KR101333711B1 - Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device including the liquid crystal alignment film - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 2에서,
X¹, X², Y¹　및 Y²는 명세서에서 정의한 바와 같다.It provides a liquid crystal aligning agent comprising a first polymer comprising 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), or a combination thereof.
[Formula 1]

(2)

In the above Formulas 1 and 2,
X ¹ , X ² , Y ¹ and Y ² are as defined in the specification.

Description

Liquid crystal aligning agent, a liquid crystal aligning film manufactured using the same, and a liquid crystal display device comprising the liquid crystal aligning film.

The present substrate relates to a liquid crystal aligning agent, a liquid crystal aligning film prepared using the same, and a liquid crystal display device comprising the liquid crystal aligning film.

A liquid crystal display (LCD) uses a liquid crystal alignment film. As the liquid crystal alignment film, a polymer material is mainly used.

The liquid crystal alignment layer acts as a director in the array of liquid crystal molecules, thereby allowing the liquid crystal to move in an electric field to form an appropriate direction. Generally, in order to obtain uniform brightness and high contrast ratio, it is essential to orient the liquid crystal uniformly in the liquid crystal display device.

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

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

As a material that can be used in the photo-alignment method, a study has been made on diamines containing optical functional groups such as azobenzene, cumarine, chalcene, and cinnamate. To prepare a diamine having such a photofunctional group, dinitro having excellent stability should be used, but in the process of preparing diamine using dinitro, a double bond that may cause a reaction such as photocrosslinking may be broken by polarized light irradiation. There is a concern that there is a problem that is difficult to apply to the photo-alignment agent. In addition, there is a problem in that the process for producing a diamine containing a photofunctional group is too complicated and economical.

One aspect of the present invention is capable of photo-alignment at low energy, excellent texture excellent vertical alignment, chemical resistance, stable liquid crystal orientation, easy liquid crystal dropping, excellent substrate adhesion, electro-optical properties, excellent afterimage reliability, It is to provide a liquid crystal aligning agent that can exhibit a texture excellent in processability.

Another aspect of the present invention is to provide a liquid crystal aligning film produced using a liquid crystal aligning agent.

Another aspect of the present invention is to provide a liquid crystal display device including the liquid crystal alignment layer.

In one aspect of the present invention, a liquid crystal alignment 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 Offer

[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, wherein the diamine is 35 to 90 mol% of a diamine represented by the following Formula 3, and a diamine 5 represented by the following Formula 4. To 20 mol% and 5 to 45 mol% of diamine represented by the following Chemical Formula 5.

(3)

In Formula 3,

R ₁ is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, at least one -CH ₂ -group is independently -CO-, -CO-O-, -NZ-, -NZ-CO-, -CO-NZ -Or a C1 to C30 alkylene group substituted with -CH = CH-, Z is a hydrogen atom or a C1 to C10 alkyl group, oxygen atoms are not directly connected to each other,

R ₂ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group,

Q ₁ , Q ₂ and Q ₃ are each independently hydrogen or halogen,

n1 is an integer of 0 to 3,

n2 is an integer of 0-3.

[Formula 4]

In Formula 4,

Each R ₇ is independently a single bond, O, COO, NHCO or CONH,

n3 is an integer of 0 to 3,

n4 is an integer of 0 to 3,

n7 is an integer of 0 to 2,

R ₈ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group; Or a C1 to C30 alkyl group including -O-, -COO-, -CONH-, -OCO- or a combination thereof, -O-, -COO-, -CONH-, -OCO- or a combination thereof C2 to C30 heteroaryl group including C6 to C30 aryl group, -O-, -COO-, -CONH-, -OCO- or a combination thereof,

R ₉ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group.

[Chemical Formula 5]

In Formula 5,

R ₅ is a hydrogen atom; 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 ₆ is a substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group,

N6 is an integer of 0 to 3.

The diamine represented by Formula 3 may be a diamine represented by Formula 16 below.

[Chemical Formula 16]

In Formula 16,

l is an integer of 0 to 10.

The diamine represented by Formula 4 may be a diamine represented by Formula 17 below.

[Chemical Formula 17]

In Formula 17,

m is an integer of 1 to 5;

The polyamic acid and the polyimide may have a weight average molecular weight of 50,000 to 500,000.

