KR20160034391A - Liquid crystal aligning agent and liquid crystal aligning film using same - Google Patents

Abstract

(R₁ : 탄소수 1 ∼ 5 의 알킬기, R₂ : 하이드록실기 등, Me : 메틸기 등, A₁ : 결합 등, A₂ : 할로겐 원자 등, a : 1 ∼ 4 의 정수)
(B) 성분 : 테트라카르복실산 2 무수물과 디아민으로부터의 중축합 반응에 의해 얻어지는 폴리아믹산.
(C) 성분 : 2 관능 혹은 다관능의 (메트)아크릴산 또는 그 유도체.Provided is a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a high adhesiveness to a sealant and a substrate used in the production of a liquid crystal display element and having improved interfacial characteristics with liquid crystals.
A liquid crystal aligning agent containing the following components (A), (B) and (C).
(A): a tetracarboxylic acid dialkyl ester derivative containing at least 60 mol% of a tetracarboxylic acid dialkyl ester derivative represented by the formula (1) and a diamine represented by the following formulas (2) to (5) A polyamic acid ester obtained by a polycondensation reaction of a diamine containing at least one diamine.

(Wherein R ₁ is an alkyl group having 1 to 5 carbon atoms; R _{2 is a} hydroxyl group; Me is a methyl group; A _{1 is a} bond; A _{2 is a} halogen atom; a is an integer of 1 to 4)
Component (B): Polyamic acid obtained by polycondensation reaction of a tetracarboxylic acid dianhydride with a diamine.
Component (C): bifunctional or polyfunctional (meth) acrylic acid or its derivative.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent and a liquid crystal alignment film using the liquid crystal alignment agent.

The present invention relates to a liquid crystal aligning agent containing a polyamic acid ester for producing a liquid crystal alignment film, and a liquid crystal alignment film obtained from the liquid crystal aligning agent.

In a liquid crystal display element used in a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually formed in the element. As the liquid crystal alignment film, a polyimide-based liquid crystal alignment film in which a liquid crystal aligning agent having a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide as a main component is applied to a glass substrate or the like and fired is mainly used have.

From the demand for suppressing lowering of the contrast of the liquid crystal display element and reducing the afterimage phenomenon accompanying the fixation of the liquid crystal display element, the liquid crystal alignment film is required to exhibit excellent liquid crystal alignability and a stable pretilt angle, Such as the suppression of the afterimage caused by the AC drive, the small residual charge when the direct current voltage is applied, and / or the rapid relaxation of the accumulated residual charge due to the direct current voltage.

In the polyimide-based liquid crystal alignment film, various proposals have been made in order to meet the above-mentioned demands. For example, a liquid crystal alignment film containing a tertiary amine having a specific structure may be used in addition to a polyamic acid or an imide group-containing polyamic acid as a liquid crystal alignment film having a short time until the after- (See, for example, Patent Document 1), and those using a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine compound having a pyridine skeleton or the like is used as a raw material (see, for example, Patent Document 2) Has been proposed. In addition, a liquid crystal alignment film having a high voltage holding ratio and a short time until the after-image caused by the direct current voltage disappears, includes a compound containing one carboxylic acid group in the molecule in addition to polyamic acid and imidized polymer thereof, A liquid crystal aligning agent containing a very small amount of a compound containing one carboxylic acid anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (see, for example, Patent Document 3) .

Further, as a liquid crystal alignment film having excellent liquid crystal alignability, high voltage holding ratio, low residual image, excellent reliability, and exhibiting a high pretilt angle, tetracarboxylic acid dianhydride having a specific structure and tetracarboxylic acid having cyclobutane There is known a polyamic acid obtained from an acid dianhydride and a specific diamine compound or a liquid crystal aligning agent containing the imidized polymer (see, for example, Patent Document 4). As a method for suppressing the afterimage due to the AC driving which occurs in the liquid crystal display element of the transversal electric field driving system, there is a method using a specific liquid crystal alignment film having good liquid crystal alignability and high interaction with liquid crystal molecules 5) has been proposed.

However, in recent years, liquid crystal televisions, which are large in size and large in size, have become main subjects, and the demand for afterimage has become more stringent, and characteristics capable of withstanding long-term use in a severe use environment have been demanded. In addition to this, the liquid crystal alignment film used needs to have higher reliability than that of the conventional liquid crystal alignment film. In addition, the liquid crystal alignment film is required to have good initial characteristics as well as to maintain good properties even after prolonged exposure, for example, .

On the other hand, it has been reported that the polyamic acid ester as a polymer component constituting the polyimide-based liquid crystal aligning agent does not cause a decrease in the molecular weight by the heat treatment at the time of imidation thereof, and thus has excellent alignment stability and reliability of the liquid crystal (See Patent Document 6). The polyamic acid ester generally has a high volume resistivity and a large residual charge when a direct current voltage is applied. Therefore, a liquid crystal aligning agent in which a polyamic acid ester and a polyamic acid excellent in electrical characteristics are blended is disclosed (See Patent Document 7).

Japanese Patent Application Laid-Open No. 9-316200 Japanese Patent Application Laid-Open No. 10-104633 Japanese Patent Application Laid-Open No. 8-76128 Japanese Patent Application Laid-Open No. 9-138414 Japanese Laid-Open Patent Publication No. 11-38415 Japanese Patent Application Laid-Open No. 2003-26918 WO 2011/15080

As described above, it has been reported that a liquid crystal alignment film obtained from a liquid crystal aligning agent in which such a polyamic acid ester and a polyamic acid are blended has excellent properties in liquid crystal alignability and electrical characteristics. That is, a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid has improved characteristics in terms of afterimage characteristics and long-term reliability in AC / DC driving.

However, when a sealing agent is applied to the surface of the liquid crystal alignment film on the substrate on which the liquid crystal alignment film is formed and the two substrates are adhered to each other to produce a liquid crystal display element, the liquid crystal alignment film obtained from the liquid crystal aligning agent containing such polyamic acid ester and polyamic acid, It has been found that the adhesiveness (adhesiveness) to the sealant and the substrate can not be satisfied.

From the above, in order to enlarge the effective pixel area in recent liquid crystal display elements, it is required to further reduce the so-called frame area in which pixels are not formed at the peripheral edge portion on the substrate. For this purpose, It is a problem to improve the adhesiveness of a liquid crystal alignment film obtained from a liquid crystal aligning agent blended with a mixed acid ester and a polyamic acid to a sealant or a substrate.

In addition, it is required that the improvement of the adhesiveness of the liquid crystal alignment film with the sealant and the substrate is required to be achieved without deteriorating the liquid crystal alignment property and the electric property of the liquid crystal alignment film, and if possible, to further improve these properties.

The present invention has been made in order to achieve the above object, and has the following points.

1. A liquid crystal aligning agent comprising the following components (A), (B), and (C).

(A): a tetracarboxylic acid dialkyl ester derivative containing 60 mol% or more of a tetracarboxylic acid dialkyl ester derivative represented by the following formula (1) and a diamine represented by the following formulas (2) to (5) A polyamic acid ester obtained by a polycondensation reaction of a diamine containing at least one diamine selected.

[Chemical Formula 1]

(R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is a hydroxyl group or a chlorine atom, and R _X is an alkyl group having 1 to 6 carbon atoms.)

(2)

(3)

(Wherein A ₁ represents a single bond, an ester bond, an amide bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms, A ₂ represents a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, A is an integer of 1 to 4, and when a is 2 or more, the structure of A ₂ may be the same or different.)

Component (B): Polyamic acid obtained by polycondensation reaction of tetracarboxylic acid dianhydride with diamine.

Component (C): bifunctional or polyfunctional (meth) acrylic acid or its derivative.

Wherein the content ratio of the component (A) to the component (B) is 1/9 to 9/1 as a mass ratio (A / B), and the content of the component (C) (100% by mass) of the liquid crystal aligning agent.

3. The polyamide resin composition according to claim 1, wherein the component (A) is a polyamine obtained by using a diamine containing 40 to 100 mol% of at least one diamine selected from the group consisting of diamines represented by the above formulas (2) to (5) The liquid crystal aligning agent according to the above 1 or 2, wherein the liquid crystal aligning agent is a mixed acid ester.

Wherein the component (A) is at least one kind of diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3), a diamine represented by the formula (4) 3. The liquid crystal aligning agent according to any one of 1 to 3 above, which is a polyamic acid ester obtained by using a diamine containing a diamine containing at least one diamine selected from the group consisting of diamines.

5. The polyamic acid ester of claim 1, wherein the component (A) is a polyamic acid ester obtained by using a diamine containing at least one diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (4) The liquid crystal aligning agent described in any one of < 1 >

6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein A ₂ in the formula (4) is a structure represented by the following formula (6).

[Chemical Formula 4]

(Formula (6) in A ₃ is a single _{bond, -O-, -S-, -NR '3} -, an ester bond, amide bond, thioester bond, a urea bond, a carbonate bond, or a carbamic mate bond, R ₃ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group, an alkynyl group, is selected from an aryl group, and a combination of groups thereof, which may have a substituent. R _'3 is a hydrogen atom or an alkyl group, An alkenyl group, an alkynyl group, an aryl group, and combinations thereof, and they may have a substituent.

7. The polyamic acid ester according to any one of the above 1 to 6, wherein the component (A) is a polyamic acid ester obtained by using a diamine containing at least one diamine selected from the group consisting of diamines (A-1) to (A- A liquid crystal aligning agent according to any one of claims 1 to 3.

[Chemical Formula 5]

8. The polyamic acid composition according to any one of claims 1 to 8, wherein the component (A) is a polyamic acid obtained by using a diamine containing the diamine of the formula (2) and at least one diamine selected from the group consisting of the formulas (A-1) 7. The liquid crystal aligning agent according to 7 above, which is an ester.

