KR20130070228A - Liquid crystal alignment agent, liquid crystal alignment film manufactured using same, and liquid crystal display device including liquid crystal alignment film - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to improve permeability and response speed, to have excellent electrical characteristics such as voltage holding ratio and residual DC, and to easily control pretilt angle. CONSTITUTION: A liquid crystal alignment agent comprises 'polyamic acids with a repeating unit indicated as the chemical formula 1', 'polyimides with a repeating unit indicated as the chemical formula 2', and 'polymers with combinations of polymers selected from the group of their combinations. In the chemical formula 1 and 2, X^1 and X^2 are 'tetravalent organic radicals respectively induced from alicyclic acid dianhydrides or aromatic acid dianhydrides' and Y^1 and Y^2 are 'divalent organic radicals respectively induced from diamines', and the diamines contains 'a diamine capable of cross-linking indicated as the chemical formula 3'.

Description

Liquid crystal aligning agent, the liquid crystal aligning film manufactured using the same, and the liquid crystal display device containing the liquid crystal aligning film TECHNICAL FIELD

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 into a liquid crystal aligning agent for producing a high-performance liquid crystal alignment film 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 has been made.

One embodiment of the present invention provides a liquid crystal aligning agent that can improve the transmittance and response speed, is excellent in electrical characteristics such as voltage retention and residual DC, and can easily control the pretilt angle.

Another embodiment of the present invention provides a liquid crystal alignment layer manufactured using the liquid crystal alignment agent.

Another embodiment of the present invention provides a liquid crystal display device including the liquid crystal alignment layer.

According to one embodiment of the present invention, a polyamic acid including a repeating unit represented by the following Chemical Formula 1, a polyimide comprising a repeating unit represented by the following Chemical Formula 2 and a polymer selected from the group consisting of a combination thereof It provides a liquid crystal aligning agent.

[Formula 1]

[Formula 2]

In the above 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 crosslinkable diamine represented by the following Formula (3).

(3)

In Formula 3,

R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group,

n ₁ is an integer of 0 to 3,

Q ¹ is a divalent organic group represented by -O-, -CO0-, -NHCO-, -CONH- or -OCO-,

Z ¹ is a single bond, a substituted or unsubstituted divalent C3 to C30 aliphatic organic group, a substituted or unsubstituted divalent C3 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group Or a divalent C3 to C30 aromatic and alicyclic organic group,

Q ² is -O-, -COO-, -NHCO-, -CONH-, -OCO- or ^a -COOR - and (R is ^a cycloaliphatic organic group of C2 to C10) 2-valent organic group represented by the

Z ² is a divalent C 2 to C 20 aliphatic organic group,

Q ³ is a divalent organic group represented by -O-, -COO-, -NHCO-, -CONH- or -OCO-,

R ² is hydrogen (H) or methyl group (CH ₃ ).)

Specific examples of the crosslinkable diamine represented by Chemical Formula 3 may include at least one selected from the group consisting of compounds represented by Chemical Formulas 4 to 6 and combinations thereof.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

In addition, the diamine may further include one selected from the group consisting of aromatic diamines, functional diamines, and combinations thereof.

When the diamine includes a diamine selected from the group consisting of aromatic diamines, functional diamines, and combinations thereof, together with the crosslinkable diamine represented by Formula 3, the content of crosslinkable diamine represented by Formula 3 is It may be 0.05 mol% to 99 mol%, and may be 5 mol% to 90 mol% with respect to the total weight of the diamine.

When the diamine includes all of the crosslinkable diamines, aromatic diamines, and functional diamines represented by Formula 3, 0.05 to 99 mol% of the crosslinkable diamines represented by Formula 3, based on the total amount of the diamines, 0.05 to 99 mol% of the aromatic diamine, and 0.05 to 99 mol% of the functional diamine may be included. The content of the crosslinkable diamine may be 5 mol% to 90 mol%, the content of the aromatic diamine may be 5 mol% to 90 mol%, and the content of the functional diamine may be 5 mol% to 30 mol%.

