 R²는 각각 독립적으로, 하기의 3가의 기의 군으로부터 선택되는 1개이며;
[화학식 178]

이들 기 중 적어도 1개의 수소는 메틸, 에틸 또는 페닐로 치환될 수도 있다.An object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film which does not easily peel or scrape.
In order to solve the above problems, the present invention provides a tetracarboxylic dianhydride represented by the following formula (1).
[177]

In the formula (1), X is a divalent organic group containing at least one triazole ring;
R ¹ and R ² are each independently one selected from the group of the following trivalent groups;
[178]

At least one of these groups may be substituted with methyl, ethyl or phenyl.

Description

TECHNICAL FIELD [0001] The present invention relates to a tetrazole-containing tetracarboxylic dianhydride, a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element,

The present invention relates to a novel tetracarboxylic dianhydride, a polyamic acid obtained by using the same, a derivative thereof, and a use thereof. 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 display, etc., and optoelectronic devices such as an optical printer head, an optical Fourier transform device and a light valve, As the display element, a display element using a nematic liquid crystal is mainstream. 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. Among liquid crystal display elements, liquid crystal alignment layers are one of important materials related to the display quality, and it is important to improve the performance of the alignment layer as the liquid crystal display element is improved in quality.

The liquid crystal alignment film is formed by a liquid crystal aligning agent. At present, a liquid crystal aligning agent mainly used is a solution (varnish) in which polyamic acid or 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.

Industrially, a rubbing method which is simple and capable of high-speed processing at a large area is widely used as an orientation treatment method. The rubbing process is a process in which the surface of the liquid crystal alignment film is rubbed in one direction by using a fabric obtained by planting fibers such as nylon, rayon, and polyester, thereby making it possible to obtain a uniform orientation of the liquid crystal molecules. However, in the rubbing treatment, problems such as dust generated by cutting off the liquid crystal alignment film, scratches formed on the liquid crystal alignment film, lowering the display quality, and occurrence of static electricity are pointed out. Development is becoming more active.

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. There are many alignment mechanisms (mechanisms) such as photolysis, photoisomerization, photo-dimerization, photo-crosslinking and the like, which are proposed in the photo-alignment treatment method (see Non-Patent Document 1 and Patent Documents 1 and 2, for example). Since the photo alignment method has a higher alignment uniformity than the rubbing method and is 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 causing scratches on the film There are advantages. However, compared to the rubbing method, the anchoring energy is small and the orientation is low. This causes a decrease in the response speed of the liquid crystal molecules or baking, and therefore improvement has been required.

In order to overcome the drawbacks of such a photo-alignment treatment method, there has been proposed a material which amplifies the anisotropy of a film by using polyimide having liquid crystallinity and heat-treating the material at the time of film formation (see, for example, 3 to 7). However, the photo alignment film to which such a technique is applied is prone to peeling or scraping of the film at the time of panel production, and foreign matter generated has a problem of deteriorating display quality of the panel.

Japanese Patent Application Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 10-251646 Japanese Patent Application Laid-Open No. 2005-275364 Japanese Patent Application Laid-Open No. 2007-248637 Japanese Patent Application Laid-Open No. 2009-069493 Japanese Patent Application Laid-Open No. 2010-049230 Japanese Patent Application Laid-Open No. 2010-197999

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

A first object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film which does not easily peel off or shave by using a polymer in which a specific tetracarboxylic dianhydride is used as a raw material.

A second object of the present invention is to provide a liquid crystal display element having a liquid crystal alignment film having a high liquid crystal aligning ability and having good afterimage characteristics by coating the above liquid crystal aligning agent.

The present inventors have developed a tetracarboxylic dianhydride represented by the formula (1). It has been found that by using the liquid crystal aligning agent containing a polyamic acid or a derivative thereof containing the tetracarboxylic dianhydride as a raw material, it is possible to obtain a liquid crystal alignment film which has high film hardness and does not generate the above-mentioned foreign matter, Completed.

The present invention has the following configuration.

[1] A tetracarboxylic dianhydride represented by the formula (1).

[Chemical Formula 1]

In the formula (1), X is a divalent organic group containing at least one triazole ring;

R ¹ and R ² are each independently one selected from the group of the following trivalent groups;

(2)

At least one of these groups may be substituted with methyl, ethyl or phenyl.

[2] The tetracarboxylic dianhydride according to [1], which is represented by the formula (2).

(3)

In the formula (2), X is a divalent organic group containing at least one triazole ring.

[3] The tetracarboxylic dianhydride according to [1], which is represented by the formula (3).

[Chemical Formula 4]

In the formula (3), X ¹ is a triazole ring;

A ¹ and A ² are each independently a single bond or alkylene having 1 to 12 carbon atoms;

At least one hydrogen in the alkylene may be substituted with fluorine; And,

At least one -CH ₂ - may be substituted with -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH-, or -C≡C-.

[4] The tetracarboxylic dianhydride according to [1], which is represented by the formula (4).

[Chemical Formula 5]

In the above formula (4), X ¹ and X ² are triazole rings;

A ^{1 to} A ³ are each independently a single bond or alkylene having 1 to 12 carbon atoms;

At least one hydrogen in the alkylene may be substituted with fluorine; And,

At least one -CH ₂ - in the alkylene may be substituted with -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH-, or -C≡C-.

[5] A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride having at least one tetracarboxylic dianhydride described in any one of [1] to [4] above with a diamine.

[6] A liquid crystal aligning agent containing the polyamic acid according to [5] or a derivative thereof.

[7] The liquid crystal aligning agent according to the above [6], which contains the polyamic acid or derivative thereof according to the above-mentioned [5] and other polymer.

[8] A liquid crystal aligning agent for photo-alignment as described in [6] or [7] above.

[9] The liquid crystal aligning agent for rubbing according to the above [6] or [7].

[10] A liquid crystal aligning agent for a liquid crystal display element of a transverse electric field system according to any one of [6] to [9] above.

[11] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [6] to [10] above.

[12] A liquid crystal display device having the liquid crystal alignment film according to [11] above.

The liquid crystal alignment film formed by coating the liquid crystal aligning agent containing the polymer obtained by using the tetracarboxylic dianhydride of the present invention as a raw material has high 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.

1 is a sectional view of a test panel.

The terms used in the present invention will be described. The compound represented by the formula (I-1) may be referred to as the compound (I-1). The compounds represented by other formulas may be similarly abbreviated. The term " arbitrary " used to define the chemical structural formula indicates arbitrary not only the position but also the number. In the chemical structural formula, a group in which a letter (for example, A) is surrounded by a circle or a hexagonal means a ring group (ring A).

The tetracarboxylic dianhydride of the present invention will be described. In the present specification, the term "tetracarboxylic dianhydride" is sometimes referred to simply as "acid anhydride" or "acid dianhydride".

The tetracarboxylic dianhydride of the present invention is represented by the following formula (1).

[Chemical Formula 6]

In the formula (1), X is a divalent organic group containing at least one triazole ring, and R ¹ and R ² are each independently selected from the group consisting of the following trivalent groups,

(7)

At least one of these groups may be substituted with methyl, ethyl or phenyl.

The tetracarboxylic dianhydride of the present invention is a tetracarboxylic dianhydride having two acid anhydride moieties and having a spacer containing a triazole ring between the acid anhydride moieties as described above. A liquid crystal aligning agent containing a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride having an alkyl chain spacer such as 5,5 '- (octane-1,8-diyl) bis (phtharic acid anhydride) , The film hardness is not sufficient and there is a case where a foreign substance is generated due to shrinkage. On the other hand, by using the tetracarboxylic dianhydride of the present invention in place of the tetracarboxylic dianhydride, the interaction between the polymer chains is enhanced by the interaction of the triazole rings, and the film hardness of the liquid crystal alignment film can be improved .

In the tetracarboxylic dianhydride represented by the formula (1), the tetracarboxylic dianhydride represented by the formula (3) or (4) is preferable in view of the easiness of obtaining the raw material.

[Chemical Formula 8]

In formula (3), X ¹ is a triazole ring, A ¹ and A ² are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine , Arbitrary -CH ₂ - may be substituted with -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH- or -C≡C-.

[Chemical Formula 9]

In formula (4), X ¹ and X ² are triazole rings, A ^{1 to} A ³ are each independently a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene is substituted with fluorine , And arbitrary -CH ₂ - may be substituted with -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH- or -C≡C-.

The tetracarboxylic dianhydride of the formula (3) can be synthesized, for example, by the following route (Synthesis Example 1).

[Chemical formula 10]

Wherein A is a single bond or alkylene having 1 to 12 carbon atoms, and any hydrogen in the alkylene may be substituted with fluorine, and arbitrary -CH ₂ - may be replaced by -O-, -COO-, -OCO- , -CONH-, -NHCO-, -CH = CH- or -C? C-.