The liquid crystal aligning agent may include the polyamic acid and the polyimide in a weight ratio of 1:99 to 50:50.

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

The liquid crystal aligning agent may have a viscosity of 5 to 30 cps.

In another aspect of the invention, there is provided a liquid crystal alignment film prepared by applying the liquid crystal alignment agent to a substrate.

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

The liquid crystal aligning agent is capable of photoalignment even at low energy, and it is possible to provide an aligning agent exhibiting excellent texture.

1 is a cross-sectional view of a liquid crystal display according to an exemplary embodiment of the present invention.

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

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 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, and the "alkoxy group" means a C1 to C30 alkoxy group, specifically a C1 to C20 alkoxy group, and the "cycloalkylene group" means a C3 to C30 cycloalkylene group Means a C3 to C20 cycloalkylene group, and the "heterocycloalkylene group" means a C2 to C30 heterocycloalkylene group Quot; means 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 Quot; means a heteroaryl group, specifically, a C2 to C18 heteroaryl group, and the "arylene" group means a C6 to C30 arylene group, specifically a C6 to C20 arylene group, Refers to a C2 to C30 heteroarylene group, specifically a C2 to C20 heteroarylene group, the "alkylaryl group" means a C7 to C30 alkylaryl group, specifically 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" C6 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 < / RTI >

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]

(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, wherein the diamine is 35 to 90 mol% of a diamine represented by the following Formula 3, and a diamine 5 represented by the following Formula 4. To 20 mol% and 5 to 45 mol% of diamine represented by the following Chemical Formula 5.

(3)

In Formula 3,

R ₁ is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, at least one -CH ₂ -group is independently -CO-, -CO-O-, -NZ-, -NZ-CO-, -CO-NZ -Or a C1 to C30 alkylene group substituted with -CH = CH-, Z is a hydrogen atom or a C1 to C10 alkyl group, oxygen atoms are not directly connected to each other,

R ₂ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group,

Q ₁ , Q ₂ and Q ₃ are each independently hydrogen or halogen,

n1 is an integer of 0 to 3,

n2 is an integer of 0-3.

[Formula 4]

In Formula 4,

Each R ₇ is independently a single bond, O, COO, NHCO or CONH,

n3 is an integer of 0 to 3,

n4 is an integer of 0 to 3,

n7 is an integer of 0 to 2,

R ₈ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group; Or a C1 to C30 alkyl group including -O-, -COO-, -CONH-, -OCO- or a combination thereof, -O-, -COO-, -CONH-, -OCO- or a combination thereof C2 to C30 heteroaryl group including C6 to C30 aryl group, -O-, -COO-, -CONH-, -OCO- or a combination thereof,

R ₉ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group.

[Chemical Formula 5]

In Formula 5,

R ₅ is a hydrogen atom; 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 ₆ is a substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group,

N6 is an integer of 0 to 3.

Specific examples of the diamine represented by Chemical Formula 3 include a compound represented by the following Chemical Formula 16, but is not limited thereto.

[Chemical Formula 16]

In Formula 16,

l is an integer of 0 to 10.

Specific examples of the diamine represented by Formula 4 include, but are not limited to, a compound represented by Formula 17 below.

[Chemical Formula 17]

In Formula 17,

m is an integer of 1 to 3;

When the diamine is included in the content ratio of 35 to 90 mol% of the diamine represented by the formula (3), 5 to 20 mol% of the diamine represented by the formula (4) and 5 to 45 mol% of the diamine represented by the formula (5) There may be an advantage in afterimages.

It is possible to use the diamine derived from the formula (3) to enable photo-alignment, wherein the diamine derived from the formula (4) and the diamine derived from the formula (5) can be used to enhance the vertical alignment force, less energy Even in the photo-alignment is possible, it can exhibit an excellent texture.

The liquid crystal aligning agent may further include a solvent and other additives in addition to the polymer. Hereinafter, the components will be described in detail.

Polymer

The polymer is a photopolymer including a polyamic acid including a repeating unit represented by Formula 1, a polyimide including a repeating unit represented by Formula 2, or a combination thereof.

The polymers are anisotropically reacted by photoisomerization or photocrosslinking due to polarized light irradiation, thereby causing anisotropy on the surface of the polymer and inducing molecular alignment of the liquid crystal in one direction.

