KR20110072174A - Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device including the liquid crystal alignment film - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to improve printability, chemical resistance, liquid crystal alignment, and electrooptical characteristic, to control a pretilt angle, and to produce a vertical alignment mode liquid crystal alignment film and a twisted nematic mode liquid crystal alignment film. CONSTITUTION: A liquid crystal alignment agent includes a polymer selected from the group consisting of polyamic acids including a repeating unit represented by chemical formula 1, polyimide including a repeating unit represented by chemical formula 2, and combination thereof. In chemical formulas 1 and 2, X1 and X2 are the same or different and represent tetravalent organic groups induced from cycloaliphatic acid anhydrides or aromatic acid dianhydrides; Y1 and Y2 are the same or different and represent divalent organic groups induced from diamines.

Description

LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM MANUFACTURED USING THE SAME, AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE LIQUID CRYSTAL ALIGNMENT FILM}

The present disclosure relates to a liquid crystal aligning agent, a liquid crystal aligning film manufactured using the same, and a liquid crystal display device including the liquid crystal aligning film.

A liquid crystal display device (LCD) uses a liquid crystal alignment layer, and a polymer material is mainly used as the liquid crystal alignment layer. The liquid crystal alignment layer acts as a director in the arrangement of the liquid crystal molecules, so that the liquid crystal is moved by an electric field to form an image when the image is formed. In general, in order to obtain uniform brightness and high contrast ratio in the liquid crystal display, it is essential to orient the liquid crystal uniformly.

With the recent growth of the liquid crystal display device market, the demand for high quality liquid crystal display devices is increasing, and as the large area of liquid crystal display devices is advanced, the demand for high productivity liquid crystal alignment films is increasing. Therefore, research has been conducted on the liquid crystal aligning agent for producing a high-performance liquid crystal alignment layer that has a low defect rate in the liquid crystal display device production process and can express excellent electro-optical characteristics, reliability, and the like.

Provided are liquid crystal aligning agents excellent in printability and chemical resistance and capable of easily controlling the pretilt angle.

It provides the liquid crystal aligning film manufactured using the said liquid crystal aligning agent.

A liquid crystal display device comprising the liquid crystal alignment layer is provided.

According to an aspect of the present invention, a liquid crystal alignment including a polymer selected from the group consisting of a polyamic acid including a repeating unit represented by the following Chemical Formula 1, a polyimide including the repeating unit represented by the following Chemical Formula 2, and a combination thereof Offer

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

X ₁ and X ₂ are the same or different from each other, and each independently a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride,

Y ₁ and Y ₂ are the same or different from each other, and each independently a divalent organic group derived from a diamine, and the diamine includes a functional diamine represented by the following Formula (3).

(3)

In Chemical Formula 3,

A ₁ is the same or different from each other, and each independently a single bond, O, COO, CONH, OCO, or a substituted or unsubstituted C1 to C10 alkylene group,

R ₁ is the same or different from each other, and each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group,

R ₂ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₁ is an integer of 1 to 4,

n ₂ is an integer of 0 to 3.

The diamine may further include at least one of aromatic diamines represented by the following Chemical Formulas 4 to 7.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 4 to 7,

R ₃ to R ₁₂ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group, and the hetero The aryl group may further include one selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and combinations thereof,

A ₂ to A ₇ are the same or different from each other, and each independently a single bond, O, SO ₂ or C (R ₁₀₃ ) (R ₁₀₄ ), wherein R ₁₀₃ and R ₁₀₄ are the same or different from each other, each independently Hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n ₃ to n ₁₂ are each independently an integer of 0 to 4;

In addition, the diamine may include the functional diamine and the aromatic diamine in a molar ratio of 1:99 to 40:60.

The polyamic acid may have a weight average molecular weight (Mw) of 10,000 to 300,000.

The polyimide may have a weight average molecular weight of 10,000 to 300,000.

When the liquid crystal aligning agent includes the polyamic acid and the polyimide, the polyamic acid and the polyimide may be included in a weight ratio of 1:99 to 50:50.

The liquid crystal aligning agent may have a solid content of 1 to 15% by weight, and may have a viscosity of 3 to 30 cps.

According to another aspect of the invention provides a liquid crystal alignment film prepared by applying the liquid crystal aligning agent to a substrate.

According to still another aspect of the present invention, a liquid crystal display device including the liquid crystal alignment layer is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

Printability, chemical resistance, liquid crystal alignment and electro-optical characteristics can be improved, and the pretilt angle can be easily adjusted, so that the vertical alignment mode (VA mode) liquid crystal alignment layer and twisted nematic mode, TN mode ) It provides a liquid crystal aligning agent which can be used to manufacture a liquid crystal aligning film.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group (NH ₂ , NH (R ₁₀₀ ) or N (R ₁₀₁ ) (R ₁₀₂ ), wherein R ₁₀₀ , R ₁₀₁ and R ₁₀₂ are the same or different from each other, and are each independently C 1 to C 10 alkyl groups, amidino groups , Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted haloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group , Substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocycloalkyl group means one substituted with one or more substituents selected from the group do.

