KR101474794B1 - Liquid crystal alignment agent, liquid crystal alignment film manufactured using same, and liquid crystal display device including the liquid crystal alignment film - Google Patents

Abstract

A polyamic acid containing a repeating unit represented by the formula (1) and having a terminal end group at both terminals, a polyimide containing a repeating unit represented by the formula (2) and having terminal end groups at both terminals, and combinations thereof And a liquid crystal aligning agent containing the polymer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device, and more particularly, to a liquid crystal display device including the liquid crystal alignment layer, the liquid crystal alignment layer, the liquid crystal alignment layer, and the liquid crystal alignment layer.

A liquid crystal alignment film produced using the liquid crystal alignment film, and a liquid crystal display device including the liquid crystal alignment film.

A liquid crystal display device (LCD) uses a liquid crystal alignment film, and a polymeric material is mainly used for the liquid crystal alignment film. The liquid crystal alignment layer serves as a director for the arrangement of the liquid crystal molecules, so that when the liquid crystal moves due to an electric field to form an image, the liquid crystal alignment layer is oriented appropriately. In general, it is essential to uniformly orient the liquid crystal in order to obtain a uniform brightness and a high contrast ratio in a liquid crystal display device.

Conventionally, a rubbing method in which a polymer film such as polyimide is applied to a substrate such as glass and the surface of the polymer film is rubbed with a fiber such as nylon or polyester in a predetermined direction is used as a conventional method of orienting the liquid crystal. However, the rubbing method may cause fine dust or electrostatic discharge (ESD) when the fiber and the polymer film are rubbed, which can cause a serious problem in manufacturing the liquid crystal panel.

In order to solve the problems of the rubbing method, recently, an optical alignment method for inducing anisotropy (anisotropy) in a polymer film by light irradiation instead of friction and arranging liquid crystals using the anisotropy has been studied.

Polymers containing photo-functional groups such as azobenzene, cumarine, chalcone, and cinnamate have been developed as materials that can be used for the photo-alignment method. These polymers undergo anisotropic reactions such as photoisomerization and photocatalytic reaction by polarized light irradiation, resulting in anisotropy on the surface of the polymer and inducing the molecular arrangement of the liquid crystal in one direction.

In order to improve the vertical alignment property, a polymer prepared by using a functional diamine containing an alkyl group is used for a liquid crystal aligning agent.

However, when the polymer contains a large amount of the photo-functional group and the alkyl group, the printing property is deteriorated and a problem may occur in the processability.

Therefore, it is necessary to develop a polymer which can improve the processability while maintaining excellent electrical characteristics, optical properties, and liquid crystal alignment properties of the liquid crystal aligning agent.

Disclosed is a liquid crystal aligning agent excellent in printability, electrical characteristics, optical characteristics and liquid crystal alignability.

And a liquid crystal alignment layer produced using the liquid crystal aligning agent.

And a liquid crystal display element including the liquid crystal alignment layer.

According to one embodiment, there is provided a polyimide comprising a repeating unit represented by the following general formula (1) and having a terminal end group at both terminals, a polyimide including a repeating unit represented by the following general formula (2) And a polymer selected from the group consisting of a combination of a polymerizable monomer and a polymerizable monomer.

[Chemical 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 is a tetravalent organic group derived from an alicyclic acid anhydride or an aromatic acid dianhydride,

Y ¹ and Y ² are the same or different from each other and are each independently a divalent organic group derived from a diamine.

The endblocker may be derived from monoamines or endblocking monomers of monoanhydrides.

The monoamines may include one selected from compounds represented by the following formulas (3-1) to (3-5) and combinations thereof, and the monoanhydrides may be represented by the following formulas (4-1) to ≪ / RTI > and combinations thereof.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

In the above formulas (3-1) to (3-5)

R ^a1 to R ^a8 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

w1 is an integer of 0 to 5,

w2, w3 and w4 are each independently an integer of 0 to 4,

w5 is an integer of 0 to 2,

w6 and w7 are each independently an integer of 0 to 3;

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

In Formulas 4-1 to 4-7,

R ^b1 to R ^b33 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ² and L ³ are the same or different and are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

Specifically, the monoamines may include one selected from aniline, toluidine, dimethyl aniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetophenone, and combinations thereof, Unahydrides are norbornene-2,3-dicarboxylic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, 3,6-epoxy -1,2,3,6-tetrahydrophthalic anhydride, isobutenylsuccinic anhydride, maleic anhydride, aconitic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, cis-1,2,3,6, -tetrahydrophthalic anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride) anhydride, itaconic anhydride (IA), citraconic anhydride, CA), 2,3-dimethylmaleic anhydride (DMMA), and combinations thereof.

The terminal endblock may be contained in an amount of 0.5 to 10 moles per 100 moles of the repeating unit contained in the polyamic acid and the polyimide.

The polyamic acid may include one selected from the compounds represented by the following formulas (1-1) to (1-3) and combinations thereof, and the polyimide may be a compound represented by the following formulas (2-1) to And the like.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above formulas 1-1 to 2-3,

The definitions for X ¹ , X ² , Y ¹ and Y ² are as defined in formulas (1) and (2)

R ¹ , R ² , R ²³ and R ²⁴ are the same or different and each independently represents a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C3 to C30 cycloaliphatic group, C7 to C30 fused cycloalkylaryl group,

R ³ to R ²² and R ²⁵ to R ⁴⁴ are the same or different and each independently represents hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

m1 to m3 and k1 to k3 are the same or different from each other and each independently an integer of 1 to 100;

The diamine is an aromatic diamine represented by the following formulas (5) to (8); Functional diamines represented by the following formulas (9) to (12); A photodiamine comprising one selected from the group consisting of azobenzene-based optical diamines, cinnamate-based optical diamines, chalcone-based optical diamines, cumarine-based optical diamines, and combinations thereof; And combinations thereof.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above formulas 5 to 8,

R ⁵⁰ to R ⁵⁹ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl Wherein the alkyl group, the aryl group and the heteroaryl group are selected from the group consisting of -O-, -CO-O-, -CO-NH-, -O-CO-, -NH-CO- and combinations thereof , ≪ / RTI >

A ¹ to A ⁶ are the same or different and each independently represents a single bond, -O-, -SO ₂ - or -C (R ²⁰³ ) (R ²⁰⁴ ) -, wherein R ²⁰³ and R ²⁰⁴ are the same Are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n1 to n10 each independently represent an integer of 0 to 4;

[Chemical Formula 9]

In the above formula (9)

R ⁶⁰ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ⁶¹ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n11 is an integer of 0 to 3;

[Chemical formula 10]

In Formula 10,

R ⁶¹ , R ⁶² and R ⁶³ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 A heteroaryl group,

A ⁷ is a single bond, -O-, -CO-O-, -CO-NH-, -O-CO-, -NH-CO- or a substituted or unsubstituted C1-

R ⁶⁴ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and the alkyl group, the aryl group, and the heteroaryl The group may further include one selected from the group consisting of -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO-,

n12 is an integer of 0 or 3,

n13 and n14 are each independently an integer of 0 to 4;

(11)

In Formula 11,

R ⁶⁵ and R ⁶⁶ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

n15 and n16 are each independently an integer of 0 to 4,

R ⁶⁷ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

A ⁸ and A ⁹ are the same or different and are each independently a single bond, -O-, -CO-O- or -O-CO-,

A ¹⁰ is a single bond, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O-CO-.