The polyamic acid including the repeating unit represented by Formula 1 may be synthesized from an acid dianhydride, a diamine represented by Formula 3, and / or a diamine represented by Formula 4. The method of preparing the polyamic acid by copolymerizing the acid dianhydride with the diamine represented by Chemical Formula 3 and / or the diamine represented by Chemical Formula 4 may be applied without being limited to a method known to be usable for the synthesis of polyamic acid.

In addition, the polyimide including the repeating unit represented by the formula (2) can be synthesized from an acid dianhydride, the diamine represented by the formula (3) and / or the diamine represented by the formula (4). Since a method of preparing a polyimide by copolymerizing and imidizing the acid dianhydride and the diamine represented by Chemical Formula 3 and / or the diamine represented by Chemical Formula 4 is well known in the art, detailed description thereof will be omitted.

As the acid anhydride, an alicyclic acid anhydride, an aromatic acid dianhydride, or a mixture of at least one thereof can be used.

The alicyclic acid dianhydride includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene-1,2- Dicarboxylic anhydride (DOCDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), 1,2,4-tricarboxy-3-methylcarboxy cyclopentane dianhydride, 1,2,3,4-tetracarboxy cyclopentane dianhydride , 4,10-dioxa-tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone or a mixture of one or more thereof may be used, but is not limited thereto.

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 polyamic acid and the polyimide may have a weight average molecular weight of 50,000 kPa to 500,000. When the weight average molecular weight of the polyamic acid and the polyimide is within the above range, solubility, thermal stability and chemical resistance can be effectively improved, an appropriate viscosity can be maintained to have excellent printability, and a uniform film can be easily formed. have.

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 3 wt% to 20 wt%.

menstruum

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

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 to 70% by weight, specifically, 20 to 60% by weight, 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 coating.

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

Specific examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl Acetate, diethyl oxalate, malonic ester, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenylmethyl ether, ethylene glycol phenylethyl ether, di Ethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl on Le acetate, 4-hydroxy-4-methyl-2-pentanone, 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy acetate ethyl, hydroxy ethyl acetate, 2-hydroxy- Methyl 3-methyl butyrate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate, methyl 3-ethoxy propionate, methyl methoxy butanol, ethyl methoxy butanol, methyl ethoxy butanol, Ethyl ethoxy butanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, 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 from 1 to 30% by weight, specifically, the content of solids is from 3 to 20% by weight. Can be used. 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.

The liquid crystal aligning agent may have a viscosity of 5 to 30 cps, specifically, may have a viscosity of 10 to 20 cps. 　 When the viscosity of a liquid crystal aligning agent exists in the said range, coating film uniformity and applicability | paintability can be improved.

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 0.1 to 50 parts by weight, specifically 1 to 30 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.

Examples of the epoxy compound may include a compound represented by the following Formula 18, but is not limited thereto.

[Chemical Formula 18]

In Formula 18,

A ₁₂ is a substituted or unsubstituted C6 to C12 aromatic organic group, or a substituted or unsubstituted divalent C6 to C12 alicyclic organic group, or a substituted or unsubstituted divalent C6 to C12 aliphatic organic group such as substituted or unsubstituted It is a ring C1-C6 alkylene group.

Specific examples of the epoxy compound include N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylmethane (TGDDM), N, N, N', N'-tetraglycidyl- 4,4'-diaminophenylethane, N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylpropane, N, N, N', N'-tetraglycidyl- 4,4'-diaminophenylbutane, N, N, N ', N'-tetraglycidyl-4,4'-diaminobenzene, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin 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.

The liquid crystal alignment layer may be manufactured using the liquid crystal alignment agent.

Although the liquid crystal aligning film can apply | coat the liquid crystal aligning agent melt | dissolved in the said organic solvent to a board | substrate, and form it, 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. Can be. 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 the liquid crystal aligning agent through the temporary drying, a uniform and uneven coating film 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.

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

Specifically, the liquid crystal alignment layer according to the exemplary embodiment of the present invention may be subjected to uniaxial alignment treatment by exposing for 0.1 to 180 minutes at an energy of 10 mJ to 5,000 mJ.