Unless stated otherwise in the present specification, "alkyl group" means a C1 to C30 alkyl group, specifically, a C1 to C20 alkyl group, and "cycloalkyl group" means a C3 to C30 cycloalkyl group, and specifically C3 To C20 cycloalkyl group, "heterocycloalkyl group" means C2 to C30 heterocycloalkyl group, specifically C2 to C20 heterocycloalkyl group, "alkylene group" means C1 to C30 alkylene group , Specifically, a C1 to C20 alkylene group, "alkoxy group" means a C1 to C30 alkoxy group, specifically a C1 to C20 alkoxy group, and a "cycloalkylene group" refers to a C3 to C30 cycloalkylene group It means, specifically, C3 to C20 cycloalkylene group, "heterocycloalkylene group" means C2 to C30 heterocycloalkylene group It means, specifically, C2 to C20 heterocycloalkylene group, "aryl group" means C6 to C30 aryl group, specifically C6 to C20 aryl group, "heteroaryl group" means C2 to C30 It means a heteroaryl group, specifically means a C2 to C18 heteroaryl group, "arylene" group means a C6 to C30 arylene group, specifically means a C6 to C20 arylene group, "heteroarylene group" Means a C2 to C30 heteroarylene group, specifically means a C2 to C20 heteroarylene group, "alkylaryl group" means a C7 to C30 alkylaryl group, specifically means a C7 to C20 alkylaryl group, "Halogen" means F, Cl, Br or I.

Also, unless stated otherwise in the present specification, a heterocycloalkyl group, a heterocycloalkylene group, a heteroaryl group, and a heteroarylene group each independently represent one or more heteroatoms of N, O, S, Si, or P in one ring. It contains three, and the rest means a cycloalkyl group, a cycloalkylene group, an aryl group, and an arylene group which are carbon.

Also, unless stated otherwise, "aliphatic" means C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C1 to C30 alkylene, C2 to C30 alkenylene, or C2 to C30 alkynylene Specifically, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkylene, C2 to C20 alkenylene, or C2 to C20 alkynylene, and "alicyclic" C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl, C3 to C30 cycloalkynyl, C3 to C30 cycloalkylene, C3 to C30 cycloalkenylene, or C3 to C30 cycloalkynylene, specifically C3 to C30 cycloalkynylene C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C3 to C20 cycloalkylene, C3 to C20 cycloalkenylene, or C3 to C20 cycloalkynylene, meaning "aromatic" 6 to C30 aryl, C2 to C30 heteroaryl, C6 to C30 arylene or C2 to C30 heteroarylene, specifically C6 to C16 aryl, C2 to C16 heteroaryl, C6 to C16 arylene or C2 to C16 Heteroarylene means.

Unless otherwise defined herein, “combination” generally means mixing or copolymerizing, in an alicyclic organic group and an aromatic organic group, at least two rings form a fused ring, or at least two rings are single Bond, O, S, C (= O), CH (OH), S (= O), S (= O) ₂ , Si (CH ₃ ) ₂ , (CH ₂ ) _p (where 1≤p≤2 ), (CF ₂ ) _q (where 1 ≦ _q ≦ 2), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) (CF ₃ ) or C (═O) NH It means that they are connected to each other by. Here, "copolymerization" means block copolymer to random copolymer, and "copolymer" means block copolymer to random copolymer.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

Liquid crystal aligning agent according to an embodiment of the present invention is a polymer selected from the group consisting of polyamic acid containing a repeating unit represented by the following formula (1), polyimide comprising a repeating unit represented by the following formula (2) and combinations thereof It includes.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

X ₁ and X ₂ are the same or different and are each independently a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride. X ₁ may be the same or different from each repeating unit, and X ₂ may be the same or different from each other.

Y ₁ and Y ₂ are the same or different from each other, and each independently a divalent organic group derived from a diamine, and the diamine includes a functional diamine represented by the following Formula (3). The Y ₁ may be the same or different from each repeating unit, and the Y ₂ may be the same or different from each other.

(3)

In Chemical Formula 3,

A ₁ is the same or different from each other, and each independently a single bond, O, COO, CONH, OCO, or a substituted or unsubstituted C1 to C10 alkylene group,

R ₁ is the same or different from each other, each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, specifically, a fluoroalkyl group,

R ₂ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₁ is an integer of 1 to 4,

n ₂ is an integer of 0 to 3.

When n ₁ is an integer of 2 or more, A ₁ may be the same or different from each other, and R ₁ may be the same or different from each other. When n ₂ is an integer of 2 or more. R ₂ may be the same or different from each other.

The diamine may further include at least one of aromatic diamines represented by the following Chemical Formulas 4 to 7.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 4 to 7,

R ₃ to R ₁₂ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group, and the hetero The aryl group may further include one selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and combinations thereof,

A ₂ to A ₇ are the same or different from each other, and each independently a single bond, O, SO ₂ or C (R ₁₀₃ ) (R ₁₀₄ ), wherein R ₁₀₃ and R ₁₀₄ are the same or different from each other, each independently Hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n ₃ to n ₁₂ are each independently an integer of 0 to 4;

When n ₃ is an integer of 2 or more, the R ₃ may be the same or different from each other. Similarly, when n ₄ to n ₁₂ are each an integer of 2 or more, the R ₄ to R ₁₂ may be the same or different from each other.

The polyamic acid and the polyimide may be present simply mixed or may be present by copolymerization.

Hereinafter, each component will be described in detail.