The polymer may have a weight average molecular weight (Mw) of 10,000 to 500,000.

The liquid crystal aligning agent may have a solid content of 1% by weight to 30% by weight.

According to another embodiment of the present invention to provide a liquid crystal alignment film prepared by applying the liquid crystal aligning agent to a substrate.

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

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

Transmittance, response speed, 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 the 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 the present specification, "*" means the same or different atom or part connected to a chemical 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 the above 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 crosslinkable 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 Formula 3,

R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group,

n ₁ is an integer of 0 to 3,

Q ¹ is a divalent organic group represented by -O-, -CO0-, -NHCO-, -CONH- or -OCO-,

Z ¹ is a single bond, a substituted or unsubstituted divalent C3 to C30 aliphatic organic group, a substituted or unsubstituted divalent C3 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group Or a divalent C3 to C30 aromatic and alicyclic organic group,

Q ² is -O-, -COO-, -NHCO-, -CONH-, -OCO- or ^a -COOR - and (R is ^a cycloaliphatic organic group of C2 to C5) 2-valent organic group represented by the

Z ² is a divalent C 2 to C 20 aliphatic organic group,

Q ³ is a divalent organic group represented by -O-, -COO-, -NHCO-, -CONH-, or -OCO-,

R ² is hydrogen (H) or methyl group (CH ₃ ).

The crosslinkable diamine represented by Formula 3 includes residues derived from acrylate or methacrylate at the terminal, and residues derived from acrylate or residues derived from methacrylate react with light irradiation. Cause Therefore, when the liquid crystal aligning agent is prepared using the crosslinkable diamine represented by the above formula (3), when the light irradiation is applied to the liquid crystal aligning agent, the molecular shape of the liquid crystal can be induced in one direction, and thus the alignment property is effectively It can be improved.

Specifically, the crosslinkable diamine represented by Formula 3 may include at least one selected from the group consisting of a compound represented by Formula 4 to Formula 6 and a combination thereof, but is not limited thereto.

  [Formula 4]

[Chemical Formula 5]

[Formula 6]

The diamine may further include at least one of a reactive diamine and a functional diamine, in addition to the crosslinkable diamine represented by Chemical Formula 3.

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 for producing 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 the diamine, a crosslinkable diamine represented by the formula (3) may be used, and at least one of predetermined functional diamines and predetermined aromatic diamines may be further mixed and used therein.

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 , 2,3,5-tricarboxycyclopentylacetic dianhydride or a mixture of one or more thereof may be used, but is not limited thereto.

The tetravalent organic group derived from the alicyclic acid dianhydride may include at least one of functional groups represented by the following Chemical Formulas 9 to 13, but is not limited thereto.

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

In Chemical Formulas 9 to 13,

R ³ 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 ₂ is an integer of 0 to 3,

R ⁴ to R ¹⁰ are the same or different from each other, and are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

When n ₂ is an integer of 2 or more, R ³ 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 Formula 14 and a functional group represented by the following Formula 15, but is not limited thereto.

[Formula 14]

[Formula 15]

In Chemical Formulas 14 and 15,

R ¹¹ and R ¹² 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 ¹³ and R ¹⁴ 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 ₃ and n ₄ are each independently an integer of 0 to 3,

A ³ 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 ₃ is an integer of 2 or more, R ¹³ may be the same or different from each other. Similarly, when n ₄ is an integer of 2 or more, R ¹⁴ 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 aromatic diamine may include at least one of the compounds represented by the following Chemical Formulas 16 to 19, but is not limited thereto. In this case, the polyamic acid and the polyimide may include 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.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

In Chemical Formulas 16 to 19,

R ¹⁵ to 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, 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 ⁴ to A ⁹ are the same or different from each other, and 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 ₅ to n ₁₄ are each independently an integer of 0 to 4;

When n ₅ is an integer of 2 or more, R ¹⁵ may be the same or different from each other. Similarly, when n ₆ to n ₁₄ are each an integer of 2 or more, the R ¹⁶ to R ²⁴ may be the same or different from each other.