The compound represented by (c) can be obtained by azidizing the phthalic acid derivative (a) and reacting the copper sulfate pentahydrate with sodium ascorbate in the presence of (b). Next, the tetracarboxylic dianhydride represented by the formula (3) of the present invention can be obtained by reacting with sodium hydroxide, hydrolyzing the ester group and dehydrating it by reacting with acetic anhydride.

The tetracarboxylic dianhydride of the formula (4) can be synthesized, for example, by the following route (Synthesis Example 2).

(11)

The compound represented by (e) can be obtained by azidizing the alkyl dibromide (d), and reacting the copper sulfate pentahydrate with sodium ascorbate in the presence of (c). Next, the tetracarboxylic dianhydride represented by the formula (4) of the present invention can be obtained by reacting with sodium hydroxide, hydrolyzing the ester group and dehydrating it by reacting with acetic anhydride.

The tetracarboxylic dianhydride of the present invention may be purified by various purification methods such as recrystallization and column chromatography. The polyamic acid or derivatives thereof of the present invention can be used for various polyimide coatings, polyimide resin molded articles, films, fibers and the like in addition to liquid crystal aligning agents.

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

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

When the anchoring energy is high in the tetracarboxylic dianhydride, that is, when it is important to further improve the orientation of the liquid crystal, it is preferable that the formula (1-1), the formula (1-5) The tetracarboxylic dianhydrides represented by the general formulas (1-26) to (1-34) are preferable. When the improvement of the transmittance is emphasized, the compounds represented by formulas (1-2) to (1-4) In order to obtain the tetracarboxylic dianhydride of the present invention of (6) to (1-8) with higher solubility as a solvent, the tetracarboxylic acid of the present invention represented by the formulas (1-9) to (1-11) By using dianhydride, an alignment film capable of achieving desired characteristics can be obtained.

(1-1), (1-5) and (1-22) to (1-28) are preferable from the viewpoints of ease of synthesis and inhibition of coloration, 1-5) is particularly preferable.

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

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

The tetracarboxylic dianhydride used to prepare the polyamic acid and derivatives thereof of the present invention will be described.

The tetracarboxylic dianhydride used in the present invention can be selected without limitation 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).

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

[Chemical Formula 22]

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

(23)

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

More specifically, the tetracarboxylic dianhydrides represented by the following formulas (AN-1) to (AN-16-14) are exemplified.

≪ EMI ID =

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 independently any one of the following trivalent groups.

(25)

When G ¹² is > CH-, the hydrogen of > CH- may be substituted with -CH ₃ . When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And, R ¹¹ is hydrogen or -CH _3. Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas.

(26)

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

(27)

In formula (AN-2), R ¹² is independently hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include the compounds represented by the following formulas.

(28)

[Chemical Formula 29]

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include the compounds represented by the following formulas.

(30)

(31)

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.

(32)

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.

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

(33)

(34)

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

(35)

(36)

(37)

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.

(38)

[Chemical Formula 39]

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.

(40)

(41)

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include the compounds represented by the following formulas.

(42)

(43)

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.

(44)

[Chemical Formula 45]

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.

(46)

The formula (AN-10) is the following tetracarboxylic dianhydride.

(47)

(48)

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.

(49)

(50)

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.

(51)

(52)

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.

(53)

(54)

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.

(55)

(56)

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.

(57)

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

(58)

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.

In the present invention, the tetracarboxylic dianhydride of formula (1) and a photosensitive material can be used in combination, and can be selected without limitation from known photosensitive tetracarboxylic dianhydrides. Examples of such photosensitive tetracarboxylic dianhydrides include the following formulas (PAN-1) to (PAN-8).

[Chemical Formula 59]

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

The diamine can be divided into two types according to its structure. That is, when a skeleton connecting two amino groups is regarded as a main chain, it is a group branching from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms. Specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and a group having a steroid skeleton. Has an effect as an airway side chain group having at least one ring, and the ring at the terminal thereof has any one of an alkyl group having a carbon number of 1 or more, an alkoxy group having a carbon number of 1 or more, and an alkoxyalkyl group having a carbon number of 2 or more. In the following description, the diamine having such a side chain group is sometimes referred to as a side chain type diamine. The diamine having no side chain group may be referred to as a non-branched chain diamine.

By properly using the non-branched diamine and the branched-chain diamine separately, it is possible to cope with the pre-tilt angle required for each. The side chain type diamine is preferably used in combination so as not to impair the characteristics of the present invention. It is also preferable to select and use the side chain type diamine and the non-side chain type diamine for the purpose of improving the vertical alignment property, the voltage holding ratio, the burning property and the orientation property to the liquid crystal.

The non-branched diamine will be explained. Examples of the diamine having no side chain include diamines of the following formulas (DI-1) to (DI-16).

(60)

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

(61)

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

(62)

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.

(63)

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 group and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, And is an integer of 0 to 4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), the bonding position of -NH 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.

≪ EMI ID =

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.

(65)

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

(66)

(67)

(68)

(69)

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

(70)

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

(71)

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

(72)

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

(73)

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

≪ EMI ID =

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.

(75)

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

[Formula 76]

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.

[Formula 77]

(78)

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

(79)

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

(80)

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

[Formula 81]

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

(82)

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

(83)

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

(84)

(85)

≪ EMI ID =

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

[Chemical Formula 87]

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

[Formula 88]

(89)

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

(90)

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

[Formula 91]

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 the formula (DIH-2), the 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.

≪ EMI ID =

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

≪ EMI ID =

(94)

Such non-branched-chain diamines and dihydroazides 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. In these groups, alkyl, alkenyl and alkynyl 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 terminal ring thereof has 1 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 cyclohexyl bis (phenyl) oxycarbonyl, and the like.

Further, a group having two or more benzene rings, a group having two or more cyclohexane rings, or 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).

≪ EMI ID =

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, and m' is an integer of 1 to 12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH ₂ - and -CH ₂ CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be substituted with -O-, -CH = CH- or -C≡C-. Hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, 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. That is, when the coupling position of the group " R ²⁵ -G ²⁶ - " is set to the first position, it is preferable that the two coupling positions are the third position and the fifth position or the second position and the fifth position.

≪ EMI ID =

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).

[Formula 97]

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

(98)

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. At least one hydrogen in the benzene ring of formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl. The 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. Equation 2 groups in (DI-32) "- phenylene -G ³⁰ -O-" is one of bonded to position 3 of the steroid nucleus, and the other is preferably bonded to the 6-position of the steroid nucleus Do. 2 groups in the formula (DI-33) "- phenylene -G ³⁰ -O-", binding position of the benzene ring of the, with respect to the bonding position of the steroid nucleus, preferably in the meta-position or para-position, respectively. In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

[Formula 99]

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 diamine 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.

(100)

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.

(101)

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.

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

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.

≪ EMI ID =

(108)

(109)

(110)

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

(111)

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

(112)

(113)

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

(114)

(115)

≪ EMI ID =

(117)

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.

(118)

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).

(119)

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

(120)

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 = 2, 4 or 6 is preferable, and m = 4 (DI-5-12), m is preferably 2 to 6, m is particularly preferably 5, and m = 1 or 2 in the formula (DI-5-13) , 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, (DI-5-28), the formula (DI-5-30), and the formula (DI- Diamine represented by the formula (DI-2-1), the formula (DI-5-1) and the formula (DI-13-1) is particularly preferable Do. 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 formulas (DI-4-1), (DI-5-1), (DI-5-12) and (DI-5-13) Is particularly preferable. Among them, in the formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and m = 2 to 6 is preferable in the formula And m = 5 is particularly preferable. In formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

In the present invention, a photosensitive material can be used in combination, and the photosensitive diamine can be selected without limitation from known photosensitive diamines. For example, azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. Examples of such photosensitive diamine compounds include the following formulas (PDI-1) to (PDI-12).

(121)

(122)

(123)

(124)

In the formula (PDI-7), R ⁵¹ is independently -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer from 0 to 2, and, in formula (PDI-12) Wherein R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine.

Of the photosensitive diamines, the formula (PDI-7) is preferred when it is important to improve the orientation of the liquid crystal. In the aspect of reacting the tetracarboxylic dianhydride of the present invention with the photosensitive diamine, in consideration of the improvement of the orientation property and the transmittance, the ratio of the photosensitive diamine / photosensitive diamine to the diamine is from 100/0 (mol%) to 50/50 Mol%). Further, two or more other photosensitive diamines may be used in combination in order to improve the above-mentioned various characteristics such as electrical characteristics and afterimage characteristics.