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

Liquid crystal display devices (LCDs) use liquid crystals that are twisted at 90 degrees between polarizers and analyzers whose polarization directions are perpendicular to each other. In the absence of voltage, linearly polarized light passing through the polarizer is rotated along the direction of the locally different liquid crystal aligner and deflected by 90 degrees. As a result, the light rotates while passing through the liquid crystal layer and passes through the analyzer. When voltage is applied, the liquid crystals are lined up in a direction parallel to the electric field direction so that the linearly flattened light passes through the liquid crystal layer without rotation, so that the liquid crystals collide perpendicularly to the polarization direction of the analyzer and cannot pass. Since the control of the liquid crystal can produce a selective transmission of light, in general, in order to obtain uniform brightness and high contrast ratio in the LCD, uniform alignment of the liquid crystal over the LCD panel is very important. The liquid crystal alignment layer can be usefully applied in this respect.

In addition, the liquid crystal display device, for example, by applying a liquid crystal alignment agent to a glass substrate on which a transparent indium tin oxide (ITO) conductive film is deposited, and curing it with heat to form an alignment layer, and then bonded the two substrates in opposite directions It can manufacture by the method of inject | pouring a liquid crystal, a liquid crystal dropping method which drips a liquid crystal to one board | substrate, or attaches and opposes a counter substrate.

1 is a cross-sectional view of the liquid crystal display device.

Referring to FIG. 1, the liquid crystal display device 1 may include a lower panel 100, an upper panel 200, and a liquid crystal layer 3.

The lower panel 100 includes a gate conductor including a plurality of gate lines (not shown) and a plurality of storage electrodes 133 on an upper surface of the first substrate 110. . On the gate conductor, a gate insulating layer 140, a plurality of semiconductors 154, a plurality of pairs of ohmic contacts 163 and 165, a plurality of source electrodes 173, And a plurality of drain electrodes 175 are formed in this order.

One gate electrode 124, one source electrode 173, and one drain electrode 175 together with the semiconductor 154 form one thin film transistor (TFT).

A passivation layer 180 is formed on the exposed portion of the semiconductor 154, the source electrode 173, the drain electrode 175, and the gate insulating layer 140. A plurality of pixel electrodes 191 are formed on the passivation layer 180.

Next, the upper panel 200 will be described.

In the upper panel 200, a light blocking member 220 is formed on the second substrate 210. A plurality of color filters 230 are formed on the second substrate 210 and the light blocking member 220, and an overcoat 250 is formed on the color filters 230. The overcoat 250 may prevent the color filter 230 from being exposed to the liquid crystal layer 3, and the overcoat 250 may be omitted.

The first liquid crystal alignment layer 12 and the second liquid crystal alignment layer 22 are formed on the pixel electrode 191 of the lower panel 100 and the common electrode 270 of the upper panel 200, respectively. The first liquid crystal alignment layer 12 and the second liquid crystal alignment layer 22 are manufactured by using the liquid crystal alignment agent according to the embodiment of the present invention.

In FIG. 1, the liquid crystal alignment layers 12 and 22 are formed on both the lower panel 100 and the upper panel 200. However, the liquid crystal alignment layers 12 and 22 may be the upper panel 200 or the lower panel. It may be formed only in any one of the (100).

Hereinafter, specific embodiments of the present invention will be described. However, the examples described below are merely to specifically illustrate or explain the present invention, and the present invention is not limited thereto.

( Example )

Comparative Example  One: Polyamic acid  Produce

4- (4,4,4-trifluorobutoxy) -benzoic acid 4- represented by the following Chemical Formula 3a while passing nitrogen under dark conditions in a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler 0.5 mmol of {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl ester was added, and N-methyl-2-pyrrolidone (NMP) was added to the flask. Thus, the compound of Formula 3a was dissolved in NMP.

To the solution, 4,10-dioxa-tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone ("2,3,5-tricarboxycyclopentyl) in the solid state Acetic anhydride) 　 1.0 mol was added and vigorously stirred.

After stirring for 1 hour, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) represented by Chemical Formula 3a was added to the stirred product. -0.5 mmol of ethoxycarbonyl] -vinyl} -phenyl ester was added and reacted to the appropriate viscosity (about 150 cps).