[Chemical Formula 12]

In Formula 12,

R ⁶⁸ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n17 is an integer of 0 to 3,

R ⁶⁹ is hydrogen, a substituted or unsubstituted C1 to C40 aliphatic organic group, a substituted or unsubstituted C2 to C40 aromatic organic group, or a substituted or unsubstituted C3 to C40 cycloaliphatic group,

A ¹¹ is a single bond, -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -CO-NH- or -NH-CO-.

Specifically, the photodiamine may include one selected from the compounds represented by the following general formulas (13) to (21) and combinations thereof.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In the above formulas 13 to 18,

S ¹ , S ² , S ⁴ , S ⁷ , S ⁸ , S ¹¹ , S ¹² , S ¹³ , S ¹⁶ , S ¹⁷ , S ¹⁸ , S ¹⁹ , S ²² , S ²⁴ , S ²⁵ , S ²⁶ , ²⁷ are the same or different and each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O- -ego,

S ³ , S ⁵ , S ⁶ , S ⁹ , S ¹⁰ , S ¹⁴ , S ²⁰ , S ²¹ and S ²³ are the same or different and each independently represents a substituted or unsubstituted C 1 to C 30 alkyl group, A C1 to C30 alkoxy group, or a substituted or unsubstituted C2 to C30 ether group,

R ⁷⁰ to R ⁹² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

n20, n23, n30 and n41 are each independently an integer of 0 to 3,

n21, n22, n24 to n29, n31 to n40 and n42 are each independently an integer of 0 to 4,

n43 is an integer of 0 to 5;

[Chemical Formula 19]

In the above formula (19)

R ⁹³ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

R ⁹⁴ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n44 is an integer of 0 to 4,

R ⁹⁵ and R ⁹⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,

R ⁹⁷ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 alicyclic A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group.

[Chemical Formula 20]

In the above formula (20)

R ⁹⁸ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

R ¹⁰² and R ¹⁰³ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

n45 and n46 are each independently an integer of 0 to 4,

R ⁹⁹ and R ¹⁰⁰ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,

R ¹⁰¹ represents hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloaliphatic group , A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group.

[Chemical Formula 21]

In Formula 21,

R ¹⁰⁴ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

R ¹⁰⁷ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n47 is an integer of 0 to 3,

R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group.

The functional diamine may include one selected from compounds represented by the following formulas (22-1) to (22-4) and combinations thereof, wherein the photo diamine is a compound represented by the following formula (23-1), a compound represented by the following formula ≪ / RTI > and combinations thereof.

[Formula 22-1]

[Formula 22-2]

[Formula 22-3]

[Chemical Formula 22-4]

[Formula 23-1]

[Formula 23-2]

.

.

In the liquid crystal aligning agent, the diamine may include the light diamine or the light diamine and the functional diamine.

When the diamine comprises the optical diamine and the functional diamine, the diamine may contain the optical diamine and the functional diamine in a molar ratio of 95: 5 to 5:95.

The polymer may have a weight average molecular weight (Mw) of 50,000 to 500,000 g / mol.

The liquid crystal aligning agent may have a solid content of 0.1 to 30% by weight.

The liquid crystal aligning agent may have a viscosity of 3 to 35 cps.

According to another embodiment, there is provided a liquid crystal alignment film prepared by applying the liquid crystal aligning agent to a substrate.

According to another embodiment, there is provided a liquid crystal display device including the liquid crystal alignment layer.

The liquid crystal aligning agent according to one embodiment can improve printability, electrical properties, optical properties and liquid crystal alignment properties.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one of the functional groups of the present invention is substituted with at least one substituent selected from halogen (-F, -Cl, -Br, or -I), a hydroxyl group, a nitro group, a cyano group, an amino group ^{_{(NH 2, NH (R 200}} ) , or N (R ²⁰¹⁾ (R ^202), wherein R ^200, R ²⁰¹ and R ²⁰² are the same or different, being each independently selected from C1 to C10 alkyl group) , A substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted alkyl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocycloalkyl group Substituted "

Unless otherwise specified in the present specification, the "alkyl group" means a C1 to C30 alkyl group, specifically a C1 to C20 alkyl group, the "cycloalkyl group" means a C3 to C30 cycloalkyl group, Means a C2 to C30 heterocycloalkyl group, specifically, a C2 to C20 heterocycloalkyl group, and the "alkylene group" means a C1 to C30 alkylene group, Specifically, a C1 to C20 alkylene group, an "alkoxy group" means a C1 to C30 alkoxy group, specifically a C1 to C20 alkoxy group, an "ether group" means a C2 to C30 ether group, Specifically refers to a C2 to C20 ether group, and the "cycloalkylene group" means a C3 to C30 cycloalkylene group, specifically C3 to C20 Means a C2 to C30 heterocycloalkylene group, specifically a C2 to C20 heterocycloalkylene group, and the "aryl group" means a C6 to C30 aryl group, Specifically, a C6 to C20 aryl group, and the "heteroaryl group" means a C2 to C30 heteroaryl group, specifically a C2 to C20 heteroaryl group, and the "arylene" group means a C6 to C30 arylene Quot; means a C6 to C20 arylene group, and the "heteroarylene group" means a C2 to C30 heteroarylene group, specifically, a C2 to C20 heteroarylene group, Means a C7 to C30 alkylaryl group, specifically a C7 to C20 alkylaryl group, and "halogen" means F, Cl, Br or I.

Also, unless otherwise specified herein, the heterocycloalkyl, heterocycloalkylene, heteroaryl and heteroarylene groups are each independently selected from the group consisting of N, O, S, Si or P heteroatoms in one ring in one Means a cycloalkyl group, cycloalkylene group, aryl group and arylene group which contain 3 carbon atoms and the remainder carbon.

"Aliphatic" as used herein, unless otherwise specified, refers to a C 1 to C 30 alkyl, a C 2 to C 30 alkenyl, a C 2 to C 30 alkynyl, a C 1 to C 30 alkylene, a C 2 to C 30 alkenylene, or a C 2 to C 30 alkynylene Means a C1 to C20 alkyl, a C2 to C20 alkenyl, a C2 to C20 alkynyl, a C1 to C20 alkylene, a C2 to C20 alkenylene or a C2 to C20 alkynylene, and the term "alicyclic" Means a C3 to C30 cycloalkyl, a C3 to C30 cycloalkenyl, a C3 to C30 cycloalkynyl, a C3 to C30 cycloalkylene, a C3 to C30 cycloalkenylene, or a 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, and "aromatic & C6 to C30 aryl, C2 to C30 heteroaryl, C6 to C30 arylene or C2 to C30 heteroarylene, specifically C6 to C20 aryl, C2 to C20 heteroaryl, C6 to C20 arylene or C2 to C20 Heteroarylene " means < / RTI >

Unless defined otherwise herein, the term "combination" generally means mixing or copolymerization, and in the case of alicyclic organic groups and aromatic organic groups, two or more rings may form a fused ring, or two or more rings may be single bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) -, -S (= O) 2 -, -Si (CH 3) 2 - _{, - (CH 2) p -} ( _{wherein, 1≤p≤2), - (CF 2} ) q - ( _{wherein, 1≤q≤2), -C (CH 3} ) 2 -, -C (CF 3) Means that they are connected to each other by a functional group of -C (O) ₂ -, -C (CH ₃ ) (CF ₃ ) - or -C (= O) NH-. Here, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

The liquid crystal aligning agent according to one embodiment comprises a polyamic acid having a repeating unit represented by the following formula (1) and having terminal end groups at both terminals, a polyimide having a repeating unit represented by the following formula (2) , And combinations thereof. ≪ / RTI >

[Chemical 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 is a tetravalent organic group derived from an alicyclic acid anhydride or an aromatic acid dianhydride,

Y ¹ and Y ² are the same or different from each other and are each independently a divalent organic group derived from a diamine.