9. A polyarylate obtained by using a tetracarboxylic acid dianhydride having at least one member selected from the group consisting of tetracarboxylic acid dianhydrides of the following formulas (B-1) to (B-9) The liquid crystal aligning agent according to any one of 1 to 8 above, which is a mica acid.

[Chemical Formula 6]

Wherein the component (B) is at least one tetracarboxylic acid dianhydride containing at least 20 mol% of at least one tetracarboxylic acid dianhydride selected from the group consisting of the above-mentioned formulas (B-1) to (B-9) The liquid crystal aligning agent according to any one of 1 to 9 above, which is a polyamic acid obtained by a polycondensation reaction of a diamine and a diamine.

11. The polyamic acid according to any one of (1) to (10) above, wherein the component (B) is a polyamic acid obtained by using a diamine containing at least one member selected from the group consisting of the following formulas (B-10) to Liquid crystal aligning agent.

(7)

Wherein the component (B) is a polyamic acid obtained by using a diamine having at least one kind of diamine selected from the group consisting of the above-mentioned formulas (B-10) to (B-14) 11. The liquid crystal aligning agent according to 11 above.

13. The liquid crystal aligning agent according to any one of 1 to 12 above, wherein the component (C) is dipentaerythritol hexaacrylate, or a glycerin diglycidyl ether acrylic acid adduct.

14. The composition according to claim 1, further comprising at least one organic solvent (D1) selected from the group consisting of? -Butyrolactone and its derivatives and at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, (D2) selected from the group consisting of an organic solvent (D1) and an organic solvent (D2), wherein the content of the organic solvent (D1) is 2 to 30% by mass relative to the total amount of the organic solvent Wherein the liquid crystal aligning agent is a liquid crystal aligning agent according to any one of the above items 1 to 13,

15. The liquid crystal aligning agent according to any one of 1 to 14 above, which is used for a liquid crystal alignment film subjected to photo alignment treatment.

16. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of 1 to 15 above to a substrate and firing.

According to the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal alignment film having a sufficiently high adhesiveness (adhesiveness) with the sealant and the substrate used in the production of the liquid crystal display element. This makes it possible to sufficiently cope with the narrowing of the frame region in the liquid crystal display element.

Further, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is improved in the electrical characteristics such as the interface characteristics between the liquid crystal and the liquid crystal alignment film, such as reduction of the afterimage due to the AC drive, and the voltage retention rate, ion density, do.

[Component (A)] [

The polyamic acid ester used in the present invention is a polyimide precursor for obtaining a polyimide and is a polymer having a site capable of undergoing an imidization reaction as described below by heating.

[Chemical Formula 8]

The component (A) of the present invention is obtained by reacting a tetracarboxylic acid dialkyl ester derivative represented by the following formula (1) with a tetracarboxylic acid dialkyl ester derivative containing not less than 60 mol% of the total tetracarboxylic acid dialkyl ester derivative and a tetracarboxylic acid dialkyl ester derivative represented by the following formula ) To a diamine represented by the formula (5). ≪ EMI ID = 2.0 >

[Chemical Formula 9]

[Chemical formula 10]

(11)

In the formula (1), R ₁ is an alkyl group having 1 to 4 carbon atoms, and R ₂ is a hydroxyl group or a chlorine atom. R _x is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

Specific examples of R ₁ include a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group. As the polyamic acid ester, the temperature at which the imidization proceeds becomes higher as the number of carbon atoms in the alkyl group increases. Therefore, R ₁ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of easiness of imidization by heat .

When R ₂ is a chlorine atom, a bis (chlorocarbonyl) compound having high reactivity with diamine is more preferable.

The diamine to be polycondensed with the tetracarboxylic acid dialkyl ester derivative represented by the formula (1) preferably contains at least one diamine selected from the group consisting of diamines represented by the formulas (2) to (5). Among them, at least one kind of diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3), a diamine represented by the formula (4) and a diamine represented by the formula (5) , The solubility of? -Butyrolactone can be enhanced, and therefore, it is preferable. Particularly, in the case of a diamine containing at least one diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (4), a liquid crystal alignment film having a high liquid crystal alignability can be obtained.

In the formulas (3) and (5), A ₁ is a single bond, an ester bond, an amide bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms.

In A ₁ , the ester bond is represented by -C (O) O-, or -OC (O) -.

The amide bond may represent a structure represented by -C (O) NH-, -C (O) NR-, -NHC (O) - or -NRC (O) -. R is an alkyl group, alkenyl group, alkynyl group, aryl group, thioester bond, or a combination thereof having 1 to 10 carbon atoms.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group.

Examples of the alkenyl group include those wherein at least one CH ₂ -CH ₂ structure existing in the alkyl group is substituted with a CH═CH structure, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, A phenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group and a cyclohexenyl group.

Examples of the alkynyl group include those obtained by substituting at least one CH ₂ -CH ₂ structure existing in the alkyl group with a C≡C structure. More specifically, ethynyl, 1-propynyl, 2-propynyl, .

The aryl group includes, for example, a phenyl group.

The thioester bond may represent a structure represented by -C (O) S-, or -SC (O) -.

When A < _{1 >} is a divalent organic group having 2 to 10 carbon atoms, it may be represented by the following formula (6).

[Chemical Formula 12]

In formula (6), A ₄ , A ₅ and A ₆ each independently represent a single bond, -O-, -S-, -NR ₈ -, ester bond, amide bond, thioester bond, urea bond, A carbonate bond, or a carbamate bond. R ₈ is a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl groups, alkenyl groups, alkynyl groups and aryl groups.

The ester bond, amide bond and thioester bond in A ₄ , A ₅ and A ₆ may have the same structure as the ester bond, amide bond and thioester bond.

The urea bond may represent a structure represented by -NH-C (O) NH-, or -NR-C (O) NR-. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

The carbonate bond may represent a structure represented by -O-C (O) -O-.

The carbamate bond includes a structure represented by -NH-C (O) -O-, -OC (O) -NH-, -NR-C (O) -O-, or -OC Lt; / RTI > R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

R ₄ and R ₅ in the formula (6) each independently represent a single bond or an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof having 1 to 10 carbon atoms, . When R ₄ and R ₅ of which one is a single bond of, R ₄ or R ₅ is selected from the group which alkylene group, alkenylene group, alkynylene group, arylene group, and combinations thereof having 2 to 10 carbon atoms, these substituents .

Examples of the alkylene group include a structure in which one hydrogen atom is removed from the alkyl group. Specific examples thereof include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, Propylene group, a 1,2-cyclopentylene group, a 1,2-cyclobutylene group, a 1,3-cyclohexylene group, a 1,2- Butylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group and the like.

Examples of the alkenylene group include a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, examples thereof include a 1,1-ethenylene group, a 1,2-ethenylene group, a 1,2-ethenylene methylene group, a 1-methyl-1,2-ethenylene group, 1-ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2- 2-ethenylene-1,4-butylene group, 1,2-ethenylene-1,2-butylene group and the like.

Examples of the alkynylene group include a structure in which one hydrogen atom is removed from the alkynyl group. Specific examples thereof include an ethynylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene- -Propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group and the like.

Examples of the arylene group include a structure in which one hydrogen atom is removed from the aryl group. More specifically, examples thereof include a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group.

The alkylene group, alkenylene group, alkynylene group, arylene group, and a combination thereof may have a substituent group when the number of carbon atoms is generally from 1 to 20, and may form a ring structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, an amide group, , An alkenyl group, and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the organoxy group as a substituent include a structure represented by -O-R such as an alkoxy group, an alkenyloxy group, an aryloxy group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

Examples of the organotio group as a substituent include a structure represented by -S-R, such as an alkylthio group, an alkenylthio group, an arylthio group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group.

The organosilyl group as a substituent may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, and a tributylsilyl group.

The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group as a substituent may represent a structure represented by -C (O) O-R or -OC (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

The thioester group which is a substituent may represent a structure represented by -C (S) O-R or -OC (S) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents.

The amide group which is a substituent includes a structure represented by -C (O) NH ₂ , or -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC Lt; / RTI > These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents.

Examples of the aryl group as the substituent include the same aryl groups as those described above. These aryl groups may be further substituted with other substituents described above.

Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

Examples of the alkynyl group as the substituent include the same alkynyl groups as mentioned above. These alkynyl groups may be further substituted with other substituents described above.

When a diamine having a high linearity or a rigid structure is used, a liquid crystal alignment film having good liquid crystal alignability can be obtained. Therefore, as the structure of A ₁ , a single bond or a structure represented by the following formulas (A1-1) to ) Is more preferable.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

In the formulas (4) and (5), A ₂ is a halogen atom, a hydroxyl group, an amino group, a thiol group, a nitro group, And when a is 2 or more, the structure of A ₂ may be the same or different.

Examples of the halogen atom include the same ones as the examples of the halogen atom.

The amino group may be represented by -NH ₂ , -NHR, or -NR (R) -. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

Examples of the monovalent organic group having 1 to 20 carbon atoms include an organoxy group, an organoxy group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, an amide group, an alkyl group, an alkenyl group, And an aryl group.

Examples of the organoxy group include a structure represented by -O-R such as an alkoxy group, an alkenyloxy group, an aryloxy group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

Examples of the organotitanium moiety include a structure represented by -S-R such as an alkylthio group, an alkenylthio group, an arylthio group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group.

The organosilyl group may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, and a tributylsilyl group.

The acyl group may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group may represent a structure represented by -C (O) O-R or -OC (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned.

The thioester group can be represented by -C (S) O-R or -OC (S) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

The phosphate ester group may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like.

The amide group may represent a structure represented by -C (O) NH ₂ , -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC have. These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like.