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, so that further progress of the polymerization reaction can be suppressed. 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 diamines substituted with monoamines may be used alone or in combination of two or more, 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 polyamic acid of the terminal modification type or a derivative thereof, 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 content of the monoisocyanate compound in the monomer is preferably 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 the tetracarboxylic dianhydride and 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. The other polymer is a polymer other than a polyamic acid or a derivative thereof obtained by reacting the tetracarboxylic dianhydride of the present invention with a diamine, wherein the tetracarboxylic dianhydride not containing the tetracarboxylic dianhydride of the formula (1) Polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) obtained by reacting polyamic acid or its derivative (hereinafter referred to as "other polyamic acid or derivative thereof" Derivatives, poly (meth) acrylates, and the like. It may be one kind or two kinds or more. Of these, other polyamic acid or derivatives thereof and polysiloxane are preferable, and other polyamic acids or derivatives thereof are more preferable.

By controlling the structure and the molecular weight of each polymer 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 and applying the preliminary drying to the substrate as described later, The polyamic acid or its derivative component [A] of the present invention can be separated into the upper layer and the other polyamic acid or its derivative component [B] 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. The confirmation of the layer separation can be confirmed by the fact that the surface energy of the formed alignment film is the same or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component.

An alignment film separated into an upper layer and a lower layer can be formed by controlling the structure and molecular weight of each polymer in the alignment agent in which the polyamic acid or its derivative of the present invention is blended with other polyamic acid or its derivative have. For example, an alignment film in which the polyamic acid or its derivative component [A] of the present invention is separated into the upper layer and the other polyamic acid or its derivative component [B] is separated into lower layers can be formed. This can be controlled by applying the blended alignment agent to the substrate and, at the time of heating and drying, separating the polymer having a small surface energy into an upper layer and the polymer having a large surface energy into a lower layer. The confirmation of the layer separation can be confirmed by the fact that the surface energy of the formed alignment film is the same or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component.

As the tetracarboxylic dianhydride used for synthesizing the other polyamic acid or its derivative, tetracarboxylic dianhydride which is used for synthesizing polyamic acid or its derivative, which is an essential component of the liquid crystal aligning agent of the present invention, Can be selected from the carboxylic acid dianhydride without limitation and include those exemplified above.

Among them, in the case where the acid anhydride has an importance to improve the layer separability, the formula (AN-3-2), the formula (AN-1-13) and the formula (AN-4-30) Do.

(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-1-2), AN-2-1, AN-7-2, and AN-7-2 in the above acid anhydride, when it is important to improve the VHR of the liquid crystal display element. (AN-16) and (AN-16-4) are preferable. Among them, in the formula (AN-1-2), when m = 4 or 8, desirable.

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.

Examples of the diamines and hydrazides used for synthesizing the other polyamic acid or derivatives thereof include other diamines which can be used for synthesizing the polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention And the like.

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

(DI-2-1), (DI-2-1), (DI-5-1), and (DI-5-1) among the diamines and dihydrazides described above, DI-7-3), and the diamine represented by the formula (DI-2-1) is particularly preferable. In the formula (DI-5-1), m = 1, 2 or 4 is preferable, m = 1 or 2 is particularly preferable, and in the formula (DI-7-3), 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-4-15), the formula (DI-5-1), the formula (DI-5-28), the formula (DI- 5-30) And diamines represented by the formulas (DI-2-1), (DI-5-1) and (DI-13-1) are particularly preferable. Among them, in the formula (DI-5-1), m = 1 or 2 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, 5-15), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-1), (DI-5-1), and (DI-16-1) 5-12), the formula (DI-5-13), and the formula (DI-5-30) are particularly preferable. In the formula (DI-5-1), m = 1 or 2 is preferable, m = 2 to 6, m = 5 is particularly preferable in the formula (DI-5-12) , M = 1 or 2 is preferable and m = 1 is particularly preferable in the formula (DI-5-13), and in the formula (DI-5-30), k = 2 is particularly preferable.

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

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

As the polysiloxane, there can be mentioned, for example, Japanese Patent Laid-Open Nos. 2009-036966, 2010-185001, 2011-102963, 2011-253175, 2012- 159825 publication, International Publication No. 2008/044644 pamphlet, International Publication No. 2009/148099 pamphlet, International Publication No. 2010/074261 pamphlet, International Publication No. 2010/074264 pamphlet, International Publication No. 2010/126108 pamphlet, International Publication No. 2011/068123 A pamphlet, a pamphlet of International Publication No. 2011/068127, a pamphlet of International Publication No. 2011/068128, a pamphlet of International Publication No. 2012/115157, a pamphlet of International Publication No. 2012/165354, and the like.

≪ Alkenyl-substituted nadimide compound &

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

The nadimide compound will be specifically described below.

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

(125)

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

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

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

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

In this case, preferred W is an alkylene, cyclohexylene, phenylene, tolylene, xylene, -C ₃ H ₆ -O- (Z ² -O) _n -OC ₃ H ₆ - Z ² is alkylene having 2 to 6 carbon atoms and n is 1 or 2, -BTB- (wherein B is phenylene and T is -CH ₂ -, -O- or - SO ₂ -), -BOBC ₃ H ₆ -BOB- (wherein B is phenyl), and groups in which one or two hydrogens of these groups are substituted with -OH.

Such an alkenyl-substituted nadimide compound may be prepared by reacting an alkenyl-substituted nadic tetracarboxylic dianhydride derivative and a diamine at a temperature of 80 to 220 캜 for 0.5 to 20 hours Or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadimide compound include the following compounds.

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

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

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

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

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

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

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

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

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

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

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

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

Di-hydroxybenzene, N, N'-p- (2-hydroxycyclohexyl) -2,5-dihydroxybenzene, Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-p- (2- hydroxy) xylene- bis (allylmethylcyclo [ 2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene- bis (allylbicyclo [ 2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene-bis (metallylbicyclo [2.2.1] hepto- , N'-p- (2,3-dihydroxy) xylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

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

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

(126)

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

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

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

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

More preferred alkenyl substituted nadimide compounds are shown below.

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

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

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

Examples of particularly preferable alkenyl-substituted nadimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl } Methane, N, N'-m-xylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) represented by the formula (NA- -3, N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by the formula

(127)

<Compound Having Radically Polymerizable Unsaturated Double Bond>

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

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is preferably in the range of from 0.1 to 5 parts by weight based on 100 parts by weight of the liquid crystal display element, The compound having a radically polymerizable unsaturated double bond / alkenyl substituted nadimide compound is preferably in a weight ratio of 0.1 to 10, more preferably 0.5 to 5.

Hereinafter, the compound having a radically polymerizable unsaturated double bond will be specifically described.

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

Specific examples of the (meth) acrylic acid ester include (meth) acrylate such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

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

Specific examples of the trifunctional or more polyfunctional (meth) acrylic acid esters include 4,4'-methylene bis (N, N-dihydroxyethylene acrylate aniline), ARONIX (trade name, KAYARADDPCA-20, KAYARADDPCA-30, ARONIX M-405, ARONIX M-450, Aronix M-7100, Aronix M-8030, ARONIX M- , KAYARADDPCA-60, KAYARADDPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropyl acrylamide, N Methacrylamide, N-ethoxyethyl methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N Acrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N- N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, , N-phenylmethacrylamide, N-butyl methacrylamide, N- (i (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethyl methacrylamide, N- [3- (dimethylamino) propyl] (Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide and N, N'-methylenebis have.

Among the above (meth) acrylic acid derivatives, preferred are N, N'-methylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, ethylenebisacrylate and 4,4'- Dihydroxyethylene acrylate aniline) is particularly preferred.

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

&Lt;

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound in order to stabilize the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be a single compound or may be a compound of two or more kinds. 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 ring-opening polymerisability, which is soluble in a solvent for dissolving polyamic acid or a derivative thereof.

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 of the oxazine compound include structures of an 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.

(128)

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 is that even independently _{-F, -CH 3, -OH, -COOH} , and substituted with _{-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.

&Lt; EMI ID =

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.

(130)

[Formula 131]

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

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

(132)

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.

(133)

(134)

(135)

&Lt; EMI ID =

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.

(137)

&Lt; EMI ID =

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

[Chemical Formula 139]

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

&Lt; EMI ID =

(141)

(142)

(OX-2-1), Formula (OX-3-1), Formula (OX-3-3), Formula (OX- 3-5) (OX-5-4), formula (OX-3-9), formula (OX-4-1) OX-6-2) to (OX-6-4).

The oxazine compound can be produced by the same method as described in the pamphlet of 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 pamphlet of International Publication No. 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 See brochure).