Since the polymer includes a terminal endblock, it is possible to control the amount of the photo functional group and the alkyl group contained in the polymer, thereby improving the fairness such as printability while maintaining excellent electrical characteristics, optical characteristics, and liquid crystal orientation of the liquid crystal aligning agent have. Since the anhydride functional groups are not exposed at the ends of the polymer, the deterioration of the printability can be prevented or alleviated. In addition, since the amine group is not exposed at the end of the polymer, deterioration or deterioration of physical properties of the liquid crystal aligning agent, which may occur due to oxidation of the amine group, can be prevented. In some cases, when the terminal sealing group contains a polymerizable functional group such as a thermally polymerizable functional group or a photopolymerizable functional group, the mechanical properties of the liquid crystal alignment layer produced using the liquid crystal aligning agent may be improved.

Hereinafter, each component will be described in detail.

Polymer

The polymer is a polyamic acid having a repeating unit represented by the formula (1) and having a terminal end group at both terminals, a polyimide having a repeating unit represented by the formula (2) and having terminal end groups at both terminals, and combinations thereof And includes one selected.

The polyamic acid containing the repeating unit represented by the above formula (1) can be synthesized from an acid dianhydride and a diamine. The method of preparing a polyamic acid by copolymerizing the acid dianhydride with the diamine is not limited to the method known to be usable for the synthesis of polyamic acid.

As the acid anhydride, an alicyclic acid anhydride, an aromatic acid dianhydride, or a combination thereof may be used.

As the diamine, an aromatic diamine, a functional diamine, a photodiamine, and a combination thereof may be used. Specifically, as the diamine, the above-mentioned light diamine can be used, or the above-mentioned light diamine and the above-mentioned functional diamine can be mixed and used.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (CBDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene- Tetracarboxylic acid dianhydride (BODA), 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride (CPDA), 1, 2, 3, , 2,4,5-cyclohexanetetracarboxylic acid dianhydride (CHDA), 1,2,4-tricarboxy-3-methylcarboxycyclopentane dianhydride, 1,2,3,4-tetracarboxycyclopentane dianhydride , 2,3,5-tricarboxycyclopentyl acetic dianhydride (TCA-AH), and combinations thereof. However, the present invention is not limited thereto.

The tetravalent organic group derived from the alicyclic acid anhydride may include at least one of the functional groups represented by the following formulas (A) to (E), but is not limited thereto.

[Chemical Formula B] [Chemical Formula C]

[Chemical Formula D] [Chemical Formula E]

In Formulas A through E above,

R ^c1 are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

t1 is an integer of 0 to 3,

R ^c2 to R ^c8 are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group to be.

When t1 is an integer of 2 or more, the ^Rc1 may be the same or different from each other.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride (PMDA), biphthalic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), benzophenone tetracarboxylic acid dianhydride (BTDA), hexafluoroisopropylidenediphthalic acid Dianhydride (6-FDA), and combinations thereof. However, the present invention 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 (F) and a functional group represented by the following formula (G), but is not limited thereto.

[Chemical Formula F] [Chemical Formula G]

In the above formulas F and G,

R ^c9 and R ^c10 are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

R ^c11 and R ^c12 are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

t2 and t3 are each independently an integer of 0 to 3,

D ¹ is a single bond, -O-, -CO-, a substituted or unsubstituted C1 to C6 alkylene group (e.g. _{-C (CF 3) 2 -)} , substituted or unsubstituted C3 to C30 cycloalkylene group, Or a substituted or unsubstituted C2 to C30 heterocycloalkylene group.

When t2 is an integer of 2 or more, the ^Rc11 may be the same or different from each other. Similarly, when t3 is an integer of 2 or more, the ^Rc12 may be the same or different from each other.

Examples of the aromatic diamine include para-phenylenediamine (p-PDA), 4,4-methylenedianiline (MDA), 4,4-oxydianiline (ODA), meta bisaminophenoxydiphenyl sulfone (m- (P-BAPS), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafluoropropane (HF-BAPP), 1,4- Diamino-2-methoxybenzene, and combinations thereof, but is not limited thereto.

The aromatic diamine may be selected from compounds represented by the following formulas (5) to (8), and combinations thereof, but is not limited thereto.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above formulas 5 to 8,

R ⁵⁰ to R ⁵⁹ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , The alkyl group, the aryl group and the heteroaryl group are selected from the group consisting of -O-, -CO-O-, -CO-NH-, -O-CO-, -NH-CO- and combinations thereof Further,

A ¹ to A ⁶ are the same or different from each other, and each independently a single bond, -O-, -SO ₂ -, and the - or ^{-C (R 203) (R 204} ) -, for example -C (CF _{3) 2} Here, R ²⁰³ and R ²⁰⁴ are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n1 to n10 each independently represent an integer of 0 to 4;

If the n1 to n10 are each an integer of 2 or more, the R ⁵⁰ to R ⁵⁹ may be the same or different from each other, respectively.

Examples of the functional diamine include compounds represented by the following formulas (9) to (12), and combinations thereof, but are not limited thereto. In this case, some of the polyamic acids include a divalent organic group derived from the functional diamine. By including the divalent organic group derived from the functional diamine, the pretilt angle of the liquid crystal molecules in the liquid crystal alignment layer can be easily controlled, and the orientation property can be improved.

[Chemical Formula 9]

In the above formula (9)

R ⁶⁰ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ⁶¹ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n11 is an integer of 0 to 3;

When n11 is an integer of 2 or more, the R ^{61 's} may be the same or different from each other.

[Chemical formula 10]

In Formula 10,

R ⁶¹ , R ⁶² and R ⁶³ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 A heteroaryl group,

A ⁷ is a single bond, -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO- or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁶⁴ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and the alkyl group, the aryl group, and the heteroaryl The group may further include one selected from the group consisting of -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO-,

n12 is an integer of 0 or 3,

n13 and n14 are each independently an integer of 0 to 4;

When n12 to n14 are each an integer of 2 or more, R ⁶¹ to R ⁶³ may be the same or different from each other.

(11)

In Formula 11,

R ⁶⁵ and R ⁶⁶ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

n15 and n16 are each independently an integer of 0 to 4,

R ⁶⁷ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

A ⁸ and A ⁹ are the same or different and are each independently a single bond, -O-, -CO-O- or -O-CO-,

A ¹⁰ is a single bond, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O-CO-.

If the n15 and n16 are each an integer of 2 or more, the R ⁶⁵ and R ⁶⁶ may be the same or different from each other, respectively.