Examples of the alkyl group, alkenyl group, alkynyl group and aryl group include the same groups as the above-mentioned alkyl group, alkenyl group, alkynyl group and aryl group.

The alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent group when the number of carbon atoms is generally from 1 to 20, and may further form a cyclic structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, An aryl group, an alkyl group, an alkenyl group, and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the organoxy group as a substituent include a structure represented by -O-R such as an alkoxy group, an alkenyloxy group, an aryloxy group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the alkyloxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, lauryloxy And the like.

Examples of the organotio group as a substituent include a structure represented by -S-R, such as an alkylthio group, an alkenylthio group, an arylthio group, and the like. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, And the like.

The organosilyl group as a substituent may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, Silyl group, decyldimethylsilyl group and the like.

The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group as a substituent may represent a structure represented by -C (O) O-R or -OC (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

The thioester group which is a substituent may represent a structure represented by -C (S) O-R or -OC (S) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents.

The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents.

The amide group which is a substituent includes a structure represented by -C (O) NH ₂ , -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC . These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents.

The carbamate group as the substituent may represent a structure represented by -OC (O) NH ₂ , -OC (O) NHR, -NHC (O) -OR, or -NR-C (O) OR. These R may be the same or different and may be exemplified by the above-mentioned alkyl group, aryl group and the like. These R may be further substituted with the aforementioned substituents.

Examples of the aryl group as the substituent include the same aryl groups as those described above. These aryl groups may be further substituted with other substituents described above.

Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

Examples of the alkynyl group as the substituent include the same alkynyl groups as mentioned above. These alkynyl groups may be further substituted with other substituents described above.

When A ₂ in the formulas (4) and (5) has an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, the number of carbon atoms is preferably 1 to 14. When A ₂ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having a carbon number of 15 or more, there is a possibility that the liquid crystal alignability is deteriorated or the control of the pretilt angle becomes difficult depending on the content of the diamine to be used.

It is preferable that A ₂ in the formulas (4) and (5) is a structure represented by the following formula (6).

[Chemical Formula 18]

Equation (6) in A ₃ is a single _{bond, -O-, -S-, -NR '3} -, an ester bond, amide bond, thioester bond, a urea bond, a carbonate bond, or a carbamic mate bond, R ₃ is selected from alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and combinations thereof having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may have a substituent, and these groups may have substituents. R ' ₃ is a hydrogen atom or a group selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a combination thereof, and they may have a substituent.

When the structure of A ₂ is a diamine of a structure having a leaving group which is desorbed by heating, the solubility of the polymer is improved, and the liquid crystal alignability and the pretilt angle are not affected. The structure represented by the following formulas (A2-1) to (A2-24) is preferable for the structure of A ₂ having a leaving group which is desorbed by heating.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

The proportion of the diamine represented by the above formulas (2) to (5) is preferably 5 to 100 mol% in the total diamine. The higher the proportion of the diamine represented by the above formulas (2) to (5) is, the more preferably 40 to 100 mol% is more preferable and 60 to 100 mol% is more preferable since a liquid crystal alignment film having good liquid crystal alignability can be obtained.

Among them, as the diamine as a raw material of the component (A), at least one kind of diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3), a diamine represented by the formula (4) And at least one diamine selected from the group consisting of diamines represented by the formula (5). The diamine as the raw material of the component (A) preferably contains at least one diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (4). This makes it possible to increase solubility particularly in? -Butyrolactone as a solvent.

In this case, the amount of the diamine represented by the formula (2), the total amount of the diamine represented by the formula (2) and the diamine represented by the formula (3), the amount of the diamine represented by the formula (4) And the diamine represented by the formula (5) is preferably 95/5 to 60/40, more preferably 90/10 to 80/20 in terms of the molar ratio.

As the diamine has a rigid structure, a liquid crystal alignment film having excellent liquid crystal alignability can be obtained. The diamine for obtaining the polyamic acid ester of the present invention is preferably a diamine represented by the following formulas (A-1) to (A-5) Is preferably a diamine containing at least one diamine selected from the group consisting of a diamine and a diamine represented by the formula (2). In this case, the molar ratio of the amount of the diamine represented by the formula (2) to the amount of the diamine selected from the group consisting of the diamine formulas (A-1) to (A-5) 95/5 to 60/40, and more preferably 90/10 to 80/20.

≪ EMI ID =

In the present invention, the tetracarboxylic acid dialkyl ester represented by the above formula (1) is preferably at least 60 mol%, more preferably at least 80 mol%, of the total tetracarboxylic acid dialkyl ester. Among them, more preferably 90 to 100 mol%. In this case, the tetracarboxylic acid dialkyl ester derivative represented by the following formulas (10) to (11) may be used as the tetracarboxylic acid derivative together with the tetracarboxylic acid dialkyl ester derivative represented by the above formula (1).

(25)

In the above formulas (10) to (11), X is a tetravalent organic group, and R ₁ is the same as in the formula (1) including preferred examples. X is not particularly limited, and specific examples thereof include the structures represented by the following X-1 to X-46. Two or more of these tetracarboxylic acid derivatives may be used.

(26)

(27)

(28)

In the present invention, the diamines represented by the above formulas (2) to (5) are preferably 5 to 100 mol%, more preferably 50 to 100 mol%, of the total diamine. The diamine represented by the following formula (12) may be used together with the diamine represented by the above formulas (2) to (5).

[Chemical Formula 29]

In the formula (12), R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent. Specific examples of these alkyl groups, alkenyl groups, and alkynyl groups include the same ones as described above.

The alkyl group, alkenyl group, or alkynyl group may have a substituent group when the number of carbon atoms is generally from 1 to 10, and may further form a cyclic structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organoxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, , An alkenyl group, and an alkynyl group. Specific examples of each substituent include the same ones as described above.

In general, when introducing a bulky structure, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as R ₆ and R ₇ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In the formula (12), Y is a divalent organic group. Y is not particularly limited, but specific examples include the structures represented by the following formulas Y-1 to Y-113. Two or more kinds of diamines having these Y may be used. Y-7, Y-10, Y-11, Y-12, Y-13, Y-13, and Y are preferably used as Y in order to obtain a good liquid crystal alignability. 21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y- More preferred are diamines of Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98. When it is desired to increase the pretilt angle, it is preferable to introduce a diamine having a long-chain alkyl group, aromatic ring, aliphatic ring, steroid skeleton, or a combination thereof in the side chain into the polyamic acid ester, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-80, , Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97. An arbitrary pretilt angle can be expressed by adding 1 to 50 mol%, more preferably 5 to 20 mol%, of these diamines to the total diamine.

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

[Component (B)] [

The polyamic acid used in the present invention is a polyimide precursor for obtaining a polyimide and is a polymer having a site capable of undergoing an imidization reaction as described below by heating.

(48)

The component (B) of the present invention is a polyamic acid obtained by a polycondensation reaction of a tetracarboxylic acid dianhydride and a diamine. The tetracarboxylic acid dianhydride can be represented by the following formula (13), wherein X ₁ is a tetravalent organic group and its structure is not particularly limited. Specific examples include the structures of the above formulas (X-1) to (X-46).

(49)

The diamine compound can be represented by the following formula (14), wherein Y ₁ is a divalent organic group and its structure is not particularly limited. Specific examples include the structures of the above formulas (Y-1) to (Y-99) and (Y-110) to (Y-113).

(50)

(Wherein R ₆ and R ₇ are the same as the respective definitions of the formula (12)).

If the component (B) is localized on the surface of the film, there is a possibility that orientation of the liquid crystal is inhibited. On the other hand, if component (A) can be localized on the surface of the film, a liquid crystal alignment film excellent in not only liquid crystal alignability but also reliability and afterimage characteristics can be obtained. Therefore, as the polyamic acid as the component (B), a polyamic acid having a high polarity and a high solubility, which improves the surface migration of the component (A), is preferable. From this point of view, it is possible to obtain a polycondensation reaction of a tetracarboxylic acid dianhydride containing at least one tetracarboxylic acid dianhydride selected from the group consisting of the above-mentioned formulas (B-1) to (B-9) Is preferably a polyamic acid.

The proportion of the at least one tetracarboxylic acid dianhydride selected from the group consisting of the formulas (B-1) to (B-9) is preferably 5 to 100 mol% based on the total tetracarboxylic acid dianhydride . The higher the ratio of use, the higher the polarity and the solubility of the polymer. Therefore, it is more preferably 20 to 100 mol%, and still more preferably 40 to 100 mol%.

From the same viewpoint, by using a diamine having a substituent having a high polarity, it is possible to localize the polyamic acid as the component (B) in the film and at the substrate interface. As the diamine having a substituent having a high polarity, a diamine containing a secondary or tertiary amino group, a hydroxyl group, an amide group, a urea group or a carboxyl group is preferable. Y ₁ , Y-31, Y-40, Y-45, Y-49 to Y-51, Y-61, Y-98 or Y-99 And Y-98 or Y-99 containing a carboxyl group is more preferable.

The amount of the diamine compound having a substituent having a high polarity is preferably 5 to 100 mol% based on the total diamine. The higher the amount used, the better the polarity of the polymer and the higher the film surface ratio of the component (A), so 10 to 100 mol% is more preferable, and 30 to 100 mol% is more preferable.

The tetracarboxylic acid dianhydride which is a raw material of the component (B) is preferably a tetracarboxylic acid dianhydride containing at least one tetracarboxylic acid dianhydride selected from the group consisting of tetracarboxylic dianhydrides of the following formulas (B-1) to (B-9) Bicarboxylic acid dianhydride is preferred.