The functional diamine may include at least one of the compounds represented by the following Chemical Formulas 20 to 23, but is not limited thereto. In this case, the polyamic acid and the polyimide will include 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.

[Chemical Formula 20]

In the above formula (20)

R ²⁵ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ²⁶ are the same or different from each other, and each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n ₁₅ is an integer from 0 to 3.

When n ₁₅ is an integer of 2 or more, each of R ²⁶ may be the same or different from each other.

[Chemical Formula 21]

In Formula 21,

R ²⁷ , R ²⁸ and R ²⁹ 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 ¹⁰ is a single bond, O, COO, CONH, OCO, or a substituted or unsubstituted C1 to C10 alkylene group,

R ³⁰ 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 ²⁷ 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 ²⁸ and R ²⁹ may be the same or different from each other.

[Chemical Formula 22]

In Formula 22,

R ³¹ and R ³² 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 ³³ is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

A ¹¹ and A ¹² are the same or different from each other, and each independently a single bond, O or COO,

A ¹³ is a single bond, O, COO, CONH or OCO.

When n ₁₉ is an integer of 2 or more, R ³¹ may be the same or different from each other. Similarly, when n ₂₀ is an integer of 2 or more, R ³² may be the same or different from each other.

(23)

In Formula 23, A ¹⁴ is a divalent organic group represented by -O-, -CO-, -COO-, -NH-, -NHCO-, -CONH-, -S- or -OCO-, and R ³⁴ Is hydrogen, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, the alicyclic organic group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and a steroid skeleton It is a monovalent organic group which has, and 1-15 of the hydrogen atoms which R <^34> has may be substituted by a fluorine atom.

When the diamine includes the aromatic diamine, the functional diamine, or a combination thereof together with the crosslinkable diamine represented by Formula 3, the content of crosslinkable diamine represented by Formula 3 is 0.05 based on the total amount of diamine. It may be from mol% to 99 mol%, may be from 5 mol% to 90 mol%. When the content of the crosslinkable diamine represented by Chemical Formula 3 is included in the above range, there may be an advantage that a fast response speed may be realized.

When the diamine includes all of the crosslinkable diamine represented by Formula 3, the aromatic diamine, and the functional diamine, the crosslinkable diamine represented by Formula 3 is 0.05 mol% to 99 mol based on the total amount of the diamine. %, The aromatic diamine may be 0.05 mol% to 99 mol%, the functional diamine may be 0.05 mol% to 99 mol%. In addition, the crosslinkable diamine represented by the formula (3) is 5 mol% to 90 mol%, the aromatic diamine may be 5 mol% to 90 mol%, the functional diamine may be 5 mol% to 30 mol%.

When the amount of each diamine is within the above range, it is possible to effectively control the pretilt angle and the expression of the high pretilt angle, and also to effectively improve the liquid crystal alignment, chemical resistance, electro-optical properties, thermal stability and mechanical properties. In addition, the processability can be improved by increasing the solubility.

The polymer, ie, polyamic acid and polyimide, may each have a weight average molecular weight (Mw) of 10,000 to 500,000.

When the weight average molecular weight of the polymer is within the above range, it is possible to effectively improve reliability and electro-optical properties, have excellent chemical resistance, and maintain the pretilt angle stably 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 contained within the above ranges, the orientation stability can be improved. Specifically, the polyamic acid and the polyimide may be included in a weight ratio of 10:90 to 50:50.

In the liquid crystal aligning agent, the polymer may be included in an amount of 1 wt% to 30 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 1% by weight to 25% 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; ? -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 wt% to 60 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.