[Chemical Formula 12]

In Formula 12,

R ⁶⁸ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n17 is an integer of 0 to 3;

R ⁶⁹ is hydrogen, a substituted or unsubstituted C1 to C40 aliphatic organic group, a substituted or unsubstituted C2 to C40 aromatic organic group, or a substituted or unsubstituted C3 to C40 cycloaliphatic group, Or a substituted C3 to C30 alicyclic organic group. In one example, R ⁶⁹ may be an organic group having a steroid skeleton, and in another example, R ⁶⁹ may be substituted with 1 to 15 fluorine atoms.

A ¹¹ is a single bond, -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -CO-NH- or -NH-CO-.

When n17 is an integer of 2 or more, the R < ⁶⁸ > s may be the same or different from each other.

As the above-mentioned light diamines, azobenzene-based light diamines, cinnamate-based light diamines, kallar-based light diamines, coumarin-based light diamines, and combinations thereof may be used.

The cinnamate-based optical diamine may include but is not limited to one selected from the compounds represented by the following formulas (13) to (19) and combinations thereof.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In the above formulas 13 to 18,

S ¹ , S ² , S ⁴ , S ⁷ , S ⁸ , S ¹¹ , S ¹² , S ¹³ , S ¹⁶ , S ¹⁷ , S ¹⁸ , S ¹⁹ , S ²² , S ²⁴ , S ²⁵ , S ²⁶ , ²⁷ are the same or different and each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O- -ego,

S ³ , S ⁵ , S ⁶ , S ⁹ , S ¹⁰ , S ¹⁴ , S ²⁰ , S ²¹ and S ²³ are the same or different and each independently represents a substituted or unsubstituted C 1 to C 30 alkyl group, A C1 to C30 alkoxy group, or a substituted or unsubstituted C2 to C30 ether group, especially a fluorine-substituted C1 to C30 alkoxy group,

R ⁷⁰ to R ⁹² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

n20, n23, n30 and n41 are each independently an integer of 0 to 3,

n21, n22, n24 to n29, n31 to n40 and n42 are each independently an integer of 0 to 4,

n43 is an integer of 0 to 5;

If the n20 and n42 are each an integer of 2 or more, the R ⁷⁰ to R ⁹² may be the same or different from each other, respectively.

[Chemical Formula 19]

In the above formula (19)

R ⁹³ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

The substituted alkylene group in R ⁹³ may be an alkylene group in which hydrogen is substituted with halogen or cyano group; At least one non-adjacent -CH ₂ - group of said alkylene group is substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted cycloalkylene group, substituted or unsubstituted heterocycloalkylene group, - O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 205 -, -NR 206 -CO-, - ^{CO-NR 207 -, -NR 208} -CO-O-, -O-CO-NR 209 -, -NR 210 -CO-NR 211 -, -CH = CH-, -C≡C-, -O-, or CO-O-; Or a combination thereof, wherein R ²⁰⁵ to R ^{211, which} may be the same or different from each other, are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

R ⁹⁴ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n44 is an integer of 0 to 4,

R ⁹⁵ and R ⁹⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,

In R ⁹⁵ and R ⁹⁶ , the substituted alkyl group is an alkyl group in which hydrogen is substituted with a hetero atom or a cyano group; An alkyl group in which at least one non-adjacent -CH ₂ - group of the alkyl group is substituted with -O-, -CO-O-, -O-CO-, or -CH = CH-; Or a combination thereof,

R ⁹⁷ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 alicyclic A substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group,

The substituted alkyl group in R ⁹⁷ is preferably an alkyl group in which hydrogen is substituted with halogen or cyano group; An alkyl group in which at least one non-adjacent -CH ₂ - group of the alkyl group is substituted with -O-, -CO-O-, -O-CO-, or -CH = CH-; Or a combination thereof,

The substituted alkylaryl group in R ^{97 is selected} from the group consisting of alkyl substituted with one or more non-adjacent -CH ₂ - groups of the alkylaryl group -O-, -CO-O-, -O-CO-, or -CH = Lt; / RTI >

If the n44 is an integer 2 or more, the R ⁹⁴ may be the same or different from each other, respectively.

The calconic optical diamine may include, but is not limited to, a compound represented by the following general formula (20).

[Chemical Formula 20]

In the above formula (20)

R ⁹⁸ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

The substituted alkylene group in R < ⁹⁸ > is an alkylene group in which hydrogen is substituted with halogen or cyano group; At least one non-adjacent -CH ₂ - group of said alkylene group is substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted cycloalkylene group, substituted or unsubstituted heterocycloalkylene group, - O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 212 -, -NR 213 -CO-, - CO-NR ²¹⁴ -, -NR ²¹⁵ -CO-O-, -O-CO-NR ²¹⁶ -, -NR ²¹⁷ -CO-NR ²¹⁸ , -CH = CH-, An alkylene group substituted with -O-; Or a combination thereof, wherein R ²¹² to R ²¹⁸ are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

R ¹⁰² and R ¹⁰³ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

n45 and n46 are each independently an integer of 0 to 4,

R ⁹⁹ and R ¹⁰⁰ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,

The substituted alkyl group for R < ⁹⁹ > and R < ¹⁰⁰ > is an alkyl group in which hydrogen is substituted by halogen or cyano group; An alkyl group in which at least one non-adjacent -CH ₂ - group of the alkyl group is substituted with -O-, -CO-O-, -O-CO-, or -CH = CH-; Or a combination thereof,

R ¹⁰¹ represents hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloaliphatic group , A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group,

The substituted alkyl group in R < ¹⁰¹ > is an alkyl group in which hydrogen is substituted by halogen or cyano group; An alkyl group in which at least one non-adjacent -CH ₂ - group of the alkyl group is substituted with -O-, -CO-O-, -O-CO-, or -CH = CH-; Or a combination thereof,

The substituted alkylaryl groups are -CH ₂ adjacent to one or more of the ratio of the alkylaryl group in the R ¹⁰¹ - group -O-, -CO-O-, alkyl substituted with -O-CO-, or -CH = CH- Lt; / RTI >

When n45 and n46 are each an integer of 2 or more, R ¹⁰² and R ¹⁰³ may be the same or different from each other.

The coumarin-based optical diamine may include, but is not limited to, a compound represented by the following formula (21).

[Chemical Formula 21]

In Formula 21,

R ¹⁰⁴ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,

The substituted alkylene group in R ¹⁰⁴ is an alkylene group in which hydrogen is substituted with halogen or cyano group; At least one non-adjacent -CH ₂ - group of said alkylene group is substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted cycloalkylene group, substituted or unsubstituted heterocycloalkylene group, - O-, -CO-, -CO-O-, -O-CO-, -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, -NR ²¹⁹ -, -NR ²²⁰ -CO-, CO-NR ²²¹ -, -NR ²²² -CO-O-, -O-CO-NR ²²³ -, -NR ²²⁴ -CO-NR ²²⁵ -, -CH = CH-, CO-O-; Or a combination thereof, wherein R ²¹⁹ to R ^{225, which} may be the same or different from each other, are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

R ¹⁰⁷ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n47 is an integer of 0 to 4,

R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,

The substituted alkyl group for R < ¹⁰⁵ > and R < ¹⁰⁶ > is an alkyl group in which hydrogen is substituted by halogen or cyano group; An alkyl group in which at least one non-adjacent -CH ₂ - group of the alkyl group is substituted with -O-, -CO-O-, -O-CO-, or -CH = CH-; Or a combination thereof.