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 pamphlets of WO 2004/009708 and JP 11-12258 A).

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

<Oxazoline compound>

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the 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 preferably has two or more oxazoline compounds. The oxazoline compound may be a polymer having an oxazoline ring structure in its 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.

It is preferable that the oxazoline structure is present in the oxazoline compound so that either or both of oxygen and nitrogen in the oxazoline structure and the carbonyl group of the polyamic acid can react with each other.

Examples of the oxazoline compound include 2,2'-bis (2-oxazoline), 1,2,4-tris (2-oxazolinyl-2) (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-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). Other examples include polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.). 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 one kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, 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.

Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene ox (3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N -Butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidyl 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: TEXMORE 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 are 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 Diglycidyl ether compounds, and biphenol-type epoxy compounds.

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 compounds include epoxy resins such as jER828, jER1001, jER1002, jER1003, jER1004, jER1007 and jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), epotote YD- Epiclon 850, Epiclon 1050 (all trade names, manufactured by DIC Corporation), DER-331, DER-332 and DER-324 Epomic R-140, Epomic R-301, and Epomic R-304 (all trade names, manufactured by Mitsui Chemicals, Inc.).

Examples of the bisphenol F type epoxy compounds include ePOOTT YDF-170, ePOOTT YDF-175S, ePOTT YDF-2001 (all trade names, manufactured by Mitsubishi Chemical Corporation), jER806, jER807, jER4004P DER-354 (trade name, manufactured by Dow Chemical Company), Epiclon 830, and Epiclon 835 (all trade names, manufactured by DIC Corporation).

As the bisphenol-type epoxy compound, there is, for example, an epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

As the hydrogenated bisphenol-A type epoxy compound, there may be mentioned, for example, Sintote ST-3000 (trade name, manufactured by Toto Hoso Co., Ltd.), Rica resin HBE-100 -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), Eportot YDB-360 and Eportot YDB-400 (all trade names, DER-530, DER-538 (all trade names, manufactured by The Dow Chemical Company), Epiclon 152, and Epiclon 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 Hoso Co., Ltd.), DEN431 and DEN438 EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Gakkai Co., Ltd.).

Examples of the cresol novolak epoxy compound include epichlorone N-665, epichloron N (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701 and YDCN- EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Gyaku Co., Ltd.), which are commercially available from Nippon Kayaku 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 Corporation), and NC-7000 ).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (EP-1), catechol diglycidyl ether (EP-2), resorcinol diglycidyl ether Phenyl] -2- [4- [1,1-bis [4 - ([2,3-bistrimethylsilyloxy] (EP-4), tris (4-glycidyloxyphenyl) methane (the following formula (EP-5)), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation) (Manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase Chemtex), DPPN-503, DPPN-502H, DPPN-501H, NC6000 A compound represented by the following formula (EP-6), and a compound represented by the following formula (EP-7) are commercially available from Mitsui Chemicals, Inc. under the trade name of Nippon Kayaku Co., have.

(143)

(144)

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 compounds include cyclohexanedimethanol diglycidyl ether compounds 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 (EP-8), diethylene glycol diglycidyl ether (EP-9), polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether (EP-10), tripropylene glycol diglycidyl ether (EP-11), polypropylene glycol diglycidyl ether, Propylene glycol diglycidyl ether (EP-12), 1,4-butanediol diglycidyl ether (EP-13), 1,6-hexanediol diglycidyl ether ( (EP-14), dibromoneopentyl glycol diglycidyl ether (EP-15), Denacol EX-810, Denacol EX-851, Denacol EX-8301, (All trade names, manufactured by Nagase ChemteX Corporation), DD-503 (manufactured by Nippon Kayaku Co., Ltd.), Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX- (Trade name, manufactured by ADEKA Co., Ltd.), Rica resin W-100 Tetraglycidyl-2,4-hexanediol (EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, Pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (both trade names: Nagase Chemtex Ltd.).

(145)

(146)

Examples of the polysulfide diglycidyl ether compound include FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Scientific Co., Ltd.).

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

Examples of diglycidyl ester compounds include diglycidyl terephthalate (EP-17), diglycidyl phthalate (EP-18), bis (2-methyloxiranyl (EP-20), a compound represented by the following formula (EP-21), a compound represented by the following formula (EP-22) A compound to be displayed, and a compound represented by the following formula (EP-23).

(147)

Examples of the glycidyl ester epoxy compounds include epoxy resins such as jER871 and jER872 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epiclon 200 and Epiclon 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711 , And Denacol EX-721 (all trade names, manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidyl aniline (EP-24), N, N-diglycidyl-o-toluidine (EP- Diglycidyl-m-toluidine (EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (EP- Aminophenol (represented by the following formula (EP-28)), 3- (N, N -diglycidyl) aminopropyltrimethoxysilane -29), N, N, O-triglycidyl-m-aminophenol (following formula (EP-30)), N, N, N ', N'-tetraglycidyl- N, N, N ', N'-tetraglycidyl-m-xylenediamine (TETRAD-X (trade name) manufactured by Mitsubishi Gas Chemical Co., (EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Co., ), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (EP-35)), 1,4-bis (N, N-diglycidylamino) cyclohexane (EP- Benzene (EP-37), 1,4-bis (N, N-diglycidylamino) benzene (EP-38) -Diglycidylaminomethyl) bicyclo [2.2.1] heptane (EP-39), N, N, N ', N'-tetraglycidyl-4,4'-diaminodicycl (EP-40), 2,2'-dimethyl- (N, N, N ', N'-tetraglycidyl) -4,4'- diaminophenyl (EP- 41), N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (EP-42), 1,3,5- N, N-diglycidyl) aminophenoxy) benzene (EP-43), 2,4,4'-tris (N, N-diglycidylamino) diphenyl ether EP-44), tris (4- (N, N-diglycidyl) aminophenyl) methane (EP-45), 3,4,3'4'- tetrakis Diglycidylamino) biphenyl (EP-46), 3,4,3 ', 4'-tetrakis (N, N-diglycidylamino) diphenyl ether There are (the following formula (EP-47)) The compound represented by the following formula the compound, and the formula (EP-49) represented by (EP-48).

(148)

[Chemical Formula 149]

(150)

(151)

As a homopolymer of an oxiranyl-containing monomer, for example, there is polyglycidyl methacrylate. Examples of the copolymer of the oxiranyl-containing monomer 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-oxeta Methylmethacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

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

(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) -51)), and glycidyl isocyanurate type epoxy resin.

(152)

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 (trade name, manufactured by Daicel Co.) EP-52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate Epoxy cyclopentane-2 ', 3'-epoxycyclopentane ether (EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate , 1,2: 8,9-diepoxy limonene (Celloxide 3000 (manufactured by Daicel), the following formula (EP-55)), a compound represented by the following formula (EP- EHPD-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.) (trade name, available from The Ciba-Geigy Chemical Corp. (available from Huntmann Japan)), CY- , And cyclic aliphatic epoxy resins.

[Formula 153]

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-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. As the various additives, for example, there are a polymer compound other than a polyamic acid and a derivative thereof, and a low-molecular compound, and they 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 according to the above-mentioned purpose when it is desired to improve the coating property, (2) an antistatic agent when it is necessary to improve charging prevention, (3) A silane coupling agent or a titanium-based coupling agent, and (4) an imidation catalyst when imidization proceeds at a low temperature.

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

Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; 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 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or the derivative thereof.

The addition amount of the imidation catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents 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 gel permeation chromatography (GPC).

The polyamic acid or its derivative of the present invention can be confirmed by analyzing a solid component obtained by precipitating with a large amount of a poor solvent by IR and NMR. Further, the monomer used can be identified by analyzing 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 viewpoints 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 any 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 mixing agents.

Examples of the solvent include a solvent for the above-described polyamic acid or a derivative thereof and other solvents for the purpose of improving coatability.

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

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

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

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

The concentration of the solid content in the aligning agent of the present invention is not particularly limited, and an 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 less 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 measurement 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 a coating film of the above-mentioned liquid crystal aligning agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a conventional method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal aligning agent of the present invention, a step of heating and drying, and a step of heating and firing. For 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 a heating and drying process and a heating and firing process as described below, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating process, the heating and drying process, or by irradiating light after the heating and firing process. It is also possible to use a liquid crystal alignment film for VA 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 indium tin oxide (ITO), 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 can be similarly applied to the present invention.

The heating and drying process is generally known as a heating process in an oven or an infrared heating process, a heating process on a hot plate, or 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 baking of the coating film is generally known as a heating process in an oven or an out-room furnace, a heating process 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.