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 of the precipitation of the soluble polyimide polymer. 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 wt% to 90 wt%, specifically 1 wt% to 70 wt%, 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, Or these can be used in mixture of 1 or more types.

The content of the solvent in the liquid crystal aligning agent is not particularly limited, but may be used so that the content of solids in the liquid crystal aligning agent is 1% by weight to 30% 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 1 wt% to 25 wt%.

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 for improving the reliability and the electro-optical property, and the epoxy compound may use at least one epoxy compound containing 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.

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 digly 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 are 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.

Since the liquid crystal aligning agent can form a pretilt even by UV irradiation regardless of the rubbing method, by applying a liquid crystal aligning agent as described above to form a film and then irradiating UV to impart alignment ability to the film. A liquid crystal aligning film can be manufactured. The UV irradiation is DC 1 to 100V 　 Under voltage application, the light is irradiated with an energy of 2 to 100 J to form an orientation, but is not necessarily limited to this range.

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

Example

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 1: Preparation of liquid crystal aligning agent containing polyimide (PSPI-1)

0.79 mol of para-phenylenediamine while passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, and a functional diamine represented by the following Chemical Formula 26: 3,5-dia 0.2 mole of minophenyldecyl succinimide (3,5-diaminophenyldecyl succinimide) and 0.01 mole of diamine represented by the following Chemical Formula 4 were added thereto, and N-methyl-2-pyrrolidone (NMP) was added thereto to prepare a mixed solution.

[Formula 4]

(26)

1.0 mol of solid solid 2,3,5-tricarboxycyclopentylacetic dianhydride was added to the mixed solution, followed by vigorous stirring. Solid content at this time is 20% by weight, the reaction was carried out for 10 hours while maintaining the temperature at 30 ℃ to 50 ℃. N-methyl-2-pyrrolidone was added thereto and stirred at room temperature for 24 hours to prepare a polyamic acid solution.

3.0 mol of acetic anhydride and 5.0 mol of pyridine were added to the prepared polyamic acid solution, and the temperature was raised to 80 ° C., followed by reaction for 6 hours. The catalyst and the solvent were removed by vacuum distillation to obtain a polyimide having a solid content of 20%. The solution was prepared. A mixed organic solvent (volume ratio = 50: 40: 10) of N-methyl-2-pyrrolidone, γ-butyrolactone and 2-butyl cellosolve was added thereto, followed by stirring at room temperature for 24 hours for polyimide The liquid crystal aligning agent containing (PSPI-1) was manufactured. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-1) was 190,000.

Example 2: Preparation of liquid crystal aligning agent containing polyimide (PSPI-2)

A liquid crystal aligning agent including polyimide (PSPI-2) was prepared in the same manner as in Example 1 except for using the functional diamine represented by the following Chemical Formula 27 instead of the functional diamine represented by the Chemical Formula 26. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-2) was 200,000.

(27)

Example 3: Preparation of liquid crystal aligning agent containing polyimide (PSPI-3)

A liquid crystal aligning agent including polyimide (PSPI-3) was prepared in the same manner as in Example 1 except for using the functional diamine represented by the following Chemical Formula 28 instead of the functional diamine represented by the Chemical Formula 26. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-3) was 170,000.

(28)

Example 4: Preparation of liquid crystal aligning agent containing polyimide (PSPI-4)

A liquid crystal aligning agent including polyimide (PSPI-4) was prepared in the same manner as in Example 1 except for using the functional diamine represented by the following Chemical Formula 29 instead of the functional diamine represented by the Chemical Formula 26. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-3) was 210,000.

[Formula 29]

Example 5: Preparation of liquid crystal aligning agent containing polyimide (PSPI-5)

Polyimide (PSPI-5) was included in the same manner as in Example 1 except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 26, and 0.3 mole of diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-5) was 190,000.

Example 6: Preparation of liquid crystal aligning agent containing polyimide (PSPI-6)

Polyimide (PSPI-6) was included in the same manner as in Example 2 except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 27, and 0.3 mole of diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-6) was 200,000.