When n47 is an integer of 2 or more, R ¹⁰⁷ may be the same or different from each other.

Specifically, the functional diamine may include one selected from compounds represented by the following formulas (22-1) to (22-4) and combinations thereof, and the photo diamine may be a compound represented by the following formula 23-2, and combinations thereof. However, the present invention is not limited thereto.

[Formula 22-1]

[Formula 22-2]

[Formula 22-3]

[Chemical Formula 22-4]

[Formula 23-1]

[Formula 23-2]

When the diamine comprises the optical diamine and the functional diamine, the diamine may contain the optical diamine and the functional diamine in a molar ratio of 95: 5 to 5:95. In this case, the pretilt angle during formation of the alignment film can be adjusted as desired. Specifically, the diamine may include the light diamine and the functional diamine in a molar ratio of 95: 5 to 60:40.

The polyimide including the repeating unit represented by the formula (2) can be prepared by imidizing a polyamic acid containing the repeating unit represented by the formula (1). A method for producing polyimide by imidizing polyamic acid is well known in the art, so a detailed description thereof will be omitted.

The polyamic acid including the repeating unit represented by the formula (1) and the polyimide including the repeating unit represented by the formula (2) are encapsulated at both ends with terminal end groups.

The terminal endblock can be derived from a terminal blocking monomer, examples of which include monoamines or monoanhydrides.

For example, when the polyamic acid and the polyimide are used in the presence of an acid anhydride in an amount greater than that of the diamine, an anhydride functional group is positioned at the terminal thereof. Therefore, the monoamines are used as a terminal blocking monomer, The end of the polyimide can be sealed.

As another example, when the diamine is used in a molar amount higher than that of the acid dianhydride in the production of the polyamic acid and the polyimide, the amine group is located at the terminal, so that the monoanhydride is used as a terminal blocking monomer, And the end of the polyamic acid and the polyimide can be sealed.

The monoamines may include one selected from compounds represented by the following formulas (3-1) to (3-5) and combinations thereof, and the monoanhydrides may be represented by the following formulas (4-1) to But are not limited to, those selected from compounds and combinations thereof.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

In the above formulas (3-1) to (3-5)

R ^a1 to R ^a8 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

w1 is an integer of 0 to 5,

w2, w3 and w4 are each independently an integer of 0 to 4,

w5 is an integer of 0 to 2,

w6 and w7 are each independently an integer of 0 to 3;

When each of w1 to w7 is an integer of 2 or more, R ^a1 to R ^a3 and R ^a5 to R ^a8 may be the same or different from each other.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

In Formulas 4-1 to 4-7,

R ^b1 to R ^b33 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ² and L ³ are the same or different and are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

Specifically, the monoamines may include one selected from aniline, toluidine, dimethyl aniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetophenone, and combinations thereof. It is not.

Specifically, the monoanhydrides may be norbornene-2,3-dicarboxylic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, isobutenylsuccinic anhydride, maleic anhydride, aconitic anhydride, 3,4 , 5,6-tetrahydrophthalic anhydride, cis-1,2,3,6, -tetrahydrophthalic anhydride (cis-1,2, 3,6-tetrahydrophthalic anhydride, itaconic anhydride (IA), citraconic anhydride (CA), 2,3-dimethylmaleic anhydride , DMMA), and combinations thereof, but is not limited thereto.

Both ends of the polyamic acid and the polyimide are sealed with the end capping agent as described above so that the amine groups and the anhydride functional groups are not exposed at the ends of the polyamic acid and the polyimide. Also, the amount of the photo functional group and the alkyl group contained in the polyamic acid and the polyimide can be controlled. The above-mentioned functional groups and alkyl groups contained in the functional diamines can induce anisotropy by polarized light irradiation and improve the vertical orientation, but are functional groups that adversely affect the processability, for example, the printability.

As a result, the liquid crystal aligning agent prepared using the polyamic acid and the polyimide can have excellent processability, for example, printability, while maintaining excellent electrical characteristics, optical characteristics, and liquid crystal alignability.

On the other hand, when the terminal endblocker is formed using a polymerizable functional group such as a terminal blocking monomer containing a thermosetting functional group or a photopolymerizable functional group, the mechanical properties of the liquid crystal alignment layer produced using the liquid crystal aligning agent may be improved .

The terminal endblock may be contained in an amount of 0.5 to 10 moles per 100 moles of the repeating unit contained in the polyamic acid and the polyimide. In this case, it is possible to effectively improve the fairness, particularly the printability and spreadability. Specifically, the end capping agent may be contained in an amount of 1 to 8 moles per 100 moles of the repeating units contained in the polyamic acid and the polyimide.

The polyamic acid encapsulated with the terminal sealing group may include one selected from the compounds represented by the following general formulas (1-1) to (1-3) and combinations thereof, and the polyimide encapsulated with the terminal end- The compounds represented by formulas (2-1) to (2-3), and combinations thereof, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above formulas 1-1 to 2-3,

The definitions for X ¹ , X ² , Y ¹ and Y ² are as defined in formulas (1) and (2)

R ¹ , R ² , R ²³ and R ²⁴ are the same or different and each independently represents a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C3 to C30 cycloaliphatic group, C7 to C30 fused cycloalkylaryl group,

R ³ to R ²² and R ²⁵ to R ⁴⁴ are the same or different and each independently represents hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

m1 to m3 and k1 to k3 are the same or different from each other and each independently an integer of 1 to 100;

The polymer may have a weight average molecular weight (Mw) of 50,000 to 500,000 g / mol. When the weight average molecular weight of the polymer is within the above range, the solubility, thermal stability, and chemical resistance can be effectively improved, an appropriate viscosity can be maintained, excellent printability can be obtained, and a uniform film can be easily formed.

menstruum

The liquid crystal aligning agent includes a solvent suitable for dissolving the polymer. As a result, the liquid crystal aligning agent can have excellent spreadability and adhesiveness to a substrate.

Examples of suitable solvents for dissolving the polymer include N-methyl-2-pyrrolidone; N, N-dimethylacetamide; N, N-dimethylformamide; Dimethyl sulfoxide; ? -butyrolactone; Tetrahydrofuran (THF); And phenol-based solvents such as methacrole, phenol, and halogenated phenol, but are not limited thereto.

The solvent may further include 2-butyl cellosolve (2-BC), thereby improving printability. The 2-butyl cellosolve may be contained in an amount of 1 to 50% by weight, specifically 10 to 40% by weight based on the total weight of the solvent including 2-butyl cellosolve. When the content of 2-butyl cellosolve is within the above range, the printing property can be easily improved. 　

In addition, the solvent may further include alcohols, ketones, esters, ethers, hydrocarbons, or halogenated hydrocarbons, which are poor solvents, at an appropriate ratio within the range in which the soluble polyimide polymer is not precipitated. The poor solvent can lower the surface energy of the liquid crystal aligning agent and improve the spreadability and flatness upon application.

The poor solvent may be contained in an amount of 1 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 And examples of the solvent include acetates, diethyl oxalate, malonic acid esters, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenyl methyl ether, 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 Hydroxy-2-methylethylpropionate, ethoxyethyl acetate, hydroxyethyl acetate, 2-hydroxy-2-methylpropionate, 3-methoxypropionate, 3-methoxyethyl propionate, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, methyl methoxy propionate, Ethoxybutanol, ethylethoxybutanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene , Hexane, heptane, octane, benzene, toluene, xylene, and combinations thereof.