Solid content of the obtained liquid was 30% by weight, and the temperature of the obtained liquid was 50 ° C. 　 The copolymerization reaction was carried out for 24 hours while maintaining the polyamic acid solution.

[Chemical Formula 3]

The weight average molecular weight of the produced polyamic acid was 200,000. A mixed solvent (3: 4: 3 volume ratio) of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and 2-butyl celusolve, which are organic solvents, was added to this polyamic acid, and at room temperature for 24 hours. While stirring, a photo-aligned polyamic acid (liquid crystal aligning agent) liquid was prepared.

Example  One: Of polyamic acid (PSA-1)  Produce

4- (4,4,4-trifluorobutoxy) -benzoic acid 4 represented by the formula (3a) while passing nitrogen under a dark-room condition in a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler 0.5 mmol (primary addition amount) of-{2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl ester was added to the flask and N-methyl-2-pyrroli was added. Don (NMP) was added to dissolve the compound of Formula 3a in NMP.

To the solution, 4,10-dioxa-tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone ("2,3,5-tricarboxycyclopentyl) in the solid state 1.0 mole of acetic anhydride) was added and stirred vigorously.

After stirring for 1 hour, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl)-represented by Chemical Formula 3a was added to the stirred product. 0.3 mol (secondary amount) of oxycarbonyl] -vinyl} -phenyl ester and ((E) -10,13-dimethyl-17- (6-methylheptan-2-yl) hexadecahydro- represented by the following formula (4a): 0.05 mole of 1H-cyclopenta [a] phenanthren-3-yl 4- (3- (2,4-diaminophenethoxy) -3-oxoprop-1-enyl) benzoate and 1- represented by formula 5a 0.15 mole of (3,5-diaminophenyl) -3-octadecylsuccinimide was added thereto and reacted to an appropriate viscosity (about 150 cps).

Solid content was 30 weight% in the obtained liquid, and the obtained solution was copolymerized for 24 hours, maintaining the temperature at 50 degreeC, and the polyamic-acid solution was prepared.

[Chemical Formula 4a]

[Chemical Formula 5a]

The prepared polyamic acid solution was distilled off to obtain pure polyamic acid. The weight average molecular weight of the produced polyamic acid was 200,000. A mixed solvent (3: 4: 3 volume ratio) of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and 2-butyl celusolve, which are organic solvents, was added to this polyamic acid, and at room temperature for 24 hours. While stirring, a photo-aligned polyamic acid (PSA-1) (liquid crystal aligning agent) liquid was prepared.

Example  2 to 10: Of polyamic acid (PSA-2 to 10)  Produce

4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl represented by the above formula (3a) Ester, (E) -10,13-dimethyl-17- (6-methylheptan-2-yl) hexadecahydro-1H-cyclopenta [a] phenanthren-3-yl 4- (3) Of-(2,4-diaminophenethoxy) -3-oxoprop-1-enyl) benzoate and 1- (3,5-diaminophenyl) -3-octadecylsuccinimide represented by the above formula (5a) A photo-alignment polyamic acid (PSA-2 to 10) (liquid crystal aligning agent) liquid was prepared in the same manner as in Example 1 except that the amount of use was changed as shown in Table 1 below. In Table 1, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl represented by formula 3a: The amount of} -phenyl ester used was the sum of the first addition amount and the second addition amount, and in all the examples, the first addition amount was 0.5 mol.

Comparative Example  2: Preparation of Polyimide Polymer

4- (4,4,4-trifluorobutoxy) -benzoic acid 4- represented by Chemical Formula 3a while passing nitrogen under a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler under dark room conditions 0.5 mmol of {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl ester was added, and N-methyl-2-pyrrolidone (NMP) was added to the flask. Thus, the compound of Formula 3a was dissolved in NMP.

To the solution, 4,10-dioxa-tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone ("2,3,5-tricarboxycyclopentyl) in the solid state 1.0 mole of acetic anhydride) was added and stirred vigorously.

After stirring for 1 hour, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) -ethoxycarbo represented by Chemical Formula 3a 0.5 [mol] of nil] -vinyl} -phenyl ester was added and reacted to an appropriate viscosity (about 150 cps).

Solid content in the obtained liquid was 30% by weight, and the obtained liquid was used for 24 hours. 　 The polyamic acid solution was prepared by performing a copolymerization reaction at room temperature.