(51)

At least one kind of tetracarboxylic acid dianhydride selected from the group consisting of the formulas (B-1) to (B-9) is preferably an all tetracarboxylic acid dianhydride used as a raw material for the component (B) More preferably 20 mol% or more, and more preferably 40 mol% or more. Among them, it is particularly preferable that 60 mol% or more of (B-1) is used.

On the other hand, the diamine as a raw material of the component (B) is preferably a diamine containing at least one member selected from the group consisting of the following formulas (B-10) to (B-13).

(52)

At least one kind of diamine selected from the group consisting of the above-mentioned formulas (B-10) to (B-13) is preferably 20 mol% or more of the total diamines used in the raw material of the component (B) It is used in an amount of 40 mol% or more. Among them, it is particularly preferable that 60 mol% or more of (B-10) is used.

The diamine having a photoreactive group as described above may be classified into one kind of a liquid crystal alignment layer depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding property, accumulated charge and the like, Or two or more kinds may be mixed and used.

The diamine having such a photoreactive group is preferably used in an amount of 5 to 50 mol%, more preferably 10 to 20 mol%, based on the total diamine component used in the synthesis of the component (A) and / or the component (B) Mol%.

[Component (C)] [

Component (C) of the present invention is a bifunctional or polyfunctional (meth) acrylic acid or a derivative thereof. The content of the component (C) is preferably from 0.1 to 10 mass%, more preferably from 1 to 5 mass%, based on the sum of the components (A) and (B) (100 mass%).

Specific examples of the component (C) include Aronix M-210, M-240, M-6200 (manufactured by Toa Synthetic Chemical Industry Co., Ltd.), KAYARAD HDDA, copper HX-220, copper R- (Manufactured by Nippon Kayaku), V260, V312, V335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BA-4EA, BP-4PA and BP-2PA Functional (meth) acrylic acid derivatives; (Manufactured by Toa Kagaku Kogyo Co., Ltd.), KAYARAD TMPTA, Copper DPCA-20, Copper-30, Copper M-8060, Copper M- (Meth) acrylic acid derivatives having three or more functional groups such as D-60, D-120 (manufactured by Nippon Kayaku Co.) and VGPT (manufactured by Osaka Organic Chemical Industry Co., Ltd.). Among them, dipentaerythritol hexaacrylate, glycerin diglycidyl ether acrylic acid adduct and the like can be given.

[Organic solvents]

The liquid crystal aligning agent of the present invention usually contains an organic solvent for dissolving or dispersing the components (A) to (C). The organic solvent is not limited.

Examples of such an organic solvent include a solvent capable of dissolving a polyamic acid ester and a polyamic acid (hereinafter referred to as a good solvent) and a solvent for improving the uniformity of a coating film when the liquid crystal aligning agent is applied to a substrate (hereinafter, And a poor solvent).

The positive solvent is not particularly limited as long as it dissolves the polyamic acid ester as the component (A) and the polyamic acid as the component (B). Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2- N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, 3-methoxy-N, . These may be used alone or in combination of two or more. Further, even a solvent which does not dissolve the polymer alone may be used as long as the polymer does not precipitate, or may be a mixed solvent of two or more kinds.

The poor solvent is not particularly limited as long as it has a low surface tension and can improve coating film uniformity. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, lactic acid, isobutyl lactate, cyclohexanone, And a wheat ester. These solvents may be used in combination of two or more.

In the present invention, the organic solvent is at least one organic solvent (D1) selected from the group consisting of? -Butyrolactone and its derivatives, and at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone, At least one organic solvent (D2) selected from the group consisting of zoledinone and derivatives thereof, wherein the content of the organic solvent (D2) is in the range of from 2 To 30% by mass is preferable. The content of the organic solvent (D2) is more preferably 5 to 20% by mass.

Examples of the? -Butyrolactone or its derivative which is the organic solvent (D1) are not particularly limited as long as it is an organic solvent having a lactone structure. However, it is suitable as a solvent for dissolving the polyamic acid ester as the component (A) ,? -butyrolactone, or? -valerolactone are particularly preferable.

Examples of the organic solvent (D2) include N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, Pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, or 1,3-dimethylimidazolidinone. If the boiling point is too high, there is a possibility that the solvent remains in the film and the properties as a liquid crystal alignment film are deteriorated. Therefore, N-methyl-2-pyrrolidone or 1,3-dimethyl- , And N-methyl-2-pyrrolidone are more preferred.

The polyamic acid ester as the component (A) of the present invention has high affinity for the organic solvent (D1) and can be easily dissolved in these organic solvents. However, the polyamic acid ester as the component (A) has a low affinity for the organic solvent (D2). When the content of the polyamic acid ester increases, the polyamic acid ester as the component (A) precipitates or the phase separation of the polyamic acid ester and the polyamic acid There is a possibility to affect the state. Therefore, the content of the organic solvent (D2) is preferably 2 to 30% by mass, more preferably 2 to 20% by mass, and particularly preferably 5 to 15% by mass with respect to the total amount of the organic solvent (D1) Mass%.

The content of the organic solvent (D2) varies in a preferable range depending on the application method of the liquid crystal aligning agent. In the case of the flexographic printing method, since the solvent composition does not change well at the time of application, the content of the organic solvent , More preferably from 5 to 15 mass%.

On the other hand, in the case of the ink-jet coating method, since the liquid crystal aligning agent becomes a minute droplet upon application, there is a possibility that the solvent composition before coating and the solvent composition after the liquid crystal aligning agent is immersed in the substrate are different. Concretely,? -Butyrolactone and its derivatives having a high vapor pressure are volatilized at the time of coating, and the content of? -Butyrolactone and its derivatives when the liquid is mixed with the substrate is reduced. Therefore, the organic solvent (D1) preferably has a larger solvent composition, and the content of the organic solvent (D2) is more preferably 2 to 15 mass%, and more preferably 2 to 10 mass%.

[Production method of polyamic acid ester]

The polyamic acid ester which is the component (A) of the liquid crystal aligning agent of the present invention can be produced by a known production method. Specifically, the following methods (a) and (b) can be used, but the method is not limited thereto.

(a) a process for producing a polyamic acid ester from an acid chloride and a diamine compound

The polyamic acid ester can be prepared from a bis (chlorocarbonyl) compound and a diamine compound.

Specifically, the bis (chlorocarbonyl) compound and the diamine compound are reacted in the presence of a base and an organic solvent at -20 to 140 ° C, preferably 0 to 50 ° C, for 30 minutes to 24 hours, For 4 hours. As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but pyridine is preferred because the reaction proceeds mildly. The addition amount of the base is 2 to 4 times, preferably 2 to 2.5 times, the mole of the bis (chlorocarbonyl) compound, because the excess amount is difficult to remove and excessively small, the molecular weight becomes small.

The solvent used for the production of the polyamic acid ester is preferably N-methyl-2-pyrrolidone or? -Butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and they may be used alone or in combination of two or more .

When the concentration is too high, precipitation of the polymer tends to occur. When the concentration is too low, the molecular weight does not rise. Therefore, the total amount of the bis (chlorocarbonyl) compound and the diamine compound in the reaction liquid is preferably 1 to 30 mass% To 20% by mass is more preferable. In order to prevent the hydrolysis of the bis (chlorocarbonyl) compound, it is preferable that the solvent used for the production of the polyamic acid ester is dehydrated as much as possible. The reaction is carried out in a nitrogen atmosphere to prevent the mixture of outside air .

(b) a process for producing a polyamic acid ester from a dialkyl ester dicarboxylic acid and a diamine compound

The polyamic acid ester can be produced by condensing a tetracarboxylic acid dialkyl ester and a diamine compound with a condensing agent.

Concretely, the dialkyl ester dicarboxylic acid and the diamine compound are reacted in the presence of a condensing agent, a base and an organic solvent at 0 to 140 ° C, preferably 0 to 100 ° C for 30 minutes to 24 hours, preferably 3 To < / RTI > 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate and (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The amount of the condensing agent to be added is preferably 2 to 3 times by mole, more preferably 2 to 2.5 times by mole, based on the dialkyl ester dicarboxylic acid.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 times, more preferably 2.5 to 3 times, more preferably 2.5 to 3 times the amount of the diamine component, since the amount of the base is too large to remove and the molecular weight becomes small if the amount is too small.

Among the above-mentioned methods for producing polyamic acid esters, a polyamic acid ester having a high molecular weight can be obtained, so that the method (a) is particularly preferable.

The solution of the polyamic acid ester obtained as described above can be precipitated by pouring into a poor solvent while stirring well. Precipitation is carried out several times, washed with a poor solvent, and then dried at room temperature or heated to obtain a purified polyamic acid ester powder.

Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

[Production of polyamic acid]

The polyamic acid which is the component (B) of the liquid crystal aligning agent of the present invention and the raw material of the polyamic acid ester as the component (A) can be produced by polycondensation of a tetracarboxylic acid dianhydride and a diamine compound.

In the case of producing polyamic acid, the tetracarboxylic acid dianhydride and the diamine compound are preferably reacted in the presence of an organic solvent at -20 to 140 ° C, preferably 0 to 50 ° C, for 30 minutes to 24 hours, For 1 to 12 hours.

The organic solvent used for the production of the polyamic acid is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of monomers and polymers, A mixture of two or more species may be used. When the concentration is too high, the polymer tends to precipitate. When the concentration is too low, the molecular weight does not increase. Therefore, the total amount of the tetracarboxylic acid dianhydride and the diamine compound in the reaction liquid is preferably 1 to 30 mass% To 20% by mass is more preferable.

The polyamic acid obtained as described above can be used as the component (B) for the reaction solution. When the solvent used in the polymerization is not contained in the liquid crystal aligning agent, the polymeric acid is recovered as a solid, (B).

The polymer can be precipitated and recovered by injecting the reaction solution into a poor solvent while stirring well. Precipitation is conducted several times, washed with a poor solvent, and then heated or dried at room temperature to obtain a powder of the purified polyamic acid.

Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

The ratio of the diamine component used in the polymerization reaction to the tetracarboxylic acid derivative (tetracarboxylic acid dianhydride, tetracarboxylic acid di-alkyl derivative, etc.) is preferably 1: 0.7 to 1: 1.2 in terms of the molar ratio Do. The closer the molar ratio is to 1: 1, the larger the molecular weight of the polyimide precursor is. The molecular weight of the polyamic acid ester and the polyamic acid affects the viscosity of the varnish and the physical strength of the polyimide film, and if the molecular weight of the polyamic acid ester and the polyamic acid is excessively large, the varnish application workability and coating film uniformity are deteriorated There is a case. If the molecular weight is too small, the strength of the resulting polyimide film may be insufficient.

Accordingly, the molecular weight of the polyamic acid ester and the polyamic acid of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight.

[Liquid crystal aligning agent]

The content ratio of the component (A) and the component (B) in the liquid crystal aligning agent of the present invention is preferably 1/9 to 9/1 as the mass ratio (A / B), preferably 3/7 to 7/3 Is more preferable. When the ratio is within this range, it is possible to provide a liquid crystal aligning agent having both excellent liquid crystal alignability and electrical characteristics.

The content of the component (C) in the liquid crystal aligning agent of the present invention is preferably 0.1% by mass or more, more preferably 1.0% by mass or more relative to the sum of the components (A) and (B) And still more preferably not less than 3.0% by mass. When the content of the component (C) is small, the effect of improving the adhesiveness of the liquid crystal alignment film obtained from the liquid crystal aligning agent to the substrate is insufficient. On the other hand, the content of the component (C) is preferably 15 mass% or less, particularly preferably 10 mass% or less, from the viewpoint of liquid crystal alignability.

On the other hand, the total content (concentration) of the component (A) and the component (B) in the liquid crystal aligning agent of the present invention can be appropriately changed according to the setting of the thickness of the liquid crystal alignment film to be formed, It is preferably 0.5% by mass or more with respect to the organic solvent, and from the viewpoint of the storage stability of the solution, 15% by mass or less, particularly preferably 1 to 10% by mass, is preferable.

The liquid crystal aligning agent of the present invention may further contain various additives such as a silane coupling agent and a crosslinking agent. The silane coupling agent is added for the purpose of further improving the adhesion between the substrate to which the liquid crystal aligning agent is applied and the liquid crystal alignment film formed thereon. Specific examples of the silane coupling agent are given below, but the present invention is not limited thereto.

Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- Amine-based silane coupling agents such as phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and 3-aminopropyldiethoxymethylsilane; Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p Vinyl silane coupling agents such as styryltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 - epoxycyclohexyl) ethyl trimethoxysilane; Methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Ring agent; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; A ureido-based silane coupling agent such as 3-ureidopropyltriethoxysilane; Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide, and bis (3- (triethoxysilyl) propyl) tetrasulfide; Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane; Aldehyde-based silane coupling agents such as triethoxysilylbutylaldehyde; Carbamate-based silane coupling agents such as triethoxysilylpropylmethyl carbamate and (3-triethoxysilylpropyl) -t-butylcarbamate.

When the amount of the silane coupling agent is too large, the unreacted portion adversely affects the liquid crystal alignability. When the silane coupling agent is added in an excessively small amount, the effect on adhesiveness is not exhibited. Therefore, the added amount is preferably 0.01 to 5.0 wt% More preferably 0.1 to 1.0% by weight.

In the case of adding the silane coupling agent, it is preferable to add a solvent for improving the uniformity of the coating film before addition to prevent precipitation of the polymer. When a silane coupling agent is added, it may be added to both of the polyamic acid ester solution, the polyamic acid solution, or the polyamic acid ester solution and the polyamic acid solution before mixing the polyamic acid ester solution and the polyamic acid solution. It may also be added to a polyamic acid ester-polyamic acid mixed solution. Since the silane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, the silane coupling agent may be added to the polyamic acid solution, which may be localized in the film and at the substrate interface, It is more preferable to mix the solution with the polyamic acid ester solution after the reaction is sufficiently carried out.

An imidization accelerator may be added in order to efficiently progress the imidization of the polyamic acid ester when the coating film is baked. Specific examples of the imidization accelerator of the polyamic acid ester include, but are not limited to, the following.

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D in the formulas (D-1) to (D-17) is, independently of each other, a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. In addition, in the formulas (D-14) to (D-17), there is a plurality of D's in one formula, but they may be the same or different.

The content of the imidization promoter is not particularly limited as long as the effect of promoting thermal imidization of the polyamic acid ester can be obtained. However, the amount of the imidization promoter is not limited to 1 mol of the amic ester moiety of the formula (12) contained in the polyamic acid ester in the liquid crystal aligning agent Preferably 0.01 mol or more, more preferably 0.05 mol or more, and still more preferably 0.1 mol or more. In addition, since the imidization promoter itself remaining in the film after firing is prevented from adversely affecting the properties of the liquid crystal alignment film to the minimum, the amic ester moiety of the formula (12) contained in the polyamic acid ester in the liquid crystal aligning agent The imidization promoter is preferably 2 mol or less, more preferably 1 mol or less, and still more preferably 0.5 mol or less, per 1 mol.

(55)

When an imidization accelerator is added, since imidization may proceed by heating, it is preferably added after dilution with a good solvent and a poor solvent.

Needless to say, various additives such as a crosslinking agent may be used in the liquid crystal aligning agent of the present invention. The polyamic acid ester as the component (A) and the polyamic acid as the component (B) of the present invention may be two or more kinds, respectively.

The concentration (content) of the polymer containing the polyamic acid ester (component (A)) and the polyamic acid (component (B)) in the liquid crystal aligning agent of the present invention is appropriately determined depending on the setting of the thickness of the polyimide film to be formed But it is preferably 1 to 10% by mass, more preferably 2 to 8% by mass with respect to the organic solvent. If it is less than 1% by mass, it is difficult to form a uniform and defect-free coating film, and if it is more than 10% by mass, the storage stability of the solution may be deteriorated.

[Production method of liquid crystal aligning agent]

The liquid crystal aligning agent of the present invention contains a polyamic acid ester (component (A)) having a specific structure and a polyamic acid (component (B)).

The ratio of the component (A) to the total amount of the component (A) and the component (B) is preferably from 5 to 95% by mass. If the proportion of the component (A) is too small, sufficient liquid crystal alignability may not be obtained. If the proportion of the component (B) is small, the effect described in the present invention may not be obtained. Therefore, the proportion of the component (A) is preferably from 20 to 80 mass%, more preferably from 30 to 70 mass%.

Examples of the method of mixing the component (A) and the component (B) include a method of mixing powders of a polyamic acid ester (A) and a polyamic acid (B) and dissolving them in an organic solvent; A method of mixing a powder of a mixed acid ester and a polyamic acid solution as a component (B), a method of mixing a polyamic acid ester solution as a component (A) and a powder of a polyamic acid as a component (B), a method of mixing a polyamic acid ester And a solution of polyamic acid as component (B). (B) component, which is a homogeneous component (A), can be obtained even when the two solvents for dissolving the polyamic acid ester as the component (A) and the polyamic acid as the component (B) , A method of mixing a polyamic acid ester solution as the component (A) and a polyamic acid solution as the component (B) is more preferable.

As a method for preparing the polyamic acid ester solution as the component (A), a method of dissolving the powder of the polyamic acid ester as the component (A) in γ-butyrolactone or its derivative or another good solvent is more preferred, butyrolactone or its derivative is more preferable. At this time, the polymer concentration is preferably 10 to 30%, and particularly preferably 10 to 15%. It may also be heated when the powder of the polyamic acid ester (component (A)) is dissolved. The heating temperature is preferably 20 to 150 占 폚, particularly preferably 20 to 80 占 폚.

As a method for preparing a polyamic acid solution as the component (B), a method of dissolving a polyamic acid powder in N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidinone, or the above- A solution, a method of using the polymerization reaction solution as it is, and a method of using the polymerization reaction solution as it is is more preferable. When the polyamic acid is polymerized, the solvent is mixed with? -Butyrolactone or a derivative thereof and a mixed solvent of N-methyl-2-pyrrolidone, 1,3-dimethylpyrrolidinone or a derivative thereof, The method of obtaining is more preferable. When the polyamic acid powder is redissolved, the polymer concentration is preferably 10 to 30%, particularly preferably 10 to 15%. It is also possible to heat the polymer powder when it is dissolved. The heating temperature is preferably 20 to 150 占 폚, particularly preferably 20 to 80 占 폚.

In the case where a silane coupling agent is added, before the polyamic acid ester solution as the component (A) and the polyamic acid solution as the component (B) are mixed, the polyamic acid ester solution as the component (A), the polyamic acid solution , Or both of the polyamic acid ester solution as the component (A) and the polyamic acid solution as the component (B). Further, it can be added to the polyamic acid mixed solution of the polyamic acid ester - (B) component (A). Since the silane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, the silane coupling agent is added to the polyamic acid solution which is a component (B) that can be localized in the film and at the substrate interface, And the silane coupling agent are sufficiently reacted with each other and then mixed with the polyamic acid ester solution as the component (A). The addition amount of the silane coupling agent is preferably from 0.01 to 5.0% by mass, more preferably from 0.1 to 5.0% by mass, based on the solid content of the polymer, To 1.0% by mass is more preferable.

When the polyamic acid ester solution as the component (A) and the polyamic acid solution as the component (B) are mixed, the polymer concentration is preferably 10 to 30%, and particularly preferably 10 to 15%. The heating temperature may be 20 to 100 占 폚, particularly preferably 20 to 60 占 폚.