Although the content of the solvent in the liquid crystal aligning agent is not particularly limited, it can be used so that the solid content in the liquid crystal aligning agent is 0.1 to 30% by weight, specifically, the solid content is 1 to 10% by weight Can be used. When the content of the solid content is within the above range, the uniformity of the film can be appropriately maintained, the viscosity can be maintained properly, and the uniformity of the film due to the high viscosity during printing can be prevented And can exhibit an appropriate transmittance.

The liquid crystal aligning agent may have a viscosity of 3 to 35 cps, and more specifically, a viscosity of 5 to 25 cps. 　 When the viscosity of the liquid crystal aligning agent is within the above range, it is possible to improve the film uniformity and coatability.

Other additives

The liquid crystal aligning agent according to one embodiment may further include other additives.

Examples of 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 contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polymer, and specifically 1 to 30 parts by weight. When the epoxy compound is contained within the above range, reliability and electro-optical characteristics can be easily improved while exhibiting appropriate printing property and flatness upon application to a substrate.

Examples of the epoxy compound include compounds represented by the following formula (24), but are not limited thereto.

≪ EMI ID =

In the formula (24)

A ¹² is a substituted or unsubstituted C6 to C12 aromatic organic group or a substituted or unsubstituted divalent C6 to C12 alicyclic group or a substituted or unsubstituted divalent C6 to C12 aliphatic group such as a substituted or unsubstituted Or a substituted 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, N ', N'-tetraglycidyl-4,4'-diaminophenyl ethane, N, N, N' 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 diglycidyl ether, N, N ', N'-tetramethyl-2,2-dibromonopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Tetraglycidyl-1,4-phenylenediamine, N, N, N ', N'-tetraglycidyl-m-xylenediamine, N, N, N' N, N, N ', N'-tetramethylpiperidine, N, N'- , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,3- Diglycidylaminomethyl) benzene, and the like, but are not limited thereto.

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

A liquid crystal alignment film according to another embodiment is manufactured using the liquid crystal aligning agent.

The liquid crystal alignment layer can be formed by applying a liquid crystal aligning agent to a substrate. Examples of the method of applying the liquid crystal aligning agent to the substrate include a spin coating method, a flexo printing method, and an ink jet method. Among them, the flexographic printing method can be generally used because the uniformity of the formed coating film is excellent and it is easy to enlarge it.

The substrate is not particularly limited as long as it is a substrate having high transparency. A glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Also, if a substrate on which an indium-tin oxide (ITO) electrode for liquid crystal driving is formed is used, the manufacturing process can be simplified.

The liquid crystal aligning agent is uniformly applied on a substrate to increase the uniformity of the coating film, and then the liquid crystal aligning agent is applied to the substrate at a temperature of room temperature to 200 ° C, specifically 30 ° C to 150 ° C, more specifically 40 ° C to 120 ° C Drying can be carried out at a temperature of 1 minute to 100 minutes. By adjusting the degree of volatilization of each component of the liquid crystal aligning agent through the above drying, a uniform and uniform coating film can be obtained.

Thereafter, firing is performed again at a temperature of 80 ° C to 300 ° C, specifically, 120 ° C to 280 ° C for 5 minutes to 300 minutes to evaporate the solvent, whereby a liquid crystal alignment film can be formed.

The liquid crystal alignment layer formed by the above method can be used in a liquid crystal display device without uniaxial alignment treatment in polarizing ultraviolet irradiation or in some applications such as a vertical alignment film.

Specifically, the liquid crystal alignment layer according to one embodiment can be subjected to uniaxial alignment treatment at an energy of 10 mJ to 5,000 mJ for 0.1 minute to 180 minutes.

According to another embodiment, there is provided a liquid crystal display device including the liquid crystal alignment layer.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, 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 liquid crystal aligning agent

In a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas introducing device and a condenser, 0.5 mol of the compound represented by the following formula (23-1) was put while nitrogen was passed through the flask and N-methyl- .

[Formula 23-1]

To the mixed solution was added 1.01 mol of 2,3,5-tricarboxycyclopentyl acetic dianhydride (TCA-AH) in a solid state and stirred vigorously.

0.4 mol of the compound represented by the above formula (23-1) and 0.1 mol of the compound represented by the following formula (23-2) were placed in the mixed solution and vigorously stirred. At this time, the solid content was 20% by weight.

Then, the reaction was carried out for 10 hours while maintaining the temperature at 30 to 50 DEG C to prepare a polyamic acid solution. 0.02 mol of aniline as a terminal blocking monomer was added to the polyamic acid solution prepared above and reacted for 1 hour.

Then, 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 DEG C, followed by reaction for 6 hours. The catalyst and the solvent were removed by vacuum distillation to obtain a soluble poly .

A mixed solvent of N-methyl-2-pyrrolidone and? -Butyrolactone (volume ratio = 7: 3) was added to the prepared soluble polyimide resin and stirred at room temperature for 24 hours to obtain polyimide (SPI- ) Was prepared.

[Formula 23-2]

Example 2 to 10: Preparation of liquid crystal aligning agent

(TCA-AH), a compound represented by the above formula (23-1), a compound represented by the above formula (23-2), a compound represented by the following formula (22-1), aniline , 2-norbornene-5,6-dicarboxylic anhydride and maleic anhydride were used as shown in the following Table 1, polyimide (SPI-2 To SPI-10) was prepared.

[Formula 22-1]

Comparative Example 1 and 2: Preparation of liquid crystal aligning agent

2,3,5-tricarboxycyclopentylacetic dianhydride (TCA-AH), the compound represented by Formula 23-1, the compound represented by Formula 23-2, and the compound represented by Formula 22-1 A liquid crystal aligning agent containing polyimide (SPI-11 to SPI-12) was prepared in the same manner as in Example 1, except that the step shown in Table 1 was used and the step of using the terminal blocking monomer was not carried out. .

TCA-AH (mol) 22-1 (mol) (Mol) 21-1 (mol) End blockade
Monomer
(mol) The weight average molecular weight (Mw, g / mol) The solid content in the liquid crystal aligning agent
(weight%) Viscosity of liquid crystal aligning agent
(cps) Example 1 1.01 0.90 0.10 - aniline
(0.02) 170k 5.5 11.0 Example 2 1.01 0.80 0.20 - aniline
(0.02) 170k 5.5 11.2 Example 3 1.01 0.70 0.10 0.20 aniline
(0.02) 169k 5.5 10.9 Example 4 1.01 0.60 0.10 0.30 aniline
(0.02) 170k 5.5 11.1 Example 5 1.01 0.50 0.10 0.40 aniline
(0.02) 171k 5.5 11.2 Example 6 1.02 0.60 0.10 0.30 aniline
(0.04) 170k 5.5 11.4 Example 7 1.03 0.60 0.10 0.30 aniline
(0.06) 172k 5.5 11.2 Example 8 0.99 0.60 0.10 0.30 2-norbornene-5,6-dicarboxylic anhydride
(0.02) 170k 5.5 11.0 Example 9 0.99 0.60 0.10 0.30 2-norbornene-5,6-dicarboxylic anhydride
(0.02) 172k 5.5 11.2 Example 10 0.99 0.60 0.10 0.30 Male
Anhydride
(0.02) 171k 5.5 11.4 Comparative Example 1 1.01 0.60 0.10 0.30 - 170k 5.5 11.2 Comparative Example 2 0.99 0.60 0.10 0.30 - 168k 5.5 10.7

≪ Evaluation of physical properties &

Test Example  1: Evaluation of printability and film uniformity

A liquid crystal cell was prepared and used for evaluating the printability and film uniformity of the liquid crystal aligning agent, for example, the uniformity of the coating film at the end. The manufacture of the liquid crystal cell is as follows.