Polymer

The polymer includes a polyamic acid including a repeating unit represented by Formula 1, a polyimide including a repeating unit represented by Formula 2, and a combination thereof.

The polyamic acid including the repeating unit represented by Formula 1 may be synthesized from an acid dianhydride and a diamine. The method of preparing the polyamic acid by copolymerizing the acid dianhydride and the diamine may be applied without being limited to a method known to be usable for the synthesis of polyamic acid.

The polyimide containing the repeating unit represented by Formula 2 may be prepared by imidizing a polyamic acid including the repeating unit represented by Formula 1. Since a method of preparing polyimide by imidating polyamic acid is well known in the art, detailed description thereof will be omitted.

As said acid dianhydride, alicyclic acid dianhydride, aromatic acid dianhydride, or these can be used in mixture of 1 or more types. As said diamine, functional diamine or 1 or more types of functional diamine and aromatic diamine can be mixed and used.

The alicyclic acid dianhydride includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene-1,2- Dicarboxylic anhydride (DOCDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), 1,2,4-tricarboxy-3-methylcarboxy cyclopentane dianhydride, 1,2,3,4-tetracarboxy cyclopentane dianhydride Or may be used by mixing one or more thereof, but is not limited thereto.

The tetravalent organic group derived from the alicyclic acid dianhydride may include at least one of the functional groups represented by the following Chemical Formulas 8 to 12, but is not limited thereto.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

In Chemical Formulas 8 to 12,

R ₁₃ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₁₃ is an integer of 0 to 3,

R ₁₄ to R ₂₀ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

When n ₁₃ is an integer of 2 or more, R ₁₃ may be the same or different from each other.

The aromatic acid dianhydride may be pyromellitic dianhydride (PMDA), nonphthalic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), hexafluoroisopropylidene diphthalic acid The dianhydride (6-FDA), or a mixture of one or more thereof may be used, but is not limited thereto.

The tetravalent organic group derived from the aromatic acid dianhydride may include at least one of a functional group represented by the following Chemical Formula 13 and a functional group represented by the following Chemical Formula 14, but is not limited thereto.

[Formula 13]

[Formula 14]

In Chemical Formulas 13 and 14,

R ₂₁ and R ₂₂ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

R ₂₃ and R ₂₄ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₁₄ and n ₁₅ are each independently an integer of 0 to 3,

A ₈ is a single bond, O, CO, substituted or unsubstituted C1 to C6 alkylene group (eg C (CF ₃ ) ₂ ), substituted or unsubstituted C3 to C30 cycloalkylene group, or substituted or unsubstituted C2 to C30 heterocycloalkylene group.

When n ₁₄ is an integer of 2 or more, R ₂₃ may be the same or different from each other. Similarly, when n ₁₅ is an integer of 2 or more, the R ₂₄ may be the same or different from each other.

As the functional diamine, a compound represented by Chemical Formula 3 may be used. In addition, as the functional diamine, at least one of the compounds represented by the following Formulas 15 and 16 may be mixed with the compound represented by the above Formula 3 and used. In this case, the polyamic acid and the polyimide will contain a divalent organic group derived from the functional diamine. By the polyamic acid and the polyimide containing a divalent organic group derived from the functional diamine, it is possible to improve the liquid crystal orientation, chemical resistance and electro-optical properties, to easily adjust the pretilt angle, to express a high pretilt angle This liquid crystal aligning agent can be used in order to manufacture a vertical alignment liquid crystal aligning film and a twisted nematic type liquid crystal aligning film.

[Formula 15]

In Chemical Formula 15,

R ₂₅ , R ₂₆ and R ₂₇ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

A ₉ is a single bond, O, COO, CONH, OCO, or a substituted or unsubstituted C1 to C10 alkylene group,

R ₂₈ is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group are -O-, -COO-, It may further include selected from the group consisting of -CONH-, -OCO- and combinations thereof,

n ₁₆ is an integer of 0 or 3,

n ₁₇ and n ₁₈ are each independently an integer of 0 to 4;

When n ₁₆ is an integer of 2 or more, R ₂₅ may be the same or different from each other. Similarly, when n ₁₇ and n ₁₈ are each an integer of 2 or more, R ₂₆ and R ₂₇ may be the same or different from each other.

[Formula 16]

In Chemical Formula 16,

R ₂₉ and R ₃₀ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₁₉ and n ₂₀ are each independently an integer of 0 to 4,

R ₃₁ is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

A ₁₀ and A ₁₁ are the same or different from each other, and each independently a single bond, O or COO,

A ₁₂ is a single bond, O, COO, CONH or OCO.

When n ₁₉ is an integer of 2 or more, R ₂₉ may be the same or different from each other. Similarly, when n ₂₀ is an integer of 2 or more, R ₃₀ may be the same or different from each other.

Examples of the aromatic diamine include paraphenylenediamine (p-PDA), 4,4-methylenedianiline (MDA), 4,4-oxydianiline (ODA), metabisaminophenoxydiphenylsulfone (m-BAPS), Parabisaminophenoxydiphenylsulfone (p-BAPS), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafluoropropane (HF-BAPP), 1,4- Diamino-2-methoxybenzene, or a mixture of one or more thereof may be used, but is not limited thereto.