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

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 the rubbing treatment for the alignment treatment of a liquid crystal alignment film in normal conditions, provided 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 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 a coated film by irradiating linearly polarized light or unpolarized light of radiation after heating and drying the coated film and 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 preferably in the range of 30 ° C to 150 ° C and more preferably in the range of 50 ° C to 120 ° C. The heating and firing temperature in the above step is preferably in the range of 30 ° C to 300 ° C and more preferably in the range of 50 ° C to 250 ° C.

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 liquid crystal aligning ability as high as a low energy light irradiation. 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 developed, the light irradiated to the film may be linearly polarized light or non-lighted light as described above. When the pretilt angle is to be developed, the amount of light irradiated to 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 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 be suitably obtained by a method including a process other than the process described above. For example, in the liquid crystal alignment film of the present invention, the step of cleaning the film after baking or irradiating with the cleaning liquid is not essential, but a cleaning step can be provided taking into account the circumstances of 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. Examples of the cleaning liquid include 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, acetone, methyl ethyl ketone and the like Ketones may be used, but 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 can be used before or after the heat firing step, before or after the rubbing step, 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 in the annealing process 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 Patent Application Laid-Open 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 is characterized by being less colored and having a high transmittance. The transmittance can be evaluated using an ultraviolet visible spectrophotometer. In order to exhibit good display characteristics, the transmittance calculated from the average value of the absorbance at 380 nm to 780 nm is preferably 85% or more, more preferably 87% or more.

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. When used in a liquid crystal display device of a transverse electric field system, the lower the Pt angle and the higher the liquid crystal alignment performance, 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 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 alignment 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 device, electrodes are disposed on one side of the pair of substrates, and in the case of other liquid crystal display devices, 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 between the pair of substrates facing each other on which the liquid crystal alignment film is formed. 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 A, JP 2635435 A, JP 5-501735 A, JP 8-157826 A, JP 8-231960 A Japanese Patent Application Laid-Open No. 9-241644 (EP885272A1), Japanese Patent Application Laid-Open No. 9-302346 (EP806466A1), Japanese Patent Application Laid-Open No. 8-199168 (EP722998A1), Japanese Patent Application Laid-Open No. 9-235552 Japanese Patent Application Laid-Open Nos. 9-255956 and 9-241643 (EP885271A1), JP-A 10-204016 (EP844229A1), JP-A 10-204436, 10-231482, 2000-087040, 2001-48822, and the like.

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

(154)

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, Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl or 7,8-difluorochroman- , Wherein at least one of Ring A ² and Ring B ² is 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4- Difluoro-6-methyl-1,4-phenylene, or 7,8-dipropluorochroman-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;

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).

(155)

(156)

(157)

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 to be. 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 alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. It is preferable that the alkenyl is a trans in the case of alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for the purpose of lowering the viscosity. And is preferably a cis for alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. 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.

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, Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl and 7,8-difluorochroman- Wherein at least one of Ring A ² and Ring B ² is selected from the group consisting of 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4- Fluoro-6-methyl-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, and when j is 2 or 3, any two rings A ² may be the same And may be 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.

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. 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.

Z ¹ and Z ² are independently a single bond, - (CH ₂ ) ₂ -, -CH ₂ O-, -COO-, -CF ₂ O-, and when j is 2 or 3, any two Z ¹ may be the same or different, and when k is 2 or 3, any two Z ^{2 s} may be the same or different, and preferred Z ¹ and Z ² are -CH ₂ O-, and it is a single bond to lower the viscosity.

Z ¹¹ and Z ¹² are independently a single bond, - (CH ₂ ) ₂ -, -CH ₂ O-, or -COO-. 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.

j is 1, 2, or 3; The preferred j is 1 to lower the lower limit temperature and 2 to increase the upper limit temperature.

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

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 a most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the alignment property of the liquid crystal, a structure of the following formulas (PM-1-1) to (PM-1-6) is exemplified.

(158)

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, it is preferably 30% by weight or less in order to appropriately orient the polymer after the polymerization, or to avoid elution of the unreacted monomer or oligomer into the liquid crystal after irradiation with ultraviolet rays.

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 compounds (PAC-1-1) to (PAC-1-4). The preferred ratio of the optically active phosphorus compound is 5% by weight or less. A more preferable range is from 0.01 wt% to 2 wt%.

(159)

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

[Formula 160]

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) wherein w is 7 is effective to maintain a large voltage holding ratio at room temperature as well as at a high temperature after long use of the device because of low volatility. A preferable proportion of the antioxidant is not less than 50 ppm so as not to lower the upper limit temperature or increase the lower limit temperature to not more than 50 ppm to obtain the effect. 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 absorbents and stabilizers is not less than 50 ppm in order to obtain the effect, and not more than 10,000 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferable range is from 100 ppm to 10000 ppm.

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 is 1000 ppm or less in order to prevent defective display. A more preferable range is from 1 ppm to 500 ppm.

Polymerizable compounds may be incorporated into the compositions to 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%.

[Formula 161]

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 includes a 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 are classified into several groups. One of them is a stable radical as such itself, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine and the like, and the other is a compound which easily reacts with a radical present in the polymerization system and is converted into a stable radical Nitro, nitrite, amino, polyhydroxy compounds, and the like. 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. Viscosity

The measurement was carried out at 25 占 폚 using a viscometer (TV-22, manufactured by Toki Industries Co., Ltd.).

2. 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 a HSPgel RT MB-M (manufactured by Waters), and the mixed solution was measured as a developing agent under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

3. Pencil Hardness

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

4. Retardation of Orientation Film and Measurement of Film Thickness

And spectral Ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.). In the case of the photo alignment film in this embodiment, 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 phase difference value indicates a large degree of orientation and a high liquid crystal aligning ability. If this value is larger than 15, an alignment film having good display characteristics can be obtained.

5. Shatter resistance

The liquid crystal cell was subjected to touching with a test rod at a weight of 1000 g for 1 time / second for 1 minute, and then the presence or absence of film peeling was observed using a microscope.

6. Pretilt Angle Measurement

Were measured according to the rotation determination method.

7. Voltage maintenance rate

Quot ;, &quot; Mizushima et al., Proceedings of the 14th Liquid Crystal Display Discussion p78 (1988) &quot;. The measurement was performed by applying a rectangular wave of ± 5 V to the cell. The measurement was carried out at 60 占 폚. This value is an index indicating how much the applied voltage is maintained after the frame period. If this value is 100%, it indicates that all the charges are held.

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

Was measured by the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996) using a liquid crystal physical property measuring system Model 6254 manufactured by Toyo Technica. A triangular wave with a frequency of 0.01 Hz was used and a voltage range of ± 10 V was measured at a temperature of 60 ° C. (electrode area is 1 cm ² ). If the ion density is high, problems such as burning due to ionic impurities are likely to occur. That is, the ion density is a physical property value which is an index for predicting the occurrence of the calcination.

<Tetracarboxylic dianhydride>

Acid dianhydride (1-1): Tetracarboxylic dianhydride obtained by the synthesis route of Synthesis Example 1

Acid dianhydride (1-5): Tetracarboxylic dianhydride obtained by the synthesis route of Synthesis Example 2

Acid dianhydride (1-6): Tetracarboxylic dianhydride obtained from the synthesis route of Synthesis Example 2

Acid dianhydride (1-28): Tetracarboxylic dianhydride obtained according to the synthesis route of Synthesis Example 2

Acid anhydride (AN-2-1): 1,2,3,4-cyclobutane tetracarboxylic dianhydride

Acid dianhydride (AN-3-2): Pyromellitic dianhydride

Acid dianhydride (AN-4-1): 3,3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride

Acid anhydride (AN-4-17, m = 8): 1,8-bis (3,4-dicarboxylic acid phenyl) octane dianhydride

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

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

<Diamine>

Diamine (DI-1-3): 1,6-diaminohexane

Diamine (DI-2-1): 1,4-cyclohexanediamine

Diamine (DI-3-1): 4,4'-diaminodicyclohexylmethane

Diamine (DI-4-1): 1,4-Phenylenediamine

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

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

Diamine (DI-5-29): biphenyl-4,4'-diamine

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

Diamine (DI-6-7): 4,4'-p-phenylenediamine

Diamine (DI-7-3, m = 3, n = 1): 1,3-bis (4 - ((4-aminophenyl) methyl)

Diamine (DI-8-1): 2,6-diaminonaphthalene

Diamine (DI-12-1): 1,3-bis (3-aminopropyl) tetramethyldisiloxane

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

Diamine (DI-16-1): 1- (4-Aminophenyl) -1H-indol-5-amine

Diamine (PDI-7-a): 4,4'-diamino azobenzene

Diamine (PDI-8-a): 4,4'-bis [(4-aminophenyl) methyl] azobenzene

Diamine (PDI-9): 4-aminophenyl-4-aminocinnamate

Diamine (PDI-11): 4,4'-diamino-chalcone

(162)

<Solvent>

N-methyl-2-pyrrolidone: NMP

Butyl cellosolve (ethylene glycol monobutyl ether): BC

<Additives>

Additive (Ad1): 1,3-bis (4,5-dihydrooxazolyl) benzene

Additive (Ad2): N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive (Ad3): 3-Aminopropyltriethoxysilane

[Example 1] Synthesis of Compound (1-1)

[163]

<First Step> Azide>

Diethyl 4- (4-bromobutyl) phthalate (12.1 g, 34.0 mol) was added to a three-necked flask equipped with a thermometer and a nitrogen inlet tube, and DMF (70 mL) was added. Thereto was added sodium azide (2.4 g, 37.4 mmol). Thereafter, the solution was heated to 60 DEG C and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was poured into 400 mL of water and extracted twice with 300 mL of heptane. The organic layer was dried over magnesium sulfate and then the solvent was distilled off under reduced pressure to obtain a 4- (4-azidobutyl) -phthalic acid diethyl ester compound (yield: 10.0 g, yield: 92%).