The ITO glass substrate of the standardized size was patterned using a photolithography process to remove the ITO pattern of the square ITO shape of 1.5 cm × 1.5 cm and the ITO pattern of the electrode for voltage application.

Patterning one on the glass substrate with ITO is attached, the Examples 1 to 10 and Comparative Example 1, and the alignment film printing press for manufacturing a liquid crystal alignment agent from 2 to flexographic printing using (CZ 200 ^®, nakan社), 10 nm thickness, and then the printed substrate was allowed to stand on a hot plate at 50 ° C to 90 ° C for 2 to 5 minutes to dry the coating film.

After drying the substrate, the substrate was baked on a hot plate at 200 ° C to 230 ° C for 10 minutes to 30 minutes.

Was a film surface of the liquid crystal alignment film measuring visual and electron microscope (MX50 ^®, Olympus社) thickness variation of printability (pinhole and stain) and the coating film over the entire surface (the center portion and the end portion) substrate through, the result The results are shown in Table 2 below.

≪ Printability evaluation standard &

Good: no pinhole or stain

Poor: pinhole or stain occurs

≪ Evaluation Criteria of Coating Film Uniformity &

Good: When the variation of the film thickness in the entire coating film is less than 0.005 mu m

Normal: The variation of the film thickness in the entire coating film is 0.005 탆 to 0.01 탆

Bad: The deviation of the film thickness in the entire coating film exceeds 0.01 탆

Test Example  2: liquid crystal Orientation  evaluation

A liquid crystal cell was prepared and used to evaluate the liquid crystal alignment property of the liquid crystal aligning agent. The manufacture of the liquid crystal cell is as follows.

On the ITO glass substrate of the standardized size, a square ITO shape of 1.5 cm × 1.5 cm and an electrode for voltage application were patterned by using a photolithography process in order to leave only the ITO shape and remove ITO of the other part.

The patterned ITO substrate was coated with the liquid crystal aligning agent prepared in Examples 1 to 10 and Comparative Examples 1 and 2 and spin-coated to a thickness of 0.1 탆, followed by curing at 70 캜 and 210 캜.

The ITO substrate having undergone the curing process was exposed so that the exposure directions were opposite to each other (VA mode, 90 degrees) using an exposing machine (UIS-S2021J7-YD01, Ushio LPUV) After that, the square ITO shape was stuck up and down with keeping the cell gap of 4.75 ㎛. A 2 kW deep UV ramp (UXM-2000) was used as the light source during the exposure.

The cells thus prepared were filled with liquid crystal, and the liquid crystal alignability was observed using an orthogonal polarized optical microscope. The results are shown in Table 2 below.

<Evaluation Criteria of Liquid Crystal Orientation>

Good: No disclination

Bad: occurrence of disclination

Test Example  3: Electrical properties of liquid crystal alignment film

The electrical characteristics of the liquid crystal alignment layer were measured by measuring the voltage holding ratio (VHR) at room temperature by measuring the residual DC voltage by obtaining a voltage-transmittance curve using a liquid crystal cell having a cell gap of 4.75 μm. Also, ion density (ID) was measured. The results are shown in Table 2 below. 　

The electrical characteristics of the voltage holding ratio and the residual DC voltage will be briefly described as follows.

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

The residual DC voltage refers to the voltage applied to the liquid crystal layer even when the impurity of the ionized liquid crystal layer is adsorbed on the alignment layer and no voltage is externally applied. As a method for measuring the residual DC voltage, a method using a flicker and a method using a capacitance variation curve (C-V) of a liquid crystal layer depending on a DC voltage are common.

The ion density (ID) means the density of ionic impurities present in the liquid crystal cell, and reliability may deteriorate if the ionic density is higher than a certain level.

<Evaluation Criteria of Voltage Conservation Rate>

Good: 97% or more

Poor: Less than 97%

<Residual DC voltage evaluation criteria>

Good: Less than 100 mV

Poor: 100 mV or more

<Evaluation Criteria of Ion Density (ID)>

Good: Less than 50 pC / cm ³

Poor: 50pC / cm ³ or more

Printability Film uniformity Liquid crystal orientation Voltage holding ratio Residual DC voltage Ion density Example 1 Good Good Good Good Good Good Example 2 Good Good Good Good Good Good Example 3 Good Good Good Good Good Good Example 4 Good Good Good Good Good Good Example 5 Good Good Good Good Good Good Example 6 Good Good Good Good Good Good Example 7 Good Good Good Good Good Good Example 8 Good Good Good Good Good Good Example 9 Good Good Good Good Good Good Example 10 Good Good Good Good Good Good Comparative Example 1 Bad Bad Good Good Bad Bad Comparative Example 2 Bad Bad Good Good Good Good

As shown in Table 2, it can be confirmed that the liquid crystal detergents prepared in Examples 1 to 10 exhibited better printability and film uniformity than the liquid crystal aligning agents prepared in Comparative Examples 1 and 2. In addition, it can be confirmed that the liquid crystal detergents prepared in Examples 1 to 10 are superior to the liquid crystal aligning agents prepared in Comparative Examples 1 and 2, or have at least equivalent electrical characteristics.

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 (16)

A polyamic acid comprising a repeating unit represented by the following formula (1) and having a terminal end group at both terminals, a polyimide including a repeating unit represented by the following formula (2) and having terminal end groups at both terminals, and a &Lt; / RTI &gt;
A liquid crystal aligning agent comprising:
[Chemical 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 is a tetravalent organic group derived from an alicyclic acid anhydride or an aromatic acid dianhydride,
Y ¹ and Y ² are the same or different from each other and are each independently a divalent organic group derived from a diamine.
Provided that the terminal endblock is a monoamine containing one selected from the compounds represented by the following formulas (3-1) to (3-5) and combinations thereof, or a compound represented by the following formulas (4-1) to &Lt; RTI ID = 0.0 &gt; monoanhydride &lt; / RTI &gt;
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

In the above formulas (3-1) to (3-5)
R ^a1 to R ^a8 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,
w1 is an integer of 0 to 5,
w2, w3 and w4 are each independently an integer of 0 to 4,
w5 is an integer of 0 to 2,
w6 and w7 are each independently an integer of 0 to 3,
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