When a silane coupling agent or a crosslinking agent is added, it is preferable to add a silane coupling agent or a crosslinking agent before addition of a poor solvent in order to prevent precipitation of the polymer. An imidization accelerator may be added in order to efficiently progress the imidization of the polyamic acid ester when the coating film is baked. When an imidization accelerator is added, since imidization may proceed by heating, it is preferably added after dilution with a good solvent and a poor solvent.

The above-mentioned good solvent and poor solvent are added to the obtained mixture of the polyamic acid ester (A) and the polyamic acid (B), and the mixture is diluted to a predetermined polymer concentration to obtain the liquid crystal aligning agent of the present invention.

[Liquid Crystal Alignment Layer]

In the liquid crystal alignment film of the present invention, the above liquid crystal aligning agent can be preferably applied to the substrate after filtration, followed by drying and firing to form a coating film. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency. A glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, (Indium Tin Oxide) electrode or the like is preferably used from the viewpoint of process simplification. In the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side. In this case, a material for reflecting light such as aluminum can also be used as the electrode in this case.

Examples of the application method of the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. After applying the liquid crystal aligning agent of the present invention, the coating film is preferably dried and fired. In order to sufficiently remove the organic solvent contained in the liquid crystal aligning agent, it is preferably dried at 50 to 120 ° C, preferably for 1 to 10 minutes. Then, it is preferably baked at 150 to 300 占 폚, more preferably at 150 to 250 占 폚. The firing time varies depending on the firing temperature, but is preferably 5 to 120 minutes, and more preferably 5 to 60 minutes.

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm. This coating film surface can be used as a liquid crystal alignment film by performing orientation treatment such as rubbing. Examples of a method of orienting the coating film include a rubbing method and a photo-alignment treatment method.

The liquid crystal alignment film of the present invention is a liquid crystal alignment film imparted with liquid crystal aligning ability by irradiating with polarized radiation. In addition, it is a liquid crystal alignment film in which uniformity and good liquid crystal alignability can be obtained even when a light irradiation range that exhibits liquid crystal alignability is wider than that of a conventional photo alignment liquid crystal alignment film and irradiation intensity fluctuates in the substrate plane.

As a specific example of the photo-alignment treatment method, the surface of the coating film is irradiated with polarized radiation in a predetermined direction, and if necessary, heat treatment is further carried out at a temperature of 150 to 250 ° C to give a liquid crystal alignment capability . As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coated film substrate may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably in the range of 1 to 10,000 mJ / cm 2, and particularly preferably in the range of 100 to 5,000 mJ / cm 2.

[Liquid crystal alignment element]

Two substrates each having the liquid crystal alignment film formed thereon as described above were fabricated and the two substrates were opposed to each other with a gap (cell gap) interposed therebetween so that the alignment treatment directions in the respective liquid crystal alignment films were orthogonal or anti- The periphery of the two substrates is bonded using a sealant, liquid crystal is injected and filled in the cell gap defined by the surface of the substrate and the sealant, and the injection hole is sealed to constitute the liquid crystal cell. A polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell so that the polarizing direction is coincident with or orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate, Device is obtained.

In the present invention, as the sealant, for example, a cured resin system having both reactive groups of an epoxy group and a (meth) acryloyl group is preferably used. However, it is not particularly limited as long as the staining property to the liquid crystal is low. The sealing agent of the present invention may be blended with an inorganic filler for the purpose of improving adhesiveness and moisture resistance. Specific examples of the inorganic filler that can be used include but are not limited to spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, Examples of the inorganic filler include mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide and asbestos. Preferred examples of the binder include silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, . These inorganic fillers may be used in a mixture of two or more kinds.

Example

Hereinafter, the present invention will be described in further detail with reference to examples. However, the present invention is not limited to these examples. In the following, the abbreviations of the compounds and the measurement methods of the respective properties are as follows.

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

BCS: butyl cellosolve

IPA: 2-propanol

DE-1: see the following formula (DE-1);

DA-1: see the following formula (DA-1);

DA-2: see the following formula (DA-2);

DA-3: see the following formula (DA-3);

DA-4: see the following formula (DA-4);

Me: methyl group, Bu: n-butyl group, Boc: t-butoxy group

Additive A: dipentaerythritol hexaacrylate (manufactured by Daicel-Cotech)

Additive B: glycerin diglycidyl ether acrylic acid adduct (trade name: Epoxy ester 80 MFA, manufactured by Kyowa Chemical Industry Co., Ltd.)

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[Viscosity]

The viscosity of the polyamic acid ester and the polyamic acid solution was measured using a sample amount of 1.1 ml, cone rotor TE-1 (1 DEG 34 ', R24) and a temperature of 25 DEG C using TVE-22H (Toki Industries Co., Respectively.

[Molecular Weight]

The molecular weight of the polyamic acid ester and the polyamic acid is measured by a GPC (room temperature gel permeation chromatography) apparatus and is expressed as a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight , Also referred to as Mw).

GPC apparatus: manufactured by Shodex Corp. (GPC-101)

Column: manufactured by Shodex Corp. (serial of KD803 and KD805)

Column temperature: 50 ° C

Eluent: N, N- dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ (liters), a phosphoric acid, a 30 m㏖ anhydrous crystal (o- phosphoric acid) / ℓ, 10 ml / l of tetrahydrofuran (THF)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000 and 30,000) manufactured by Tosoh Corporation and polyethylene glycol (polymer peak molecular weight (Mp) of about 12,000, 4,000 , And 1,000) were used. In order to avoid overlapping of peaks, two samples of samples mixed with four types of 900,000, 100,000, 12,000, and 1,000 and three samples of 150,000, 30,000, and 4,000 were separately performed.

[Fabrication of FFS driven liquid crystal cell]

First, a substrate having electrodes formed thereon was prepared. The substrate is a glass substrate having a size of 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, an IZO electrode having a solid-like pattern constituting the counter electrode as the first layer is formed. On the first layer counter electrode, a SiN (silicon nitride) film formed by a CVD method is formed as a second layer. The thickness of the second-layer SiN film is 500 nm and functions as an interlayer insulating film. On the second-layer SiN film, pixel electrodes on the combs formed by patterning the IZO film as the third layer are disposed, and two pixels, i.e., the first pixel and the second pixel, are formed. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the first layer counter electrode and the third layer pixel electrode are electrically insulated by the action of the second layer SiN film.

The third-layer pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion. The width of each electrode element in the short direction is 3 占 퐉, and the interval between the electrode elements is 6 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not a rectangular shape, and the shape of the bold Shaped shape. Each pixel has a first region which is an upper side of the bent portion and a second region which is a lower side, the upper side being divided into upper and lower portions with the central bent portion as a boundary.

When the first region and the second region of each pixel are compared with each other, the formation direction of the electrode elements of the pixel electrodes constituting the first region and the second region is different. That is, when the liquid crystal alignment direction of the liquid crystal alignment layer described later is taken as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle of + 10 degrees in the first region of the pixel, 10 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation operation (in-plane switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is opposite to each other have.

Next, after the liquid crystal aligning agent was filtered with a filter of 1.0 탆, a liquid crystal aligning agent was applied by spin coating onto the prepared substrate on which the electrode was formed. Dried on a hot plate at 80 DEG C for 2 minutes and then fired in a hot air circulating oven at 230 DEG C for 14 minutes to form a coating film having a film thickness of 100 nm. This coated film surface was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 500 mJ / cm 2 to obtain a substrate having a liquid crystal alignment film formed thereon. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉 and on which no electrode was formed as a counter substrate, and the alignment treatment was carried out.

A sealant was printed on the substrate with two sets of the above substrates, and another substrate was adhered to the liquid crystal alignment film so that the alignment direction was 0 ° so as to face the liquid crystal alignment film surface. Thereafter, the sealant was cured, Respectively. A liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this vacant cell by a reduced pressure injection method and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

[AC drive burn-in of liquid crystal cell]

An AC voltage of ± 10 V was applied at a frequency of 30 Hz for 144 hours under a constant temperature environment of 60 ° C. using the liquid crystal cell prepared above. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day.

After leaving the liquid crystal cell, the liquid crystal cell was placed between two polarizers arranged so that the polarization axis thereof was orthogonal to each other, and the backlight was turned on in the voltage unapplied state, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of the transmitted light was minimized. The rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the first pixel was darkest to the angle at which the first area became darkest was calculated as the angle?. Similarly, in the second pixel, the second region and the first region were compared and a similar angle? Was calculated. Then, the average value of the angles? Of the first and second pixels was calculated as the angle? Of the liquid crystal cell. The AC drive burn-in was less than 0.1, and more than that was determined to be defective.

≪ Synthesis Example 1 &

A 500 ml four-necked flask equipped with a stirrer was charged with 4.58 g (42.4 mmol) of p-phenylenediamine, 1.79 g (4.71 mmol) of DA-1, 84.7 g of NMP, , And 8.40 g (106 mmol) of pyridine as a base were added and dissolved by stirring. Next, 14.4 g (44.2 mmol) of DE-1 was added while stirring the diamine solution, and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 1.23 g (13.6 mmol) of acryloyl chloride was added, and the mixture was reacted at 15 DEG C for 4 hours. The obtained polyamic acid ester solution was added to 1477 g of IPA while stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 738 g of IPA five times and drying to obtain 17.3 g of a white polyamic acid ester resin powder ≪ / RTI > The yield was 96.9%. The molecular weight of the polyamic acid ester was Mn = 14,288 and Mw = 29,956.

3.69 g of the obtained polyamic acid ester resin powder was taken in a 100 mL Erlenmeyer flask, and 33.2 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution PAE-1.