&Lt; Second step; Formation of triazole ring >

(4-azidobutyl) phthalic acid diethyl ester (10.0 g, 31.3 mmol) obtained in the first step and dimethyl 4- (4-ethynylphthalate) obtained in the first step were added to a three-necked flask equipped with a thermometer, 34.4 mmol), and 50 mL of methylene chloride and 50 mL of water were added. After stirring at room temperature to dissolve the compound, 0.86 g (3.1 mmol) of copper sulfate pentahydrate and 1.2 g (6.3 mmol) of sodium L-ascorbate were added and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 50 mL of water and extracted twice with 100 mL of toluene. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain the following compound (yield: 15.7 g, yield: 93%).

&Lt; EMI ID =

<Step 3> Hydrolysis>

The compound (15.7 g, 29.2 mmol) obtained in the second step was added to a three-necked flask equipped with a thermometer and a reflux tube, and 30 mL of tetrahydrofuran was added thereto. 30 mL of a 20% aqueous solution of sodium hydroxide was added to this solution, and the mixture was stirred for 2 hours under reflux. The reaction solution was cooled to room temperature, tetrahydrofuran was distilled off by an evaporator, and 6N HCl was added until the pH became 1.0. The precipitated crystals were collected by suction and washed with pure water to obtain the following compound (yield: 14.6 g, yield: 110%).

(165)

<Step 4> Anhydrous>

The compound (13.6 g, 30.0 mmol) obtained in the third step and 68 mL of acetic anhydride were added to a three-necked flask equipped with a thermometer and a reflux tube, and stirred under reflux for 6 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were collected by suction and washed with toluene to obtain compound (1-1) (yield: 9.6 g, yield: 77%).

^{1 H-NMR (500 MHz,} CDCl 3): δ 8.99 (s, 1H), 8.49-8.45 (m, 2H), 8.17 (d, J = 7.5 Hz, 1H), 8.00 (d, J = 7.8 Hz, 1H), 7.97 (s, 1H), 7.87-7.84 (m, 1H), 4.52 (t, J = 7 Hz, 2H), 2.90 (t, J = 7.6 Hz, 2H), 1.97-1.90 ), 1.73-1.65 (m, 2H);

Melting point: 200.2-201.9 占 폚.

[Example 2] Synthesis of Compound (1-5)

&Lt; EMI ID =

<First Step> Azide>

1,6-dibromohexane (5.0 g, 20.5 mmol) was added to a 100-mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, and DMF (25 mL) was added. Thereto was added sodium azide (2.9 g, 45.6 mmol). Thereafter, the solution was heated to 60 DEG C and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was poured into 200 mL of water and extracted twice with 100 mL of heptane. The organic layer was dried over magnesium sulfate and then the solvent was distilled off under reduced pressure to obtain 1,6-diazide hexane (yield: 3.2 g, yield: 93%).

&Lt; Second step; Formation of triazole ring >

Diazide hexane (2.2 g, 13.1 mmol) and dimethyl 4-ethynylphthalate (5.7 g, 26.2 mmol) obtained in the first step were added, and 5 mL of methylene chloride and 5 mL of water were added. The mixture was stirred at room temperature to dissolve the compound. Then, 0.16 g (0.65 mmol) of copper sulfate pentahydrate and 0.26 g (1.3 mmol) of sodium L-ascorbate were added and stirred at room temperature for 1 hour. The reaction solution was poured into 50 mL of water and extracted twice with 50 mL of toluene. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain the following compound (yield: 3.2 g, yield: 93%).

&Lt; EMI ID =

<Step 3> Hydrolysis>

The compound (6.8 g, 11.3 mmol) obtained in the second step was added to a three-necked flask equipped with a thermometer and a reflux tube, and 10 mL of tetrahydrofuran was added thereto. To this solution was added 10 mL of a 20% aqueous solution of sodium hydroxide, and the mixture was stirred under reflux for 2 hours. The reaction solution was cooled to room temperature, tetrahydrofuran was distilled off by an evaporator, and 6N HCl was added until the pH became 1.0. The precipitated crystals were collected by suction and washed with pure water and methanol to obtain the following compound (yield: 5.8 g, yield: 94%).

&Lt; EMI ID =

<Step 4> Anhydrous>

(5.8 g, 10.6 mmol) and acetic anhydride (29 mL) were added to a three-necked flask equipped with a stirrer, a thermometer and a reflux tube, and the mixture was stirred under reflux for 6 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were collected by suction and washed with toluene to obtain the compound (1-5) (yield: 4.9 g, yield: 91%).

^{1 H-NMR (500 MHz,} CDCl 3): δ 9.01 (s, 2H), 8.50-8.46 (m, 4H), 8.17 (d, J = 8.4 Hz, 2H), 4.46 (t, J = 7 Hz, 4H), 1.95-1.87 (m, 4H), 1.39-1.32 (m, 4H);

Melting point: 254.3-256.5 캜.

[Example 3] Synthesis of compound (1-6)

[169]

<First Step> Formation of triazole ring &gt;

Diisopropyl hexane (2.2 g, 13.1 mmol) and 4-ethynyl-1,2-cyclohexanedicarboxylic acid dimethyl (6.2 g, 27.5 mmol) were placed and 20 ml of methylene chloride and 20 ml Respectively. The mixture was stirred at room temperature to dissolve the compound. Then, 0.16 g (0.65 mmol) of copper sulfate pentahydrate and 0.26 g (1.3 mmol) of sodium L-ascorbate were added and stirred at room temperature for 1 hour. The reaction mixture was poured into 50 ml of water and extracted twice with 50 ml of toluene. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain the following compound (yield: 7.8 g, yield: 97%).

(170)

&Lt; Second step; Hydrolysis>

The compound obtained in the first step (7.0 g, 11.3 mmol) was added to a three-necked flask equipped with a thermometer and a reflux tube, and 10 mL of tetrahydrofuran was added. 10 mL of a 20% aqueous solution of sodium hydroxide was added to this solution, and the mixture was stirred for 2 hours under reflux. The reaction solution was cooled to room temperature, tetrahydrofuran was distilled off by an evaporator, and 6N HCl was added until the pH became 1.0. The precipitated crystals were collected by suction and washed with pure water and methanol to obtain the following compound (yield: 6.0 g, yield: 94%).

[171]

<Step 3> Anhydrous>

To the three-necked flask equipped with a thermometer and a reflux tube were added the compound obtained in the second step (5.9 g, 10.6 mmol) and acetic anhydride (30 ml), and the mixture was stirred under reflux for 6 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were collected by suction and washed with toluene to obtain the compound (1-6) (yield: 4.7 g, yield 84%).

[Example 4] Synthesis of compound (1-28)

(172)

<First Step> Azide>

1,4-dibromobutane (6.5 g, 30.0 mmol) was added to a 100-mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, and DMF (100 mL) was added. Sodium azide (4.2 g, 65.0 mmol) was added thereto. Thereafter, the solution was heated to 60 DEG C and stirred at the same temperature for 3 hours under a nitrogen atmosphere. The reaction solution was poured into 500 ml of water and extracted twice with 300 ml of heptane. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 1,4-diazide butane (yield: 4.0 g, yield: 95%).

&Lt; Second step; Formation of triazole ring >

Diazide butane (2.8 g, 20.0 mmol) and dimethyl 4- (5-hexynyl) phthalate (11.1 g, 40.4 mmol) obtained in the first step were added to a three-necked flask equipped with a thermometer and a nitrogen- mol) were added, and 40 ml of methylene chloride and 40 ml of water were added. After stirring at room temperature to dissolve the compound, 0.5 g (2.0 mol) of copper sulfate pentahydrate and 0.8 g (4.0 mol) of sodium L-ascorbate were added and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 100 ml of water and extracted twice with 100 ml of toluene. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain the following compound (yield: 13.2 g, yield: 96%).