The divalent organic group derived from the aromatic diamine may include at least one of the functional groups represented by the following Chemical Formulas 17 to 19, but is not limited thereto. In this case, the polyamic acid and the polyimide will contain a divalent organic group derived from the aromatic diamine. By the polyamic acid and the polyimide containing a divalent organic group derived from the aromatic diamine, it is possible to improve the chemical resistance, thermal stability and mechanical properties of the liquid crystal aligning agent and the liquid crystal aligning film formed therefrom.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

In Chemical Formulas 17 to 20,

R ₃ to R ₁₂ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group, and the hetero The aryl group may further include one selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and combinations thereof,

A ₂ to A ₇ are the same or different from each other, and are each independently a single bond, O, SO ₂ or C (R ₁₀₃ ) (R ₁₀₄ ), such as C (CF ₃ ) ₂ , wherein R ₁₀₃ and R ₁₀₄ are The same or different from each other, and each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n ₃ to n ₁₂ are each independently an integer of 0 to 4;

When n ₃ is an integer of 2 or more, the R ₃ may be the same or different from each other. Similarly, when n ₄ to n ₁₂ are each an integer of 2 or more, the R ₄ to R ₁₂ may be the same or different from each other.

When the diamine includes the functional diamine and the aromatic diamine, the functional diamine and the aromatic diamine may be included in a molar ratio of 1:99 to 40:60. In this case, the adjustment of the pretilt angle and the high pretilt angle can be effectively performed, and the liquid crystal alignment, chemical resistance, electro-optical properties, thermal stability and mechanical properties can be effectively improved. Specifically, the functional diamine and the aromatic diamine may be included in a molar ratio of 5:95 to 30:70.

The polyamic acid may have a weight average molecular weight of 10,000 to 300,000. In addition, the polyimide may have a weight average molecular weight of 10,000 to 300,000. When the weight average molecular weight of the polyamic acid and the polyimide is within the above range, it is possible to effectively improve reliability and electro-optical properties, have excellent chemical resistance, and stably maintain the pretilt angle even after driving the liquid crystal display device.

When the liquid crystal aligning agent includes both the polyamic acid and the polyimide, the polyamic acid and the polyimide may be included in a weight ratio of 1:99 to 50:50. When the polyamic acid and the polyimide are included in the above range, the orientation stability can be improved. Specifically, the polyamic acid and the polyimide may be included in a weight ratio of 20:80 to 50:50.

In the liquid crystal aligning agent, the polymer may be included in an amount of 1 to 15 wt%. When the polymer is included in the above range can improve the printability and liquid crystal alignment. Specifically, the polymer may be included in 5 to 10% by weight.

menstruum

Liquid crystal aligning agent according to an embodiment of the present invention includes a solvent suitable for dissolving the polymer.

Examples of suitable solvents for dissolving the polymer include N-methyl-2-pyrrolidone; N, N-dimethyl acetamide; N, N-dimethyl formamide; Dimethyl sulfoxide; γ-butyrolactone; Tetrahydrofuran (THF); And phenolic solvents such as meta cresol, phenol, and halogenated phenol, but are not limited thereto.

The solvent may further include 2-butyl cellosolve (2-BC), thereby improving printability. In this case, the 2-butyl cellosolve may be included in an amount of 1 to 50 wt% based on the total amount of the solvent including 2-butyl cellosolve. When 2-butyl cellosolve is included in the above range, the printability can be easily improved. Specifically, the 2-butyl cellosolve may be included in an amount of 10 to 40 wt% based on the total amount of the solvent including 2-butyl cellosolve.

In addition, the solvent may further include a poor solvent alcohols, ketones, esters, ethers, hydrocarbons, or halogenated hydrocarbons in an appropriate ratio within the limit that the soluble polyimide polymer does not precipitate. The poor solvents may lower the surface energy of the liquid crystal aligning agent to improve spreadability and flatness during application.

The poor solvent may be included in an amount of 1 kPa to 90% by weight, specifically 1 to 70% by weight, based on the total amount of the solvent including the poor solvent.

Specific examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl Acetate, diethyl oxalate, malonic ester, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenylmethyl ether, ethylene glycol phenylethyl ether, di Ethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl on Le acetate, 4-hydroxy-4-methyl-2-pentanone, 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy acetate ethyl, hydroxy ethyl acetate, 2-hydroxy- Methyl 3-methyl butyrate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate, methyl 3-ethoxy propionate, methyl methoxy butanol, ethyl methoxy butanol, methyl ethoxy butanol, Ethyl ethoxy butanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, Alternatively, one or more thereof may be mixed and used.

The content of the solvent in the liquid crystal photo-alignment agent is not particularly limited, but may be used so that the content of solids in the liquid crystal photo-alignment agent is 1 to 15% by weight. When the content of solids is within the above range, the uniformity of the film can be properly maintained and the appropriate viscosity can be maintained by being less affected by the contamination of the substrate surface at the time of printing, thereby preventing the uniformity of the film due to the high viscosity at the time of printing. Can exhibit an appropriate transmittance. Specifically, the solid content may be 3 to 10% by weight.

The liquid crystal aligning agent may have a viscosity of 3 to 30 cps. When the viscosity of a liquid crystal aligning agent exists in the said range, coating film uniformity and applicability | paintability can be improved. Specifically, the liquid crystal aligning agent may have a viscosity of 10 to 25 cps.

Other additives

Liquid crystal aligning agent according to an embodiment of the present invention may further include other additives.