Example 7: Preparation of liquid crystal aligning agent containing polyimide (PSPI-7)

Polyimide (PSPI-7) was prepared in the same manner as in Example 3, except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 28, and 0.3 mole of diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-7) was 160,000.

Example 8: Preparation of liquid crystal aligning agent containing polyimide (PSPI-8)

Polyimide (PSPI-8) was prepared in the same manner as in Example 3 except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Chemical Formula 29, and 0.3 mole of diamine of Chemical Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-8) was 185,000.

Example 9: Preparation of liquid crystal aligning agent containing polyimide (PSPI-9)

Polyimide (PSPI-9) was included in the same manner as in Example 1 except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 26, and 0.7 mol of the diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-9) was 190,000.

Example 10 Preparation of Liquid Crystal Alignment Agent Containing Polyimide (PSPI-10)

A polyimide (PSPI-10) was prepared in the same manner as in Example 2 except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 27, and 0.7 mol of the diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-10) was 170,000.

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

Polyimide (PSPI-11) was prepared in the same manner as in Example 3 except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 28, and 0.7 mol of the diamine of Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-11) was 230,000.

Example 12 Preparation of Liquid Crystal Alignment Agent Containing Polyimide (PSPI-12)

Polyimide (PSPI-12) was included in the same manner as in Example 3, except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Chemical Formula 29, and 0.7 mol of the diamine of Chemical Formula 4 were used. A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-12) was 230,000.

Example 13: Preparation of liquid crystal aligning agent containing polyimide (PSPI-13)

Polyimide (PSPI-13) in the same manner as in Example 1, except that 0.1 mol of the functional diamine represented by Formula 26 and 0.9 mol of the diamine of Formula 4 were used without using para-phenylenediamine. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-13) was 180,000.

Example 14 Preparation of Liquid Crystal Alignment Agent Containing Polyimide (PSPI-14)

Polyimide (PSPI-14) in the same manner as in Example 2, except that 0.1 mol of the functional diamine represented by Chemical Formula 27 and 0.9 mol of the diamine of Chemical Formula 4 were used without using para-phenylenediamine. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-14) was 170,000.

Example 15 Preparation of Liquid Crystal Alignment Agent Containing Polyimide (PSPI-15)

Polyimide (PSPI-15) in the same manner as in Example 3, except that 0.1 mol of the functional diamine represented by Chemical Formula 28 and 0.9 mol of the diamine of Chemical Formula 4 were used without using para-phenylenediamine. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-15) was 200,000.

Example 16: Preparation of Liquid Crystal Alignment Agent Containing Polyimide (PSPI-16)

Polyimide (PSPI-15) in the same manner as in Example 3, except that 0.1 mol of the functional diamine represented by Chemical Formula 29 and 0.9 mol of the diamine of Chemical Formula 4 were used without using para-phenylenediamine. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-16) was 180,000.

Comparative Example 1: Preparation of liquid crystal aligning agent containing polyimide (PSPI-17)

Polyimide (PSPI-17) in the same manner as in Example 1, except that 0.7 mol of para-phenylenediamine and 0.3 mol of the functional diamine represented by Chemical Formula 26 were used, and the diamine of Chemical Formula 4 was not used. ), A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-17) was 210,000.

Comparative Example 2: Preparation of liquid crystal aligning agent containing polyimide (PSPI-18)

Polyimide (PSPI-18) in the same manner as in Example 2, except that 0.7 mol of para-phenylenediamine and 0.3 mol of the functional diamine represented by Chemical Formula 27 were used, and the diamine of Chemical Formula 4 was not used. ), A liquid crystal aligning agent was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-18) was 240,000.

Comparative Example 3: Preparation of liquid crystal aligning agent containing polyimide (PSPI-19)

Polyimide (PSPI-19) in the same manner as in Example 3, except that 0.7 mol of para-phenylenediamine and 0.3 mol of the functional diamine represented by Chemical Formula 28 were used, and the diamine of Chemical Formula 4 was not used. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-19) was 220,000.