[173]

<Step 3> Hydrolysis>

The compound (11.9 g, 17.3 mol) obtained in the second step was added to a three-necked flask equipped with a thermometer and a reflux tube, and 50 ml of tetrahydrofuran was added. To this solution was added 16 ml of a 20% aqueous solution of sodium hydroxide and the mixture was stirred under reflux for 2 hours. The reaction solution was cooled to room temperature, tetrahydrofuran was distilled off by an evaporator, and 6N HCl was added until the pH became 1.0. The precipitated crystals were collected by suction and washed with pure water to obtain the following compound (Yield: 10.1 g, yield: 92%).

&Lt; EMI ID =

<Step 4> Anhydrous>

(9.6 g, 15.2 mol) obtained in the third step and 100 ml of acetic anhydride were added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and the mixture was stirred under reflux for 6 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were collected by suction and washed with toluene to obtain Compound (1-28) (yield: 8.9 g, yield: 98%).

[Example 5]

<Synthesis of polyamic acid>

3.3144 g of the compound (1-1) synthesized in Example 1 and 1.6856 g of the compound (PDI-7-a) were weighed and taken in a three-necked flask equipped with a stirrer and a thermometer, 65 g of NMP were added. The mixture was stirred at room temperature for 12 hours, 30 g of ethylene glycol monobutyl ether (BC) was added thereto, and stirring was continued at room temperature for 24 hours to obtain a solution having a polyamic acid concentration of 5% by weight. This solution is referred to as a &quot; varnish A-1 &quot;. The weight average molecular weight (MW) of the polyamic acid in the varnish was 74,000.

[Examples 6 to 34]

As shown in the following Table 1, a varnish having a polyamic acid concentration of 5% by weight to be a polymer for forming a photo alignment film was obtained in accordance with the method described in Example 5. The parentheses () indicate mol% when the total amount of the raw materials is 100 mol%. In Examples 32 to 34, the varnish was adjusted as described above, and then the additives (Ad1) to (Ad3) were added and adjusted at a ratio of 10 parts by weight per 100 parts by weight of the polymer, respectively. Example 5 is also shown in Table 1.

[Table 1-1]

[Table 1-2]

[Comparative Examples 1 to 3]

As shown in the following Table 2, a varnish having a polyamic acid concentration of 5% by weight to be a polymer for forming a photo alignment film was obtained in accordance with the method described in Example 5. The parentheses () indicate mol% when the total amount of the raw materials is 100 mol%.

[Table 2]

[Example 35]

1.0 g of the varnish A-1 was weighed into a sample bottle, and NMP / BC = 1/1 (weight ratio) was added to make 1.67 g. On the transparent glass substrate, about 3 wt% of polyamic acid solution was dropped and applied by a spinner method (2,000 rpm, 15 seconds). After the application, the substrate was heated at 80 占 폚 for 3 minutes to evaporate the solvent. Then, using Multilight ML-501C / B manufactured by Ushio Electric Co., the ultraviolet Linearly polarized light was irradiated. 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 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm , And the exposure time was adjusted. The substrate after the light irradiation was heat-treated in an oven at 210 DEG C for 15 minutes to obtain an orientation film A-1 having a film thickness of about 100 nm. The retardation of this alignment film A-1 was measured and found to be 19.8 nm. The pencil hardness of the resulting alignment film A-1 was measured and found to be 3H.

[Examples 36 to 64] and [Comparative Examples 4 to 6]

The alignment films A-2 to A-30 and B-1 to B-3 were formed in the same manner as in Example 35 by using the varnishes A-2 to A-30 and B-1 to B- The retardation and pencil hardness were measured according to the method. These results are shown in Tables 3 and 4. The results of Example 35 are also shown in Table 3.

[Table 3]

[Table 4]

In the alignment films A-1 to A-30 obtained from the varnishes A-1 to A-30, it was found that all of the alignment films had a large retardation and a high pencil hardness. The orientation film B-1 obtained from Baris B-1 had a large retardation, but it was found that the pencil hardness was low. Further, in the alignment films obtained from the varnishes B-2 and B-3, it was found that the pencil hardness was not sufficiently high and the retardation was also small.

[Example 65]

An orientation film A-1 having a film thickness of about 100 nm was obtained in the same manner as in Example 35 except that the glass substrate was changed to a transparent glass substrate provided with an ITO electrode on one side. Two substrates on which these alignment films were formed on the ITO electrode were bonded to each other by providing a gap for opposing the surface on which the alignment film was formed and for injecting the liquid crystal composition between the opposing alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The following positive-type liquid crystal composition A was injected into this cell to prepare a liquid crystal cell A-1 (liquid crystal display device) having a cell thickness of 3.5 m (FIG. 1).

&Lt; Positive type liquid crystal composition A >

(175)

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

When this liquid crystal cell A-1 was observed with naked eyes, no so-called flow orientation in which liquid crystals were arranged radially from the injection port was not observed at all. When the polarizing microscope was set in the crossed Nicols state and the liquid crystal cell A-1 was rotated, a clear light and dark state were observed. The pre-tilt angle of this liquid crystal cell A-1 (hereinafter sometimes abbreviated as Pt angle) was 0.1 degrees. The VHR (voltage holding ratio) and the ion density were 99.0% (30 Hz), 87.0% (0.3 Hz) and 80 pC. The shatter resistance of the liquid crystal cell was measured. As a result, after the touch panel treatment, the shrinkage and peeling of the alignment film were not observed at all.

[Examples 66 to 94] and [Comparative Examples 7 to 9]

Liquid crystal cells A-2 to A-30 and B-1 to B-3 were produced for the varnishes A-2 to A-30 and B-1 to B-3 in accordance with the method described in Example 65 , Orientation state, pretilt angle, VHR, ion density and shaved immunity were measured. The measurement results are shown in Tables 5 and 6. Example 65 is also shown in Table 5.

· Shatter resistance

○: No sharpening or peeling of the alignment film was observed with a microscope after the touch processing

X: After the tarnish treatment, the alignment film was scratched or peeled off with a microscope.

[Table 5]

[Table 6]

In the liquid crystal cells A-1 to A-30, a good alignment state is exhibited and good shrinkage resistance is exhibited. In addition, the electrical characteristics expressed by VHR and ion density were also good. In the liquid crystal cell B-1, a good orientation state was exhibited and an electrical property was good, but the alignment film was scraped. In the liquid crystal cells B-2 and B-3, the alignment of the alignment film was not observed, but the alignment of the liquid crystal was confirmed to be a display defective liquid crystal cell.

[Examples 95 to 109] and [Comparative Examples 10 to 12]

As shown in the following Tables 7 and 8, a varnish having a polyamic acid concentration of 5% by weight was obtained in accordance with the method described in Example 5. The parentheses () indicate mol% when the total amount of the raw materials is 100 mol%.

[Table 7]

[Table 8]

[Example 110]

1.0 g of Barnis C-1 was weighed into a sample bottle, and NMP / BC = 1/1 (weight ratio) was added to make 1.67 g. On the transparent glass substrate, about 3 wt% of polyamic acid solution was dropped and applied by a spinner method (2,000 rpm, 15 seconds). After the application, the substrate was heated at 80 占 폚 for 3 minutes to evaporate the solvent, and then heat-treated at 210 占 폚 for 15 minutes in a clean oven (PVHC-231, manufactured by Espace Kabushiki Kaisha) An orientation film C-1 of about 100 nm was obtained. Subsequently, the obtained liquid crystal alignment film was applied to a rubbing treatment apparatus manufactured by Iinuma Kogyo Seisakusho Co., Ltd., using a rubbing cloth (1.8 mm in rayon: rayon) having a moisture content of 0.20 mm, a stage moving speed of 60 mm / sec, rubbing treatment was carried out under the condition of rpm. The retardation of the obtained substrate was measured and found to be 0.26 nm. The pencil hardness of the resulting alignment film C-1 was measured and found to be 5H.

[Examples 111 to 124] and [Comparative Examples 13 to 15]

Similarly, the varnishes C-2 to C-15 and D-1 to D-3 were formed into the films C-2 to C-15 and D-1 to D-3 by the operation in accordance with Example 110, The retardation and pencil hardness were measured according to the method. These results are shown in Tables 9 and 10. The results of Example 110 are also shown in Table 9.