3.0 mol of acetic anhydride catalyst and 5.0 mol of pyridine catalyst were added to the polyamic acid solution, and the reaction mixture was heated at 80 ° C. for 6 hours. The reaction product was removed by vacuum distillation to remove acetic anhydride, pyridine catalyst and NMP solvent to prepare a soluble polyimide resin liquid having a solid content of 20% by weight.

The prepared soluble polyimide resin was distilled to prepare a pure soluble polyimide resin (weight average molecular weight 200,000). To the obtained soluble polyimide resin, a mixed solvent (3: 4: 3 volume ratio) of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and 2-butyl celusolve, which are organic solvents, is added, and at room temperature It stirred for 24 hours, and prepared the soluble photo-alignment polyimide resin (PSI-1) (liquid crystal aligning agent) liquid.

Example  11: polyimide polymer ( PSI -2) Preparation

4- (4,4,4-trifluorobutoxy) -benzoic acid 4 represented by Chemical Formula 3a while passing nitrogen under a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler under dark room conditions 0.5 mmol (primary addition amount) of-{2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl ester was added thereto, and N-methyl-2-pyrroli was added to the flask. Don (NMP) was added to dissolve the compound of Formula 3a in NMP.

To the solution, 4,10-dioxa-tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone ("2,3,5-tricarboxycyclopentyl) in the solid state Acetic anhydride) 　 1.0 mol was added and vigorously stirred.

After stirring for 1 hour, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl)-represented by Chemical Formula 3a was added to the stirred product. 0.4 mol (secondary amount) of oxycarbonyl] -vinyl} -phenyl ester and ((E) -10,13-dimethyl-17- (6-methylheptan-2-yl) hexadecahydro- represented by the following formula (4a): 0.05 mole of 1H-cyclopenta [a] phenanthren-3-yl 4- (3- (2,4-diaminophenethoxy) -3-oxoprop-1-enyl) benzoate and 1- represented by formula 5a 0.15 mole of (3,5-diaminophenyl) -3-octadecylsuccinimide was added thereto and reacted to an appropriate viscosity (about 150 cps).

Solid content in the obtained liquid was 30% by weight, and the obtained liquid was kept at room temperature for 24 hours. 　 The reaction was carried out to prepare a polyamic acid solution.

3.0 mol of acetic anhydride catalyst and 5.0 mol of pyridine catalyst were added to the polyamic acid solution, and the temperature was raised to 80 ° C., followed by reaction for 6 hours. The reaction product was removed by vacuum distillation to remove acetic anhydride, pyridine catalyst and NMP solvent to prepare a soluble polyimide resin liquid having a solid content of 20% by weight.

The prepared soluble polyimide resin was distilled to prepare a pure soluble polyimide resin (weight average molecular weight 200,000). To the obtained soluble polyimide resin, a mixed solvent (3: 4: 3 volume ratio) of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and 2-butyl celusolve, which are organic solvents, is added, and at room temperature Stirring for 24 hours to prepare a soluble photoaligned polyimide resin (PSI-1) (liquid crystal aligning agent).

Example  12 to 20: polyimide polymer ( PSI -2 to PSI -10)

4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] -vinyl} -phenyl represented by the above formula (3a) Ester, (E) -10,13-dimethyl-17- (6-methylheptan-2-yl) hexadecahydro-1H-cyclopenta [a] phenanthren-3-yl 4- (3) Of-(2,4-diaminophenethoxy) -3-oxoprop-1-enyl) benzoate and 1- (3,5-diaminophenyl) -3-octadecylsuccinimide represented by the above formula (5a) A polyamic acid was prepared in the same manner as in Example 11 except that the amount of use thereof was changed as shown in Table 1, and the same procedure as in Example 11 was carried out using this polyamic acid to produce a soluble photo-aligned polyimide. A resin liquid (liquid crystal aligning agent) was produced.

In Table 1 below, 4- (4,4,4-trifluorobutoxy) -benzoic acid 4- {2- [2- (2,4-diamino-phenyl) -ethoxycarbonyl] represented by the formula (3a)- The amount of the vinyl} -phenyl ester used was the sum of the amount of primary addition and the amount of secondary addition, and in all the examples, the amount of primary addition was 0.5 mol.