The other additives include epoxy compounds. The epoxy compound is used to improve reliability and electro-optic properties, and the epoxy compound may use one or more epoxy compounds including 2 to 8 epoxy groups, specifically, 2 to 4 epoxy groups.

The epoxy compound may be included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polymer. When the epoxy compound is included in the above range, it is possible to easily improve the reliability and electro-optical properties, while exhibiting proper printability and flatness when applied to the substrate. Specifically, the epoxy compound may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the polymer.

Examples of the epoxy compound may include a compound represented by the following Formula 21, but is not limited thereto.

[Formula 21]

In Chemical Formula 21,

A ₁₃ is a substituted or unsubstituted C6 to C12 aromatic organic group, or a substituted or unsubstituted divalent C6 to C12 alicyclic organic group, or a substituted or unsubstituted divalent C6 to C12 aliphatic organic group, specifically It may be a substituted or unsubstituted C1 to C6 alkylene group.

Specific examples of the epoxy compound include N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylmethane (TGDDM), N, N, N', N'-tetraglycidyl- 4,4'-diaminophenylethane, N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylpropane, N, N, N', N'-tetraglycidyl- 4,4'-diaminophenylbutane, N, N, N ', N'-tetraglycidyl-4,4'-diaminobenzene, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycol Cydyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'- Tetraglycidyl-1,4-phenylenediamine, N, N, N ', N'-tetraglycidyl-m-xylenediamine, N, N, N', N'-tetraglycidyl- 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy) phenyl] propane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,3-bis (N, N Diglycidylaminomethyl) benzene, and the like, but is not limited thereto.

Moreover, in order to improve printability, a suitable surfactant or coupling agent may be further used as an additive.

Liquid crystal alignment film according to another embodiment of the present invention is prepared using the liquid crystal aligning agent.

A liquid crystal aligning film can be formed by apply | coating a liquid crystal aligning agent to a board | substrate, As a method of apply | coating the said liquid crystal aligning agent to the said board | substrate, a spin coat method, a flexographic printing method, the inkjet method, etc. are mentioned. Among them, the flexographic printing method is excellent in uniformity of the formed coating film and can be easily enlarged, and therefore, it can be generally used.

The substrate can be used without particular limitation as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate or an acrylic substrate or a polycarbonate substrate can be used. In addition, using a substrate on which an indium-tin oxide (ITO) electrode or the like for driving a liquid crystal is used, the manufacturing process may be simplified.

The liquid crystal aligning agent is uniformly coated on a substrate in order to increase the uniformity of the coating film, and then at a temperature of room temperature to 200 ° C, specifically at a temperature of 30 ° C to 150 ° C, and more specifically of 40 ° C to 120 ° C. Temporary drying can be carried out for 1 to 100 minutes at a temperature. By adjusting the volatilization degree of each component of a liquid crystal aligning agent through the said temporary drying, the coating film which is uniform and there is no deviation can be obtained.

Thereafter, the liquid crystal aligning film can be formed by evaporating the solvent by firing at a temperature of 80 ° C to 300 ° C, specifically, 120 ° C to 280 ° C for 5 minutes to 300 minutes.

According to still another embodiment of the present invention, a liquid crystal display device including the liquid crystal alignment layer is provided.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.

Example

(Example 1: Preparation of the liquid crystal aligning agent containing polyamic acid (PAA-1))

Into a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector, and a cooler, 99 mmol of para-phenylenediamine and 1 mmol of diamine represented by the following Chemical Formula 22 were added while passing nitrogen. 228.66 g of methyl-2-pyrrolidone (NMP) was added to prepare a mixed solution.

[Formula 22]

80 mmol of 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene-1,2-dicarboxylic acid anhydride (DOCDA) and pyromellitic dianhydride (PMDA) were added to the mixed solution. 20 mmol was added and 34.2 g of N-methyl-2-pyrrolidone (NMP) was added thereto, followed by vigorous stirring. The reaction was carried out for 24 hours while maintaining the temperature below 60 ℃ to prepare a polyamic acid (PAA-1) solution. (Gamma) -butyrolactone and 2-butyl cellosolve (2-BC) were added here by volume ratio of 8: 2, and the liquid crystal aligning agent containing polyamic acid (PAA-1) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-1) was 160,000.

(Example 2: Preparation of the liquid crystal aligning agent containing polyamic acid (PAA-2))

Polyamic acid (PAA) was carried out in the same manner as in Example 1 except that 50 mmol of para-phenylenediamine and 48 mmol of 4,4-methylenedianiline were used, and 2 mmol g of diamine represented by Chemical Formula 22 was used. The liquid crystal aligning agent containing -2) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-2) was 160,000.

(Example 3: Preparation of the liquid crystal aligning agent containing polyamic acid (PAA-3))

Except for using 50 mmol of para-phenylenediamine and 45 mmol of 4,4-methylenedianiline, and 5 mmol of diamine represented by Formula 22, the same procedure as in Example 1 was carried out to provide polyamic acid (PAA- The liquid crystal aligning agent containing 3) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 23 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-3) was 160,000.