[Table 9]

[Table 10]

It can be seen from comparison between Examples 110 to 124 and Comparative Examples 13 to 15 that the alignment film of the present invention does not deteriorate the retardation and the pencil hardness is greatly improved.

[Example 125]

An orientation film C-1 having a film thickness of about 100 nm was obtained in the same manner as in Example 110 except that the glass substrate was changed to a transparent glass substrate provided with an ITO electrode on one side. Two substrates on which these alignment films were formed on the ITO electrode were bonded to each other by providing a gap for opposing the surface on which the alignment film was formed and for injecting the liquid crystal composition between the opposing alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The following positive-type liquid crystal composition A was injected into this cell to prepare a liquid crystal cell C-1 (liquid crystal display device) having a cell thickness of 3.5 m (Fig. 1).

&Lt; Positive type liquid crystal composition A >

[176]

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

When this liquid crystal cell C-1 was observed with naked eyes, no so-called flow orientation in which liquid crystals were arranged radially from the injection port was not observed at all. When the polarizing microscope was set to the cross-Nicol state and the liquid crystal cell C-1 was rotated, a clear light and dark state were observed. The pre-tilt angle of the liquid crystal cell C-1 (hereinafter sometimes abbreviated as Pt angle) was 0.1 degrees. The VHR (voltage holding ratio) and the ion density were 99.1% (30 Hz), 87.6% (0.3 Hz) and 75 pC. When this liquid crystal cell was observed under a microscope, no debris was found due to rubbing scratches or scabs.

[Examples 126 to 139] and [Comparative Examples 16 to 18]

Liquid crystal cells C-2 to C-15 and D-1 to D-3 were also produced for varnishes C-2 to C-15 and D-1 to D-3 in accordance with the method described in Example 125, Orientation state, pre-tilt angle, VHR, ion density and shear resistance were measured. The measurement results are shown in Tables 11 and 12. Example 125 is also shown in Table 11.

· Rub resistance

○: No scratches due to rubbing scratches or clipping were observed

X: Debris due to rubbing scratches and cuts was observed

[Table 11]

[Table 12]

Liquid crystal cells C-1 to C-15 exhibit a good alignment state and exhibit good rubbing resistance. In addition, the electrical characteristics expressed by VHR and ion density were also good. In the liquid crystal cells D-1 to D-3, a good alignment state was exhibited and electrical characteristics were good, but scrapes due to rubbing and scoring occurred.

[Examples 140 to 148]

As shown in the following Table 13, a varnish having a polyamic acid concentration of 5% by weight to be a polymer for blending was obtained in accordance with the method described in Example 5. The parentheses () indicate mol% when the total amount of the raw materials is 100 mol%.

[Table 13]

[Example 149]

2.0 g of the varnish A-1 synthesized in Example 5 and 8.0 g of the varnish E-1 synthesized in Example 140 were placed in a 50 mL eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, and N 5.0 g of methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added and stirred at room temperature for 1 hour to obtain an aligning agent (varnish A-1 / varnish E-1) having a resin concentration of 2.5% by weight. Using the obtained aligning agent, an orientation film F-1 was produced in accordance with the method described in Example 35. [ The retardation of this alignment film F-1 was measured and found to be 19.6 nm. The pencil hardness of the resulting alignment film F-1 was measured and found to be 4H.

[Examples 150 to 157 and Comparative Examples 19 to 21]

Orientation films F-2 to F-9 and G-1 to G-3 were produced in accordance with Example 149 except that the varnish used was changed, and the retardation and the pencil hardness were measured. The varnishes used and the measurement results are shown in Table 14 and Table 15 together with Example 149. In Tables 14 and 15, varnish A indicates a varnish containing a polymer using a raw material having a photo-isomerization structure, and varnish B indicates a varnish containing a blending polymer.

[Table 14]

[Table 15]

In the alignment films F-1 to F-9, it was found that all of the alignment films had a large retardation and a high pencil hardness. The alignment film G-1 had a large retardation, but the pencil hardness was low. In the alignment films G-2 and G-3, the pencil hardness was not sufficiently high, and the retardation was small.

[Example 158]

An orientation film F-1 having a film thickness of about 100 nm was obtained in the same manner as in Example 149 except that the glass substrate was changed to a transparent glass substrate provided with an ITO electrode on one side. Two substrates on which these alignment films were formed on the ITO electrode were bonded to each other by providing a gap for opposing the surface on which the alignment film was formed and for injecting the liquid crystal composition between the opposing alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The following positive-type liquid crystal composition A was injected into this cell to prepare a liquid crystal cell F-1 (liquid crystal display device) having a cell thickness of 3.5 mu m.

When this liquid crystal cell F-1 was observed with naked eyes, no so-called flow orientation in which liquid crystals were arranged radially from the injection port was not observed at all. When the polarizing microscope was set to the Cross-Nicol state and the liquid crystal cell F-1 was rotated, a clear light and dark state were observed. The pretilt angle of the liquid crystal cell F-1 was 0.1 DEG. VHR (voltage holding ratio) and ion density were 99.0% (30 Hz), 87.2% (0.3 Hz) and 80 pC. The shrinkage resistance of the liquid crystal cell was measured. As a result, after the touching treatment, the alignment film was not cut or peeled at all.

[Examples 159 to 166 and Comparative Examples 22 to 24]

A liquid crystal cell was produced in accordance with Example 158 except that the varnish used was changed, and the alignment state, pretilt angle, VHR, ion density, and cut-off resistance were measured. The varnishes used and the measurement results are shown in Table 16 and Table 17 together with Example 158.

· Shatter resistance

○: No sharpening or peeling of the alignment film was observed with a microscope after the touch processing

X: After the tarnish treatment, the alignment film was scratched or peeled off with a microscope.

[Table 16]

[Table 17]

In the liquid crystal cells F-1 to F-9, a good alignment state is exhibited and exhibits good shatter resistance. In addition, the electrical characteristics expressed by VHR and ion density were also good. In the liquid crystal cell G-1, a good alignment state was shown, and the electrical characteristics were good, but the alignment film was cut off. In the liquid crystal cells G-2 and G-3, the alignment of the alignment film was not observed, but the liquid crystal orientation of the liquid crystal was confirmed, and the liquid crystal cell became defective.

By using the alignment agent using the polyamic acid or derivatives thereof containing the triazole-containing tetracarboxylic dianhydride as a raw material according to the present invention, it is possible to obtain an alignment film having high alignment property and no scraping even in any of the photo alignment method and the rubbing method . By using this alignment film, a liquid crystal display device having excellent display characteristics and electrical characteristics can be obtained.

1: glass substrate
2: Column spacer
3: ITO substrate
4: liquid crystal
5: Sealing material
6: Orientation film

Claims (12)

A tetracarboxylic dianhydride represented by the following formula (1):
[Chemical Formula 1]

In the above formula (1), X is a divalent organic group containing at least one triazole ring;
R ¹ and R ² are each independently one selected from the group of the following trivalent groups;
(2)

At least one of these groups may be substituted with methyl, ethyl or phenyl. The method according to claim 1,
A tetracarboxylic dianhydride represented by the following formula (2):
(3)

In the formula (2), X is a divalent organic group containing at least one triazole ring. The method according to claim 1,
A tetracarboxylic dianhydride represented by the following formula (3):
[Chemical Formula 4]

In the above formula (3), X ¹ is a triazole ring;
A ¹ and A ² are each independently a single bond or alkylene having 1 to 12 carbon atoms;
At least one hydrogen in said alkylene may be substituted with fluorine; And,
At least one -CH ₂ - may be replaced by -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH-, or -C≡C-. The method according to claim 1,
A tetracarboxylic dianhydride represented by the following formula (4):
[Chemical Formula 5]

In the above formula (4), X ¹ and X ² are triazole rings;
A ^{1 to} A ³ are each independently a single bond or alkylene having 1 to 12 carbon atoms;
At least one hydrogen in said alkylene may be substituted with fluorine; And,
At least one -CH ₂ - in the alkylene may be substituted with -O-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH-, or -C≡C-. A polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride containing at least one tetracarboxylic dianhydride according to any one of claims 1 to 4 with a diamine. A liquid crystal aligning agent containing the polyamic acid according to claim 5 or a derivative thereof. The method according to claim 6,
A liquid crystal aligning agent comprising the polyamic acid or derivative thereof according to claim 5 and other polymer. 8. The method according to claim 6 or 7,
A liquid crystal culture agent for optical orientation. 8. The method according to claim 6 or 7,
Rubbing solution, liquid crystal culture agent. 10. The method according to any one of claims 6 to 9,
Liquid crystal culture agent for liquid crystal display element of transverse electric field system. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 6 to 10. A liquid crystal display device comprising the liquid crystal alignment film according to claim 11.

Images