Comparative Example 4: Preparation of liquid crystal aligning agent containing polyimide (PSPI-20)

Polyimide (PSPI-20) in the same manner as in Example 3, except that 0.7 mol of para-phenylenediamine and 0.3 mol of the functional diamine represented by Chemical Formula 29 were used, and the diamine of Chemical Formula 4 was not used. A liquid crystal aligning agent containing was prepared. Solid content of the produced liquid crystal aligning agent was 7 weight%. In addition, the weight average molecular weight of the said polyimide (PSPI-20) was 220,000.

Test Example 1: Evaluation of the vertical alignment of the liquid crystal alignment layer (difference of pretilt angle (Δ pretilt) with the standard liquid crystal cell) and electro-optical characteristics

In order to evaluate the vertical alignment property of a liquid crystal aligning agent, the liquid crystal cell was produced and used. The manufacture of the liquid crystal cell is as follows.

To remove other parts of the ITO, leaving only a 3 cm x 6 cm square ITO shape and an 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 16 and Comparative Examples 1 to 4 were applied to the patterned ITO substrates, spin-coated to a thickness of 0.1 μm, and then subjected to curing at 80 ° C. and 220 ° C.

The spacers were spread on one substrate, and the sealant was applied on the other substrate, and then assembled to maintain a cell gap of 3.25 mu m by thermal compression. The liquid crystal for VA mode was inject | poured into the empty cell using the capillary phenomenon, and then sealed with the UV hardening bond for end sealing, and the test liquid crystal cell was produced.

The vertical alignment of the liquid crystal cell produced by the above method was observed using an orthogonally polarized optical microscope. After confirming the vertical alignment, a liquid crystal cell having good vertical alignment was selected as a standard liquid crystal cell, and the pretilt angle of the standard liquid crystal cell was 90 °. Subsequently, each liquid crystal cell was irradiated with UV energy under electric field application, and a pretilt angle was measured using a crystal rotation method, and the pretilt angle measured for each liquid crystal cell and the wire diameter of the standard liquid crystal cell were measured. Table 1 shows the difference from the square as Δpretilt.

In addition, the voltage holding ratio (VHR) of each liquid crystal cell was measured at 25 ° C. by applying a voltage of 1V to the liquid crystal cell fabricated as described above, and the remaining of each liquid crystal cell was applied by applying a voltage of −10V to + 10V. DC (RDC) voltage was measured.

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

The residual DC voltage refers to a voltage applied to the liquid crystal layer even when no impurities are applied from the ionization layer to the alignment layer. The residual DC voltage was measured by the method using the capacitance change curve (CV) of the liquid crystal layer.

Test Example 2: Response Speed Evaluation

While alternatingly applying voltages of AC 6.5V and AC 0.1V to each test liquid crystal cell manufactured in Test Example 1, a change in transmittance is recorded in real time using an oscilloscope (a voltage of AC 6.5V is applied). At the moment, the transmittance rises from 0% to 100%, and when the voltage of AC 0.1V is applied, the transmittance decreases from 100% to 0%). The response rate is usually the sum of the time taken to reach from 10% to 90% of the transmission (rising time, T _on ) and the time of falling from 90% to 10% of the transmission (falling time, T _off ), where rising time (T _on ) was measured and compared. The results are shown in Table 1 below.