(Example 4: Preparation of the liquid crystal aligning agent containing polyamic acid (PAA-4))

Polyamic acid (PAA-) was carried out in the same manner as in Example 1 except that 50 mmol of para-phenylenediamine and 40 mmol of 4,4-methylenedianiline were used, and 10 mmol of diamine represented by Chemical Formula 22 was used. The liquid crystal aligning agent containing 4) was manufactured. Solid content of the said liquid crystal aligning agent was 5 weight%, and the viscosity was 24 cps. In addition, the weight average molecular weight of the polyamic acid (PAA-4) was 160,000.

(Example 5: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-5))

Except for using 50 mmol of para-phenylenediamine and 30 mmol of 4,4-methylenedianiline, and 20 mmol of diamine represented by Formula 22, the same procedure as in Example 1 was carried out to provide polyamic acid (PAA- The liquid crystal aligning agent containing 5) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 23 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-5) was 160,000.

(Example 6: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-6))

Except for using 50 mmol of para-phenylenediamine and 10 mmol of 4,4-methylenedianiline and 40 mmol of diamine represented by Formula 22, the same procedure as in Example 1 was carried out to provide polyamic acid (PAA- The liquid crystal aligning agent containing 6) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-6) was 160,000.

(Example 7: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-7))

1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) instead of 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene-1,2-dicarboxylic acid anhydride (DOCDA) A liquid crystal aligning agent including a polyamic acid (PAA-7) was prepared in the same manner as in Example 1 except for using). Solid content of the said liquid crystal aligning agent was 5 weight%, and the viscosity was 24 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-7) was 160,000.

(Example 8: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-8))

Polyamic acid (PAA-) was carried out in the same manner as in Example 7, except that 50 mmol of para-phenylenediamine and 40 mmol of 4,4-methylenedianiline were used, and 10 mmol of diamine represented by Chemical Formula 22 was used. The liquid crystal aligning agent containing 8) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 23 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-8) was 160,000.

(Example 9: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-9))

Polyamic acid (PAA-) was carried out in the same manner as in Example 7, except that 50 mmol of para-phenylenediamine and 10 mmol of 4,4-methylenedianiline were used, and 40 mmol of diamine represented by Chemical Formula 22 was used. The liquid crystal aligning agent containing 9) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-9) was 160,000.

(Example 10: Preparation of the liquid crystal aligning agent containing polyimide (PI-10))

53.3 g of the polyamic acid (PAA-5) solution prepared in Example 5 was dissolved in N-methyl-2-pyrrolidone (NMP) to 10% by weight, and then 1.7 g of pyridine and 2.2 g of acetic anhydride were added. The mixture was charged and subjected to a cyclization reaction at 80 ° C. for 2 hours, and then precipitated in methanol to obtain 49 g of a polymer powder having an imidation degree of 50%. After vacuum drying the polymer powder sufficiently, it was dissolved in N-methyl-2-pyrrolidone (NMP) to prepare a liquid crystal aligning agent containing polyimide (PI-10). Solid content of the above-mentioned liquid crystal aligning agent was 6.5 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PI-10) was 230,000.

(Example 11: Preparation of the liquid crystal aligning agent containing polyimide (PI-11))

53.3 g of the polyamic acid (PAA-8) solution prepared in Example 8 was dissolved in N-methyl-2-pyrrolidone (NMP) to 10% by weight, and then 5.1 g of pyridine and 5.5 g of acetic anhydride were added. A liquid crystal aligning agent including polyimide (PI-11) having an imidation degree of 80% was prepared in the same manner as in Example 10 except that the cyclization reaction was performed at 80 ° C. for 4 hours. Solid content of the above-mentioned liquid crystal aligning agent was 6.5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyimide (PI-11) was 230,000.

(Comparative Example 1: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-12))

Polyamic acid was carried out in the same manner as in Example 1, except that 0.5 mol of para-phenylenediamine and 0.49 mol of 4,4-methylenedianiline were used and 0.01 mmol of 2,4-diaminophenoxyoctadecane was used. The liquid crystal aligning agent containing (PAA-12) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-12) was 160,000.

(Comparative Example 2: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-13))

Polyamic acid was carried out in the same manner as in Example 1 except that 0.5 mol of para-phenylenediamine and 0.3 mol of 4,4-methylenedianiline were used and 0.2 mol of 2,4-diaminophenoxyhexadecane was used. The liquid crystal aligning agent containing (PAA-13) was manufactured. Solid content of the said liquid crystal aligning agent was 5 weight%, and the viscosity was 24 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-13) was 160,000.

(Comparative Example 3: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-14))

Polyamic acid was carried out in the same manner as in Example 7, except that 0.5 mol of para-phenylenediamine and 0.49 mol of 4,4-methylenedianiline were used and 0.01 mol of 2,4-diaminophenoxyhexadecane was used. The liquid crystal aligning agent containing (PAA-14) was manufactured. Solid content of the said liquid crystal aligning agent was 5 weight%, and the viscosity was 24 cps. Moreover, the weight average molecular weight of the said polyamic acid (PAA-14) was 160,000.

(Comparative Example 4: Preparation of liquid crystal aligning agent containing polyamic acid (PAA-15))

Polyamic acid was carried out in the same manner as in Example 7, except that 0.5 mol of para-phenylenediamine and 0.3 mol of 4,4-methylenedianiline were used and 0.2 mol of 2,4-diaminophenoxyhexadecane was used. The liquid crystal aligning agent containing (PAA-15) was manufactured. Solid content of the produced liquid crystal aligning agent was 5 weight%, and the viscosity was 23 cps. In addition, the weight average molecular weight of the said polyamic acid (PAA-15) was 160,000.