In Formulas 4-1 to 4-7,
R ^b1 to R ^b33 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L ² and L ³ are the same or different and are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
delete delete The method according to claim 1,
Wherein the monoamines include one selected from aniline, toluidine, dimethylaniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetophenone, and combinations thereof,
The monoanhydrides may be selected from the group consisting of 5-norbornene-2,3-dicarboxylic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, - epoxy-1,2,3,6-tetrahydrophthalic anhydride, isobutenylsuccinic anhydride, maleic anhydride, aconitic anhydride, 3,4,5, (3,4,5,6-tetrahydrophthalic anhydride), cis-1,2,3,6, -tetrahydrophthalic anhydride (cis-1,2,3,6 itaconic anhydride (IA), citraconic anhydride (CA), 2,3-dimethylmaleic anhydride (DMMA), tetrahydrophthalic anhydride, And combinations thereof. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
Wherein the terminal endblock is contained in an amount of 0.5 to 10 moles relative to 100 moles of the repeating unit contained in the polyamic acid and the polyimide.
The method according to claim 1,
Wherein the polyamic acid comprises one selected from the compounds represented by the following formulas (1-1) to (1-3) and combinations thereof,
Wherein the polyimide comprises one selected from the compounds represented by the following general formulas (2-1) to (2-3) and combinations thereof:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above formulas 1-1 to 2-3,
The definitions for X ¹ , X ² , Y ¹ and Y ² are as defined in formulas (1) and (2)
R ¹ , R ² , R ²³ and R ²⁴ are the same or different and each independently represents a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C3 to C30 cycloaliphatic group, C7 to C30 fused cycloalkylaryl group,
R ³ to R ²² and R ²⁵ to R ⁴⁴ are the same or different and each independently represents hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,
m1 to m3 and k1 to k3 are the same or different from each other and each independently an integer of 1 to 100;
The method according to claim 1,
The diamine is an aromatic diamine represented by the following formulas (5) to (8); Functional diamines represented by the following formulas (9) to (12); A photodiamine comprising one selected from the group consisting of azobenzene-based optical diamines, cinnamate-based optical diamines, chalcone-based optical diamines, cumarine-based optical diamines, and combinations thereof; And a combination of these.
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above formulas 5 to 8,
R ⁵⁰ to R ⁵⁹ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , The alkyl group, the aryl group and the heteroaryl group are selected from the group consisting of -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO- and combinations thereof Further,
A ¹ to A ⁶ are the same or different and each independently represents a single bond, -O-, -SO ₂ - or -C (R ²⁰³ ) (R ²⁰⁴ ) -, wherein R ²⁰³ and R ²⁰⁴ are the same Are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,
n1 to n10 each independently represents an integer of 0 to 4,
[Chemical Formula 9]

In the above formula (9)
R ⁶⁰ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
R ⁶¹ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
n11 is an integer of 0 to 3,
[Chemical formula 10]

In Formula 10,
R ⁶¹ , R ⁶² and R ⁶³ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 A heteroaryl group,
A ⁷ is a single bond, -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO- or a substituted or unsubstituted C1 to C10 alkylene group,
R ⁶⁴ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and the alkyl group, the aryl group, and the heteroaryl The group may further include one selected from the group consisting of -O-, -CO-O-, -CO-NH-, -NH-CO-, -O-CO-,
n12 is an integer of 0 or 3,
n13 and n14 are each independently an integer of 0 to 4,
(11)

In Formula 11,
R ⁶⁵ and R ⁶⁶ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,
n15 and n16 are each independently an integer of 0 to 4,
R ⁶⁷ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
A ⁸ and A ⁹ are the same or different and are each independently a single bond, -O-, -CO-O- or -O-CO-,
A ¹⁰ is a single bond, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O-
[Chemical Formula 12]

In Formula 12,
R ⁶⁸ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
n17 is an integer of 0 to 3,
R ⁶⁹ is hydrogen, a substituted or unsubstituted C1 to C40 aliphatic organic group, a substituted or unsubstituted C2 to C40 aromatic organic group, or a substituted or unsubstituted C3 to C40 cycloaliphatic group,
A ¹¹ is a single bond, -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -CO-NH- or -NH-CO-.
8. The method of claim 7,
Wherein the photoadiamine comprises one selected from the group consisting of compounds represented by the following formulas (13) to (21) and combinations thereof:
[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In the above formulas 13 to 18,
S ¹ , S ² , S ⁴ , S ⁷ , S ⁸ , S ¹¹ , S ¹² , S ¹³ , S ¹⁶ , S ¹⁷ , S ¹⁸ , S ¹⁹ , S ²² , S ²⁴ , S ²⁵ , S ²⁶ , ²⁷ are the same or different and each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-O-, -CO-NH-, -NH-CO- or -O- -ego,
S ³ , S ⁵ , S ⁶ , S ⁹ , S ¹⁰ , S ¹⁴ , S ²⁰ , S ²¹ and S ²³ are the same or different and each independently represents a substituted or unsubstituted C 1 to C 30 alkyl group, A C1 to C30 alkoxy group, or a substituted or unsubstituted C2 to C30 ether group,
R ⁷⁰ to R ⁹² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
n20, n23, n30 and n41 are each independently an integer of 0 to 3,
n21, n22, n24 to n29, n31 to n40 and n42 are each independently an integer of 0 to 4,
n43 is an integer of 0 to 5,
[Chemical Formula 19]

In the above formula (19)
R ⁹³ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,
R ⁹⁴ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
n44 is an integer of 0 to 4,
R ⁹⁵ and R ⁹⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,
R ⁹⁷ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 alicyclic A substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group,
[Chemical Formula 20]

In the above formula (20)
R ⁹⁸ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,
R ¹⁰² and R ¹⁰³ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,
n45 and n46 are each independently an integer of 0 to 4,
R ⁹⁹ and R ¹⁰⁰ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group,
R ¹⁰¹ represents hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C7 to C30 alkylaryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloaliphatic group , A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted naphthyl group,
[Chemical Formula 21]

In Formula 21,
R ¹⁰⁴ is a substituted or unsubstituted C6 to C30 aromatic diamine group or a substituted or unsubstituted C1 to C24 linear or branched alkylene group,
R ¹⁰⁷ are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
n47 is an integer of 0 to 3,
R ¹⁰⁵ and R ¹⁰⁶ are the same or different and are each independently hydrogen, halogen, cyano, or a substituted or unsubstituted C1 to C12 alkyl group.
8. The method of claim 7,
Wherein the functional diamine comprises one selected from the group consisting of compounds represented by the following formulas (22-1) to (22-4) and combinations thereof, wherein the photo diamine is a compound represented by the following formula (23-1) And a liquid crystal aligning agent which comprises one selected from the group consisting of a combination thereof,
[Formula 22-1]

[Formula 22-2]

[Formula 22-3]

[Chemical Formula 22-4]

[Formula 23-1]

[Formula 23-2]

.
8. The method of claim 7,
Wherein the diamine comprises the light diamine or the light diamine and the functional diamine.
11. The method of claim 10,
When the diamine comprises the optical diamine and the functional diamine, the diamine comprises the optical diamine and the functional diamine in a molar ratio of 95: 5 to 5:95.
The method according to claim 1,
Wherein the polymer has a weight average molecular weight (Mw) of 50,000 to 500,000 g / mol.
The method according to claim 1,
Wherein the liquid crystal aligning agent has a solid content of 0.1 to 30% by weight.
The method according to claim 1,
Wherein the liquid crystal aligning agent has a viscosity of 3 to 35 cps.
14. A liquid crystal alignment film produced by applying a liquid crystal aligning agent according to any one of claims 1 to 14 to a substrate.
A liquid crystal display device comprising the liquid crystal alignment film according to claim 15.