sample Perpendicular
Orientation Voltage
Retention rate (%) Residual DC
(mV) △ pretilt
(˚) Response speed
(rising, ms) Example 1 Good 99.2 37 0.1 39 Example 2 Good 99.0 43 0.2 37 Example 3 Good 98.9 48 0.2 35 Example 4 Good 99.0 47 0.1 33 Example 5 Good 98.9 41 0.5 28 Example 6 Good 98.8 42 0.4 29 Example 7 Good 98.9 48 0.3 31 Example 8 Good 98.9 48 0.2 32 Example 9 Good 99.0 40 0.6 22 Example 10 Good 98.8 46 0.7 19 Example 11 Good 98.6 37 0.8 16 Example 12 Good 98.7 39 0.7 20 Example 13 Good 99.1 46 1.2 10 Example 14 Good 99.0 44 1.0 13 Example 15 Good 98.9 48 1.0 11 Example 16 Good 98.8 49 1.1 11 Comparative Example 1 Good 99.0 32 0.0 46 Comparative Example 2 Good 98.8 37 0.0 43 Comparative Example 3 Good 98.7 41 0.0 47 Comparative Example 4 Good 98.6 45 0.0 43

As shown in Table 1, the liquid crystal locator prepared in Examples 1 to 16 is excellent in the vertical alignment, liquid crystal alignment and electrical properties, it can be seen that can be effectively used in the preparation of the liquid crystal alignment film.

However, as shown in Table 1, the liquid crystal cell prepared by using the liquid crystal navigator prepared in Examples 1 to 16 after light irradiation compared to the liquid crystal cell prepared using the liquid crystal aligning agent prepared in Comparative Examples 1 to 4 While Δpretilt is produced in the range of about 0.1 to 1.1 °, good liquid crystal alignment is observed, whereas in the case of the liquid crystal aligning agent prepared in Comparative Examples 1 to 4, Δpretilt is not generated, so that the liquid crystal alignment is poor. In addition, the response speed was also about 4 ms to 37 compared to the liquid crystal cell prepared using the liquid crystal aligning agent prepared in Examples 1 to 16 compared to the liquid crystal cell prepared using the liquid crystal aligning agent prepared in Comparative Examples 1 to 4. We can see that ms has improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (9)

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]

(2)

In the above 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 crosslinkable diamine represented by the following Formula (3).
(3)

(3)
R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group,
n ₁ is an integer of 0 to 3,
Q ¹ is a divalent organic group represented by -O-, -CO0-, -NHCO-, -CONH-, or -OCO-,
Z ¹ is a single bond, a substituted or unsubstituted divalent C3 to C30 aliphatic organic group, a substituted or unsubstituted divalent C3 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group Or a divalent C3 to C30 aromatic and alicyclic organic group,
Q ² is -O-, -COO-, -NHCO-, -CONH-, -OCO- or ^a -COOR - and (R is ^a cycloaliphatic organic group of C2 to C10) 2-valent organic group represented by the
Z ² is a divalent C 2 to C 20 aliphatic organic group,
Q ³ is a divalent organic group represented by -O-, -COO-, -NHCO-, -CONH- or -OCO-,
R ² is hydrogen (H) or methyl group (CH ₃ ).)
The method of claim 1,
The crosslinkable diamine represented by Chemical Formula 3 may include at least one selected from the group consisting of a compound represented by the following Chemical Formulas 4 to 6 and combinations thereof.
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The method of claim 1,
Wherein the diamine further comprises one selected from the group consisting of aromatic diamines, functional diamines, and combinations thereof.
The method of claim 3,
The diamine is a liquid crystal aligning agent containing 0.05 to 99 mol% of crosslinkable diamines represented by the formula (3) based on the total amount of the diamine.
The method of claim 1,
The diamine is 0.05 to 99 mol% of the crosslinkable diamine represented by the formula (3), 0.05 to 99 mol% of the aromatic diamine, and 0.05 to 99 mol% of the functional diamine Liquid crystal aligning agent.
The method of claim 1,
The polymer is a liquid crystal aligning agent having a weight average molecular weight of 10,000 to 500,000.
The method of claim 1,
The liquid crystal aligning agent having a solid content of 1% to 30% by weight.
The liquid crystal aligning film manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 1-7 to the board | substrate.
A liquid crystal display device comprising the liquid crystal alignment film according to claim 8.