(Comparative Example 5: Production of liquid crystal aligning agent containing polyimide (PI-16))

53.3 g of the polyamic acid (PAA-13) solution obtained in Comparative Example 2 was dissolved in N-methyl-2-pyrrolidone (NMP) to 10% by weight, and then 0.1 mole of pyridine and 0.1 mole of acetic anhydride were added. The mixture was charged and subjected to a cyclization reaction at 80 ° C. for 2 hours, and then precipitated in methanol to obtain 49 g of a polymer powder having an imidation degree of 50%. After vacuum drying this polymer powder sufficiently, it melt | dissolved in N-methyl- 2-pyrrolidone (NMP) and manufactured the liquid crystal aligning agent containing polyimide (PI-16). Solid content of the above-mentioned liquid crystal aligning agent was 6.5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyimide (PI-16) was 230,000.

(Comparative Example 6: Production of liquid crystal aligning agent containing polyimide (PI-17))

53.3 g of the polyamic acid (PAA-15) solution obtained in Comparative Example 4 was dissolved in N-methyl-2-pyrrolidone (NMP) to 10% by weight, and then 1.7 g of pyridine and 2.2 g of acetic anhydride were added. After the reaction, the reaction was carried out for 4 hours at 80 ° C., and then precipitated in methanol to obtain 49 g of polymer powder having an imidation degree of 80%. After the polymer powder was sufficiently dried in vacuo, it was dissolved in N-methyl-2-pyrrolidone (NMP) to prepare a liquid crystal aligning agent containing polyimide (PI-17). Solid content of the above-mentioned liquid crystal aligning agent was 6.5 weight%, and the viscosity was 25 cps. Moreover, the weight average molecular weight of the said polyimide (PI-17) was 230,000.

Printability rating

The liquid crystal aligning agent prepared in Examples 1 to 11 and Comparative Examples 1 to 6 was 0.1 μm thick on a 10 cm × 10 cm sized glass substrate to which indium-tin oxide (ITO) was attached. Spin-coated with. This was then placed on a hot plate and subjected to a desolvent process at 70 ° C. and a curing process at 210 ° C. Using the naked eye and an optical microscope, the spreading property of the liquid crystal aligning agent and the number of pinholes of the sample were confirmed, and the printability of the liquid crystal aligning agent was evaluated. The results are shown in Table 1 below. The evaluation criteria of printability are as follows.

Printability Evaluation Criteria

Good: Less than 15 pinholes and no radial pattern

Moderate: More than 15 pinholes and less than 30 and weak radial pattern

Poor: More than 30 pinholes and radial pattern

Chemical resistance evaluation

The liquid crystal aligning agent prepared in Examples 1 to 11 and Comparative Examples 1 to 6 was 0.1 μm thick on a 10 cm × 10 cm sized glass substrate to which indium-tin oxide (ITO) was attached. Spin-coated with. This was then placed on a hot plate and subjected to a desolvent process at 70 ° C. and a curing process at 210 ° C. Subsequently, after the rubbing process was performed, the surface of the formed liquid crystal alignment layer was sufficiently washed with isopropyl alcohol and deionized water. Subsequently, the liquid crystal cell was assembled by injecting the liquid crystal, and the driving was performed by applying a voltage of 1V to 2V to the produced liquid crystal cell, and the presence or absence of generation of spots by the cleaning solvent was observed. Shown in The evaluation criteria of chemical resistance are as follows.

<Chemical Resistance Evaluation Criteria>

Good: no stain

Poor: Spotted

Evaluation of the pretilt angle and liquid crystal alignment property of the liquid crystal aligning film

In order to evaluate the liquid-crystal orientation of the liquid crystal aligning agent, the liquid crystal cell was produced and used. The manufacture of the liquid crystal cell is as follows.

To remove ITO from other parts, leaving only 1.5 cm x 1.5 cm square ITO shape and electrode ITO shape for voltage application on a glass substrate with standardized size of indium-tin oxide (ITO) Patterned using a photolithography process.

The liquid crystal aligning agents prepared in Examples 1 to 11 and Comparative Examples 1 to 6 were applied to the patterned ITO substrate, spin-coated to a thickness of 0.1 μm, and then subjected to curing at 70 ° C. and 210 ° C.

After rubbing the two substrates rubbed using a rubbing machine (Shindo K.K.), the cells were bonded to each other so as to maintain a cell gap of 50 μm. After filling the liquid crystal in the cell prepared in this manner, the liquid crystal alignment was observed using a cross-polarized optical microscope, and then the pretilt angle was measured using a crystal rotation method. The results are shown in Table 1 below. At this time, evaluation criteria of liquid crystal alignment are as follows.

<Liquid crystal orientation evaluation criteria>

Good: no discernment

Poor: Discretion occurs

Electrical property evaluation

The electrical properties of the liquid crystal alignment film were evaluated by measuring voltage holding ratio (VHR) at room temperature and 60 ° C. using a liquid crystal cell having a 4.75 μm cell gap. The results are shown in Table 1 below.