Manufacturing example Formula 3a (mol%) Formula 4a (mol%) Formula 5a (mol%) Type Example 1 PSA-1 80 5 15 Polyamic acid Example 2 PSA-2 70 5 25 Polyamic acid Example 3 PSA-3 70 8 22 Polyamic acid Example 4 PSA-4 70 10 20 Polyamic acid Example 5 PSA-5 60 5 35 Polyamic acid Example 6 PSA-6 60 8 32 Polyamic acid Example 7 PSA-7 60 10 30 Polyamic acid Example 8 PSA-8 50 5 45 Polyamic acid Example 9 PSA-9 50 8 42 Polyamic acid Example 10 PSA-10 50 10 40 Polyamic acid Example 11 PSI-1 80 5 15 Polyimide Example 12 PSI-2 70 5 25 Polyimide Example 13 PSI-3 70 8 22 Polyimide Example 14 PSI-4 70 10 20 Polyimide Example 15 PSI-5 60 5 35 Polyimide Example 16 PSI-6 60 8 32 Polyimide Example 17 PSI-7 60 10 30 Polyimide Example 18 PSI-8 50 5 45 Polyimide Example 19 PSI-9 50 8 42 Polyimide Example 20 PSI-10 50 10 40 Polyimide

In Table 1, the usage units of the formulas 3a, 4a, and 5a are mole%, each mole% relative to the total moles of diamine used in preparing the polyamic acid. In addition, the content of the repeating unit derived from formula 3a, the repeating unit derived from formula 4a, and the repeating unit derived from formula 5a contained in the polyamic acid or polyimide prepared using the molar% amount is represented by the formula used. Equivalent to mole% of compound represented.

(Liquid crystal of liquid crystal aligning film Orientation )

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

The ITO glass substrate was patterned using a photolithography process to remove other portions of ITO, leaving only 1.5 cm × 1.5 cm square ITO shapes and electrode ITO shapes for voltage application.

The liquid crystal aligning agents prepared in Examples 1 to 20 and Comparative Examples 1 and 2 were applied to the patterned ITO substrate, spin-coated to make a thickness of 0.1 μm, and then subjected to curing at 70 ° C. and 210 ° C.

The two I substrates subjected to the curing process using an exposure machine (UIS-S2021J7-YD01, Ushio LPUV) under a certain angle and a constant energy are exposed to opposite directions (90 degrees for VA mode). Thereafter, square ITO shapes were joined up and down consistently while maintaining a cell gap of 4 mu m. In the exposure, a light source used a 2kW deep UV ramp (UXM-2000).

After filling the liquid crystal in the cell made in this way, the liquid crystal alignment was observed using an orthogonally polarized optical microscope, and the results are summarized in Table 2 below.

(Electrical and Optical Properties of Liquid Crystal Alignment Film)

Electrical and optical properties of the liquid crystal alignment film were evaluated by measuring the high temperature (60 ° C.) voltage holding ratio and the residual DC voltage (RDC) using a liquid crystal cell having a 4 μm cell gap.

The high temperature (60 ° C) voltage retention rate refers to the degree to which the liquid crystal layer in a state of floating with an external power source maintains a charged voltage during a non-selection period in an active driving type TFT-LCD at 60 ° C. Ideal. The evaluation results are shown in Table 2 below, and if it is 98% or more, it is good, and if it is less than 98%, it is described as poor.

The residual DC voltage refers to a voltage applied to the liquid crystal layer even when no impurities are applied to the alignment layer by the impurities of the ionized liquid crystal layer, and the lower the better. As a method of measuring the residual DC voltage, a method using flicker and a method using a capacitance change curve (C-V) of the liquid crystal layer according to DC voltage are common. The evaluation results are listed in Table 2 below, and are described as good if 100 mV 'or less, and bad if exceeding 100 mV'.

The electrical and optical properties of the liquid crystal alignment layer using the liquid crystal cell are shown in Table 2 below.