≪ Synthesis Example 2 &

0.91 g (5.98 mmol) of 3,5-diaminobenzoic acid and 4.78 g (23.9 mmol) of 4,4'-diaminodiphenylamine were placed in a 100 mL four-necked flask equipped with a stirrer and a nitrogen- , 13.3 g of NMP and 6.66 g of GBL were added and dissolved by stirring while nitrogen was being supplied. While the diamine solution was stirred, 4.76 g (24.0 mmol) of 1,2,3,4-butanetetracarboxylic acid dianhydride was added, 9.99 g of GBL was added, and the mixture was stirred at room temperature for 2 hours. Next, 20.0 g of GBL was added and stirred. Then, 1.31 g (6.00 mmol) of pyromellitic dianhydride was added, and 4.80 g of GBL was added and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-1 ). The viscosity of the obtained polyamic acid solution at 25 캜 was 4,147 mPa s. The molecular weight of the polyamic acid was Mn = 24,333 and Mw = 60,010.

≪ Synthesis Example 3 &

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen-introducing tube, 0.30 g (1.98 mmol) of 3,5-diaminobenzoic acid and 1.71 g (8.02 mmol ), 2.25 g of NMP and 11.3 g of GBL were added and dissolved by stirring while nitrogen was being supplied. While this diamine solution was stirred, 1.72 g (8.68 mmol) of 1,2,3,4-butanetetracarboxylic acid dianhydride was added, 4.50 g of GBL was added, and the mixture was stirred at room temperature for 2 hours. Next, 0.22 g (1.01 mmol) of pyromellitic dianhydride was added, 4.50 g of GBL was added, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-2). The viscosity of the obtained polyamic acid solution at 25 캜 was 232 mPa.. The molecular weight of the polyamic acid was Mn = 9,870 and Mw = 20,054.

≪ Synthesis Example 4 &

A 500 ml four-necked flask equipped with a stirrer was charged with 2.50 g (23.1 mmol) of p-phenylenediamine, 0.59 g (1.22 mmol) of DA-3, 42.8 g of NMP, 129 g, and 4.34 g (54.9 mmol) of pyridine as a base were added and dissolved by stirring. Next, 7.44 g (22.9 mmol) of DE-1 was added to the diamine solution while stirring, and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 0.63 g (7.01 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 574 g of IPA while stirring, and the precipitated white precipitate was collected by filtration, washed with 382 g of IPA five times, and dried to obtain 8.82 g of a white polyamic acid ester resin powder ≪ / RTI > The yield was 97.8%. The molecular weight of the polyamic acid ester was Mn = 16,617 and Mw = 37,387.

0.80 g of the obtained polyamic acid ester resin powder was taken in a 100 ml Erlenmeyer flask, and 7.20 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution PAE-2.

≪ Synthesis Example 5 &

A 500-ml four-necked flask equipped with a stirrer was charged with 1.23 g (11.3 mmol) of p-phenylenediamine, 0.80 g (3.77 mmol) of 4,4'-ethylenedianiline, NMP 27.0 g of GBL, 91.2 g of GBL, and 2.69 g (34.0 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 4.61 g (14.2 mmol) of DE-1 was added and reacted at 15 ° C overnight. After stirring overnight, 0.39 g (4.34 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 384 g of IPA while stirring, and the precipitated white precipitate was collected by filtration, washed with 256 g of IPA five times, and dried to obtain 5.11 g of a white polyamic acid ester resin powder ≪ / RTI > The yield was 89.6%. The molecular weight of the polyamic acid ester was Mn = 14,806 and Mw = 32,719.

0.80 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, and 7.20 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution PAE-3.

≪ Synthesis Example 6 &

A 500-ml four-necked flask equipped with a stirrer was charged with 2.80 g (25.9 mmol) of p-phenylenediamine, 1.45 g (6.47 mmol) of DA-2, 111 g of NMP, 6.18 g (78.1 mmol) of pyridine was added and dissolved by stirring. Next, 9.89 g (30.4 mmol) of DE-1 was added to this diamine solution while stirring, and the reaction was allowed to proceed at 15 占 폚 overnight. After stirring overnight, 0.38 g (4.21 mmol) of acryloyl chloride was added and the reaction was carried out at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 1230 g of water with stirring, and the precipitated white precipitate was collected by filtration, washed with 1230 g of IPA five times, and dried to obtain 10.2 g of a white polyamic acid ester resin powder ≪ / RTI > The yield was 83.0%. The molecular weight of the polyamic acid ester was Mn = 20,786 and Mw = 40,973.

0.798 g of the obtained polyamic acid ester resin powder was taken in a 100 ml Erlenmeyer flask, and 7.18 g of GBL was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution PAE-4.

≪ Synthesis Example 7 &

A 500-ml four-necked flask equipped with a stirrer was charged with 14.4 g (58.8 mmol) of DA-4, 2.48 g (6.53 mmol) of DA-1, 622 g of NMP, 11.6 g (147 mmol) was added and dissolved by stirring. Next, while stirring the diamine solution, 20.0 g (61.4 mmol) of DE-1 was added and reacted at 15 占 폚 overnight. After stirring overnight, 1.70 g (18.8 mmol) of acryloyl chloride was added and reacted at 15 ° C for 4 hours. The resulting polyamic acid ester solution was added to 2691 g of IPA while stirring, and the precipitated white precipitate was collected by filtration, washed with 1345 g of IPA five times, and dried to obtain 31.4 g of a white polyamic acid ester resin powder ≪ / RTI > The yield was 95.9%. The molecular weight of the polyamic acid ester was Mn = 13,012 and Mw = 25,594.

3.70 g of the obtained polyamic acid ester resin powder was placed in a 100 mL Erlenmeyer flask, and 33.3 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamic acid ester solution PAE-5.

[Preparation of liquid crystal aligning agent]

(Example 1)

4.40 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1 and 5.50 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2 were weighed, and 0.52 g of NMP, 5.58 g of GBL, 4.01 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A1.

Using this liquid crystal aligning agent A1, a substrate for evaluation of adhesion and a liquid crystal cell were produced in the following procedure.

≪ Evaluation of adhesion &

<< Sample production >>

A sample of the adhesion evaluation was prepared as follows. A liquid crystal aligning agent A1 was applied to an ITO substrate of 30 mm x 40 mm by spin coating. Dried on a hot plate at 80 DEG C for 2 minutes and then fired in a hot air circulating oven at 230 DEG C for 14 minutes to form a coating film having a film thickness of 100 nm. This coated film surface was irradiated with ultraviolet rays of 254 nm through a polarizing plate at 500 mJ / cm 2 to obtain a substrate on which a liquid crystal alignment film was formed.

Two substrates obtained as described above were prepared, and 4 mu m of bead spacers were coated on the liquid crystal alignment film surface of one of the substrates, and then a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was dropped thereon. Subsequently, the liquid crystal alignment film surface of the other substrate was faced inward and the bonding was performed so that the overlapping width of the substrate was 1 cm. At that time, the amount of the sealant was adjusted so that the diameter of the sealant after the bonding was 3 mm. Two assembled substrates were fixed with a clip and then thermally cured at 150 DEG C for one hour to prepare a sample for evaluation of adhesion.

<< Measurement of adhesion >>

Subsequently, the sample substrate was fixed with a tabletop type precision universal testing machine (AGS-X500N) manufactured by Shimadzu Corporation, and the upper and lower substrates were press-fitted from the upper part of the central portion of the substrate, ) Were measured. Observation was made on the peeling point of the measured substrate, and it was judged as &quot; Good &quot; when no peeling occurred between the seal / film or between the film and the substrate, and the whole of the sealant or the sealant was insulated. In the case of peeling between the seal / film, the adhesion between the seal / film was evaluated as x, and when the film / substrate was peeled off, the adhesion between the film and the substrate was evaluated as x.

&Lt; Example 2 &gt;

4.42 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1 and 5.48 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2 were weighed, and 0.50 g of NMP, 5.60 g of GBL, 3.99 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A2.

&Lt; Example 3 &gt;

4.40 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1 and 4.07 g of the polyamic acid solution PAA-2 obtained in Synthesis Example 3 were weighed, 0.06 g of NMP, 7.46 g of GBL, 3.98 g of BCS, and N 0.15 g of -α- (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A3.

<Example 4>

4.41 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1 and 4.04 g of the polyamic acid solution PAA-2 obtained in Synthesis Example 3 were weighed, and 0.06 g of NMP, 7.48 g of GBL, 4.00 g of BCS, and N 0.15 g of -α- (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A4 was obtained.

&Lt; Example 5 &gt;

4.41 g of the polyamic acid ester solution PAE-2 obtained in Synthesis Example 4 and 5.49 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2 were weighed, and 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A5.

&Lt; Example 6 &gt;

4.42 g of the polyamic acid ester solution PAE-2 obtained in Synthesis Example 4, 5.48 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2, and 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A6.

&Lt; Example 7 &gt;

4.42 g of the polyamic acid ester solution PAE-3 obtained in Synthetic Example 5 and 5.49 g of the polyamic acid solution PAA-1 obtained in Synthetic Example 2 were weighed, 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A7.

&Lt; Example 8 &gt;

4.42 g of the polyamic acid ester solution PAE-3 obtained in Synthetic Example 5 and 5.49 g of the polyamic acid solution PAA-1 obtained in Synthetic Example 2 were weighed, 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A8.

&Lt; Example 9 &gt;

4.42 g of the polyamic acid ester solution PAE-4 obtained in Synthesis Example 6, 5.50 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2, 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A9.

&Lt; Example 10 &gt;

4.40 g of the polyamic acid ester solution PAE-4 obtained in Synthesis Example 6 and 5.49 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2 were weighed, 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A10.