The voltage retention ratio refers to the extent to which the liquid crystal layer in the state of floating with the external power source maintains the charged voltage during the non-selection period in the active driving type TFT-LCD, and a value close to 100% is ideal.

  TABLE 1

Liquid crystal aligning agent Pretilt angle (°) Printability Liquid crystal alignment Chemical resistance Voltage retention rate (%) Room temperature 60 ℃ Example 1 4.1 Good Good Good 99.2 98.2 Example 2 6.6 Good Good Good 99.3 98.3 Example 3 89.3 Good Good Good 99.2 98.5 Example 4 89.6 Good Good Good 99.4 98.5 Example 5 89.8 Good Good Good 99.0 97.9 Example 6 89.9 Good Good Good 99.3 98.1 Example 7 4.0 Good Good Good 99.2 98.2 Example 8 89.6 Good Good Good 99.3 98.3 Example 9 89.9 Good Good Good 99.3 98.1 Example 10 89.7 Good Good Good 99.7 98.8 Example 11 89.9 Good Good Good 99.8 98.9 Comparative Example 1 3.3 Good Bad Bad 98.8 94.2 Comparative Example 2 87.6 Good Bad Bad 98.9 94.6 Comparative Example 3 3.6 Good Bad Bad 98.8 95.2 Comparative Example 4 87.6 Good Bad Bad 98.8 95.1 Comparative Example 5 87.8 Good Bad Bad 99.0 96.6 Comparative Example 6 87.7 Good Bad Bad 99.2 96.9

As shown in Table 1, the liquid crystal navigator prepared in Examples 1 to 11 is excellent in printability, liquid crystal alignment and chemical resistance, it can be confirmed that can be effectively used in the preparation of the liquid crystal alignment film. On the other hand, the liquid crystal aligning agent prepared in Comparative Examples 1 to 6 has good printability, but may be limited in use in manufacturing the liquid crystal alignment layer due to poor liquid crystal alignment and chemical resistance.

When the electrical characteristics of the liquid crystal aligning film in the case of using the liquid crystal aligning agent manufactured in Examples 1-11 and the liquid crystal aligning agent manufactured in Comparative Examples 1-6 are compared, the liquid crystal aligning manufactured in the said Examples 1-11 It can be seen that the use of the agent exhibits an excellent or equivalent level of voltage retention than the case of using the liquid crystal aligning agent prepared in Comparative Examples 1 to 6.

In addition, as shown in Table 1, the pretilt angles of the Examples 3 to 6, and Examples 8 to 11 are all 89.3 ° or more can be confirmed that can be effectively used in the vertical alignment liquid crystal alignment film, the Example In the case of 1, 2 and 7, it can be confirmed that the pretilt angle can be effectively used in the twisted nematic liquid crystal alignment film in the range of 4.0 ° to 6.6 °. On the other hand, in Comparative Example 2 and Comparative Examples 4 to 6, since the pretilt angle is in the range of 87.6 ° to 87.8 °, use of the vertical alignment type liquid crystal alignment layer may be limited.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims (10)

A liquid crystal aligning agent comprising a polymer selected from the group consisting of a polyamic acid comprising a repeating unit represented by the following formula (1), a polyimide comprising a repeating unit represented by the following formula (2), and a combination thereof: [Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, X ₁ and X ₂ are the same or different from each other, and each independently a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride, Y ₁ and Y ₂ are the same or different from each other, each independently a divalent organic group derived from a diamine, the diamine includes a functional diamine represented by the following formula (3), (3)

In Chemical Formula 3, A ₁ is the same or different from each other, and each independently a single bond, O, COO, CONH, OCO, or a substituted or unsubstituted C1 to C10 alkylene group, R ₁ is the same or different from each other, and each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, R ₂ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, n ₁ is an integer of 1 to 4, n ₂ is an integer of 0 to 3. The method of claim 1, Wherein the diamine further comprises at least one of aromatic diamines represented by the following Chemical Formulas 4 to 7: [Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 4 to 7, R ₃ to R ₁₂ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group, and the hetero The aryl group may further include one selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and combinations thereof, A ₂ to A ₇ are the same or different from each other, and each independently a single bond, O, SO ₂ or C (R ₁₀₃ ) (R ₁₀₄ ), wherein R ₁₀₃ and R ₁₀₄ are the same or different from each other, each independently Hydrogen or a substituted or unsubstituted C1 to C6 alkyl group, n ₃ to n ₁₂ are each independently an integer of 0 to 4; The method of claim 2, Wherein the diamine comprises the functional diamine and the aromatic diamine in a molar ratio of 1:99 to 40:60. The method of claim 1, The polyamic acid is a liquid crystal aligning agent having a weight average molecular weight of 10,000 to 300,000. The method of claim 1, The polyimide is a liquid crystal aligning agent having a weight average molecular weight of 10,000 to 300,000. The method of claim 1, When the liquid crystal aligning agent includes the polyamic acid and the polyimide, the liquid crystal aligning agent containing the polyamic acid and the polyimide in a weight ratio of 1:99 to 50:50. The method of claim 1, The liquid crystal aligning agent having a solid content of 1 to 15% by weight. The method of claim 1, The liquid crystal aligning agent having a viscosity of 3 to 30 cps. The liquid crystal aligning film manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 1-8 to a board | substrate. A liquid crystal display device comprising the liquid crystal alignment film according to claim 9.