Synthetic example Orientation Voltage retention rate RDC High temperature (60 ℃) Example 1 Good Good Good Example 2 Good Good Good Example 3 Good Good Good Example 4 Good Good Good Example 5 Good Good Good Example 6 Good Good Good Example 7 Good Good Good Example 8 Good Good Good Example 9 Good Good Good Example 10 Good Good Good Example 11 Good Good Good Example 12 Good Good Good Example 13 Good Good Good Example 14 Good Good Good Example 15 Good Good Good Example 16 Good Good Good Example 17 Good Good Good Example 18 Good Good Good Example 19 Good Good Good Example 20 Good Good Good Comparative Example 1 Good Bad Bad Comparative Example 2 Good Bad Bad

Referring to Table 2, it can be seen that the liquid crystal aligning agents of Examples 1 to 20 have improved high-temperature voltage retention (VHR) and RDC characteristics compared to Comparative Examples 1 and 2.

The voltage holding ratio and the residual DC serve as a criterion for evaluating the afterimage characteristic of the liquid crystal alignment layer, and the higher the voltage holding ratio and the lower the residual DC, the better the afterimage characteristic. Therefore, it can be seen that the liquid crystal aligning agent prepared in Examples 1 to 20 is superior to the afterimage property than the liquid crystal aligning agents prepared in Comparative Examples 1 and 2.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: liquid crystal display device 3: liquid crystal layer
12: first liquid crystal alignment film 22: second liquid crystal alignment film
100: lower display panel 110: first substrate
124: gate electrode 133: sustain electrode
140: gate insulating film 154: semiconductor
163 and 165: ohmic contact 173: source electrode
175: drain electrode 180: protective film
191: pixel electrode 200: upper display panel
210: second substrate 210: light blocking member
230: color filter 250: overcoat
270 common electrode

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, wherein the diamine is 35 to 90 mol% of a diamine represented by the following Formula 3, and a diamine 5 represented by the following Formula 4. To 20 mol% and 5 to 45 mol% of diamine represented by the following Formula 5,
(3)

In Formula 3,
R ₁ is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, at least one -CH ₂ -group is independently -CO-, -CO-O-, -NZ-, -NZ-CO-, -CO-NZ -Or a C1 to C30 alkylene group substituted with -CH = CH-, Z is a hydrogen atom or a C1 to C10 alkyl group, oxygen atoms are not directly connected to each other,
R ₂ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group,
Q ₁ , Q ₂ and Q ₃ are each independently hydrogen or halogen,
n1 is an integer of 0 to 3,
n2 is an integer of 0 to 3,
[Chemical Formula 4]

In Chemical Formula 4,
Each R ₇ is independently a single bond, O, COO, NHCO or CONH,
n3 is an integer of 0 to 3,
n4 is an integer of 0 to 3,
n7 is an integer of 0 to 2,
R ₈ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group; Or a C1 to C30 alkyl group including -O-, -COO-, -CONH-, -OCO- or a combination thereof, -O-, -COO-, -CONH-, -OCO- or a combination thereof C2 to C30 heteroaryl group including C6 to C30 aryl group, -O-, -COO-, -CONH-, -OCO- or a combination thereof,
R ₉ is a substituted or unsubstituted aliphatic organic group, a substituted or unsubstituted alicyclic organic group, or a substituted or unsubstituted aromatic organic group,
[Chemical Formula 5]

In Formula 5,
R ₅ is a hydrogen atom; 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 ₆ is a substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group,
N6 is an integer of 0 to 3. The method of claim 1,
The diamine represented by the formula (3) is a diamine represented by the formula (16):
[Chemical Formula 16]

In Formula 16,
l is an integer of 0 to 10. The method of claim 1,
The diamine represented by the formula (4) is a diamine represented by the formula (17):
[Chemical Formula 17]

In Formula 17,
m is an integer of 1 to 5; The method of claim 1,
Wherein said polyamic acid and said polyimide have a weight average molecular weight of 50,000 to 500,000. The method of claim 1,
The liquid crystal aligning agent comprising the polyamic acid and the polyimide in a weight ratio of 1:99 to 50:50. The method of claim 1,
The liquid crystal aligning agent having a solid content of 1 to 30% by weight. The method of claim 1,
The liquid crystal aligning agent having a viscosity of 5 to 30 cps. The liquid crystal crystal aligning film manufactured by apply | coating the liquid crystal crystal aligning agent in any one of Claims 1-7 to a board | substrate. A liquid crystal display device comprising the liquid crystal alignment film according to claim 8.

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