&Lt; Example 11 &gt;

4.42 g of the polyamic acid ester solution PAE-5 obtained in Synthetic Example 7 and 5.49 g of the polyamic acid solution PAA-1 obtained in Synthetic Example 2 were weighed, 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A11.

&Lt; Example 12 &gt;

4.42 g of the polyamic acid ester solution PAE-5 obtained in Synthesis Example 7 and 5.48 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2 were weighed, and 0.50 g of NMP, 5.60 g of GBL, 4.00 g of BCS, 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine and 0.11 g of Additive B were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent A12.

&Lt; Comparative Example 1 &

4.39 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1, 5.52 g of the polyamic acid solution PAA-1 obtained in Synthesis Example 2, 0.50 g of NMP, 5.57 g of GBL, 4.02 g of BCS, and N 0.15 g of -α- (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B1.

&Lt; Comparative Example 2 &

4.42 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1 and 4.07 g of the polyamic acid solution PAA-2 obtained in Synthesis Example 3 were weighed, and 0.06 g of NMP, 7.50 g of GBL, 4.01 g of BCS, and N 0.15 g of? - (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B2.

&Lt; Comparative Example 3 &

11.0 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1, 4.99 g of GBL, 4.02 g of BCS, and 10.0 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B3.

&Lt; Comparative Example 4 &

11.0 g of the polyamic acid ester solution PAE-1 obtained in Synthesis Example 1, 5.00 g of GBL, 4.01 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine was added, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B4.

&Lt; Comparative Example 5 &

9.17 g of the polyamic acid solution PAA-1 obtained in Synthetic Example 2 was weighed, and 1.37 g of NMP, 5.47 g of GBL, 3.99 g of BCS, and N-α- (9-fluorenylmethoxycarbonyl) 0.13 g of? - t-butoxycarbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B5.

&Lt; Comparative Example 6 &gt;

6.79 g of the polyamic acid solution PAA-2 obtained in Synthesis Example 3 was weighed, and 1.84 g of NMP, 7.37 g of GBL, 4.00 g of BCS, and N-α- (9-fluorenylmethoxycarbonyl) 0.15 g of? - t-butoxycarbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B6.

&Lt; Comparative Example 7 &

11.0 g of the polyamic acid ester solution PAE-2 obtained in Synthetic Example 4, 4.99 g of GBL, 4.01 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B7.

&Lt; Comparative Example 8 &gt;

11.0 g of the polyamic acid ester solution PAE-2 obtained in Synthetic Example 4, 5.00 g of GBL, 4.01 g of BCS, and 10.0 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B8.

&Lt; Comparative Example 9 &

11.0 g of the polyamic acid ester solution PAE-3 obtained in Synthetic Example 5, 5.00 g of GBL, 4.00 g of BCS, and 100 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B9.

&Lt; Comparative Example 10 &

11.0 g of the polyamic acid ester solution PAE-3 obtained in Synthetic Example 5, 5.00 g of GBL, 4.01 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine was added, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B10.

&Lt; Comparative Example 11 &

11.1 g of the polyamic acid ester solution PAE-4 obtained in Synthetic Example 6, 4.98 g of GBL, 4.02 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B11.

&Lt; Comparative Example 12 &gt;

11.0 g of the polyamic acid ester solution PAE-4 obtained in Synthetic Example 6, 5.00 g of GBL, 4.01 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine was added, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B12.

&Lt; Comparative Example 13 &

11.0 g of the polyamic acid ester solution PAE-5 obtained in Synthetic Example 7, 4.98 g of GBL, 4.02 g of BCS, and 10 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine and 0.11 g of Additive A were added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B13.

&Lt; Comparative Example 14 &gt;

11.0 g of the polyamic acid ester solution PAE-5 obtained in Synthetic Example 7, 5.00 g of GBL, 4.01 g of BCS, and 10.0 g of N-α- (9-fluorenylmethoxycarbonyl) -N- 0.15 g of carbonyl-L-histidine was added and stirred at room temperature for 3 hours to obtain liquid crystal aligning agent B14.

The adhesion evaluation and the AC drive burn-in evaluation were carried out in the same manner as in Example 1 except that the liquid crystal aligning agent B14 was used.

The liquid crystal aligning agent obtained in each of Examples 1 to 4 and Comparative Examples 1 to 6 was used to evaluate the adhesion to the liquid crystal cell obtained by the same method as in Example 1 and the results of the AC drive burn-in evaluation, Respectively.

Similarly, the liquid crystal aligning agent obtained in each of Examples 5 to 12 and Comparative Examples 7 to 14 was used to evaluate the adhesion to the liquid crystal cell obtained by the same method as in Example 1, Table 2 summarizes them.

Industrial availability

By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film having excellent liquid crystal alignability, electrical properties and further high seal adhesion. The liquid crystal display device having the liquid crystal alignment film is excellent in the after- It is possible to use it in an image display field such as a large-screen, high-definition liquid crystal television in which a display burn-in due to a residual charge of the liquid crystal display panel is suppressed and a high display quality is required.

Claims (16)

A liquid crystal aligning agent comprising the following components (A), (B), and (C).
(A): a tetracarboxylic acid dialkyl ester derivative containing 60 mol% or more of a tetracarboxylic acid dialkyl ester derivative represented by the following formula (1) and a diamine represented by the following formulas (2) to (5) A polyamic acid ester obtained by a polycondensation reaction of a diamine containing at least one diamine selected.
[Chemical Formula 1]

(R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is a hydroxyl group or a chlorine atom, and R _x is an alkyl group having 1 to 6 carbon atoms.)
(2)

(3)

(Wherein A ₁ represents a single bond, an ester bond, an amide bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms, A ₂ represents a halogen atom, a hydroxyl group, an amino group, a thiol group, Or a monovalent organic group having 1 to 20 carbon atoms, a is an integer of 1 to 4, and when a is 2 or more, the structure of A ₂ may be the same or different.)
Component (B): Polyamic acid obtained by polycondensation reaction of tetracarboxylic acid dianhydride with diamine.
Component (C): bifunctional or polyfunctional (meth) acrylic acid or its derivative. The method according to claim 1,
Wherein the content ratio of the component (A) to the component (B) is 1/9 to 9/1 as a mass ratio (A / B), and the content of the component (C) To 0.1% by mass of the liquid crystal aligning agent. 3. The method according to claim 1 or 2,
(A) is a polyamic acid ester obtained by using a diamine containing from 40 to 100 mol% of at least one diamine selected from the group consisting of diamines represented by the above formulas (2) to (5) Liquid crystal aligning agent. 4. The method according to any one of claims 1 to 3,
(1), wherein the component (A) comprises at least one diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (3), a diamine represented by the formula (4) Wherein the diamine is a polyamic acid ester obtained by using a diamine containing at least one kind of diamine. 5. The method according to any one of claims 1 to 4,
Wherein the component (A) is a polyamic acid ester obtained by using a diamine containing at least one diamine selected from the group consisting of a diamine represented by the formula (2) and a diamine represented by the formula (4). 6. The method according to any one of claims 1 to 5,
A ₂ in the formula (4) is a structure represented by the following formula (6).
[Chemical Formula 4]

(A ₃ is a single _{bond, -O-, -S-, -NR '3} - , and the ester bond, amide bond, thioester bond, a urea bond, a carbonate bond, a carbamate bond, or, R ₃ is a substituent R ' ₃ represents a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, an alkynyl group, an aryl group, An aryl group, and combinations thereof, and they may have a substituent.) 7. The method according to any one of claims 1 to 6,
Wherein the component (A) is a polyamic acid ester obtained by using a diamine containing at least one diamine selected from the group consisting of diamines of the following formulas (A-1) to (A-5).
[Chemical Formula 5]

8. The method of claim 7,
Wherein the component (A) is a polyamic acid ester obtained by using a diamine containing the diamine of the formula (2) and at least one diamine selected from the group consisting of the formulas (A-1) to (A-5) Lt; / RTI &gt; 9. The method according to any one of claims 1 to 8,
(B) is a polyamic acid obtained by using a tetracarboxylic acid dianhydride containing at least one member selected from the group consisting of tetracarboxylic acid dianhydrides of the following formulas (B-1) to (B-9) Acid Liquid Crystal Aligner.
[Chemical Formula 6]

10. The method according to any one of claims 1 to 9,
(B) is at least one tetracarboxylic acid dianhydride selected from the group consisting of the above-mentioned formulas (B-1) to (B-9) as a tetracarboxylic acid dianhydride having 20 mol% or more of the total tetracarboxylic acid dianhydride. A liquid crystal aligning agent which is a polyamic acid obtained by a polycondensation reaction between a carboxylic acid dianhydride and a diamine. 11. The method according to any one of claims 1 to 10,
(B) is a polyamic acid obtained by using a diamine containing at least one member selected from the group consisting of the following formulas (B-10) to (B-14).
(7)

12. The method of claim 11,
Wherein the component (B) is a polyamic acid obtained by using a diamine having 20 mol% or more of at least one diamine selected from the group consisting of the above-mentioned formulas (B-10) to (B-14). 13. The method according to any one of claims 1 to 12,
(C) is dipentaerythritol hexaacrylate, or a glycerin diglycidyl ether acrylic acid adduct. 14. The method according to any one of claims 1 to 13,
Further, at least one organic solvent (D1) selected from the group consisting of? -Butyrolactone and its derivatives and at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, (D2), wherein the content of the organic solvent (D1) is in the range of 2 to 30% by mass relative to the total amount of the organic solvent (D1) and the organic solvent (D2) A liquid crystal aligning agent containing a mixed organic solvent. 15. The method according to any one of claims 1 to 14,
Liquid crystal aligning agent for liquid crystal alignment film subjected to photo alignment treatment. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 15 to a substrate and firing the liquid crystal aligning agent.