KR20130054846A - Novel epoxy compound, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

PURPOSE: An epoxy compound and a liquid crystal alignment agent containing the same are provided to improve transmissivity, brightness, response speed, and printing property of a substrate. CONSTITUTION: An epoxy compound contains a compound of chemical formula 1. A liquid crystal alignment agent contains the epoxy compound, and a polymer containing one selected from polyamic acid, polyimide, and a combination thereof. The compound of chemical formula 1 includes a compound of chemical formula 1-1. A liquid crystal alignment film is prepared by applying the liquid crystal alignment agent on a substrate. A liquid crystal display device contains the liquid crystal alignment film.

Description

New epoxy compound, liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device {NOVEL EPOXY COMPOUND, LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID® CRYSTAL DISPLAY DEVICE}

A novel epoxy compound, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.

A liquid crystal display device (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. In general, in order to obtain uniform brightness and high contrast ratio in the liquid crystal display, it is essential to orient the liquid crystal uniformly.

Conventionally, the rubbing method which apply | coated a polymer film like polyimide to the board | substrates, such as glass, and rubbed the surface in a fixed direction with fibers, such as a nylon and polyester, was the conventional method of orienting a liquid crystal. 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 the liquid crystal panel.

In order to solve the problems of the rubbing method and improve the viewing angle, various methods have been studied. One developed for this purpose is a vertically aligned liquid crystal alignment. However, in the vertical alignment liquid crystal alignment method, photolithography of the color filter glass is required in order to obtain a wider viewing angle, thereby increasing the manufacturing process and decreasing transmittance and luminance.

One embodiment provides a novel epoxy compound that can be prepared in a simple process, and can provide a liquid crystal aligning agent having excellent transmittance, brightness, and the like.

Another embodiment provides the liquid crystal crystal aligning agent including the epoxy compound and having excellent properties such as transmittance and luminance.

Yet another embodiment provides a liquid crystal alignment layer manufactured using the liquid crystal alignment agent.

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

One embodiment provides an epoxy compound comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

A ¹ is a single bond, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, -COO-, or a substituted or unsubstituted C1 to C20 alkylene group,

A ² is a single bond, a substituted or unsubstituted divalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,

A ³ is a single bond, a substituted or unsubstituted divalent C1 to C20 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,

n1 is an integer of 0 or 1,

R ¹ is hydrogen or a methyl group,

R ² is hydrogen or a substituted or unsubstituted C 1 to C 10 alkyl group,

n2 is an integer of 0-4.

Specifically, the compound represented by Formula 1 may include a compound represented by Formula 1-1.

[Formula 1-1]

In Formula 1-1,

A ¹ , A ² , A ³ , n ¹ , R ¹ , R ^2, and n ² are the same as defined in Chemical Formula 1.

More specifically, the compound represented by Chemical Formula 1 may include one selected from compounds represented by the following Chemical Formulas 2-1 to 2-10, and a combination thereof.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

.

.

Another embodiment is an epoxy compound comprising a compound represented by Formula 1; And it provides a liquid crystal aligning agent comprising a polymer comprising one selected from polyamic acid, polyimide and combinations thereof.

In the liquid crystal aligning agent, the epoxy compound may be included in an amount of 0.01 parts by weight to 50 parts by weight based on 100 parts by weight of the epoxy compound and the polymer.

The polyamic acid may include a repeating unit represented by Formula 3 below.

(3)

In Formula 3,

X ¹ is the same or different in each repeating unit and each independently is a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride,

Y ¹ is the same or different at each repeat unit and each independently a divalent organic group derived from diamine.

The polyimide may include a repeating unit represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

X ² is the same or different at each repeating unit and is independently a tetravalent organic group derived from an alicyclic acid dianhydride or aromatic acid dianhydride,

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

Another embodiment provides a liquid crystal crystal aligning film prepared by applying the liquid crystal crystal aligning agent to a substrate.

Yet another embodiment provides a liquid crystal display device including the liquid crystal display alignment layer.

Provided are an epoxy compound capable of improving transmittance, brightness, response speed, and printability of a liquid crystal aligning agent, and a liquid crystal aligning agent comprising the epoxy compound.

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

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (-F, -Cl, -Br 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 C1 to C10 alkyl groups) , Amidino group, 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 At least one substituent selected from the group consisting of a substituted 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. It means substituted.

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

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

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

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

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

Epoxy compound according to one embodiment includes a compound represented by the formula (1).

[Formula 1]

In Formula 1,

A ¹ is a single bond, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, -COO-, or a substituted or unsubstituted C1 to C20 alkylene group, specifically, a single bond,- CO-, or a substituted or unsubstituted C1 to C10 alkylene group.

A ² is a single bond, a substituted or unsubstituted divalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group Specifically, a single bond, a substituted or unsubstituted divalent C1 to C20 aliphatic organic group, a substituted or unsubstituted divalent C2 to C20 aromatic organic group, or a substituted or unsubstituted divalent C3 to C20 alicyclic organic group Can be.

A ³ is a single bond, a substituted or unsubstituted divalent C1 to C20 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group Specifically, it may be a single bond.

n1 is an integer of 0 or 1, specifically, it may be 1.

R ¹ is hydrogen or a methyl group.

R ² is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, and specifically, it may be hydrogen or a substituted or unsubstituted C1 to C5 alkyl group.

n2 is an integer of 0-4.

The epoxy compound may be used as one component of the liquid crystal aligning agent. Details thereof will be described later.

When using an epoxy compound containing a (meth) acrylate functional group and a functional group derived from (meth) acrylate as the liquid crystal aligning agent as described above, after the upper plate and the lower plate is bonded, light irradiation is performed in a state where a voltage is applied. The molecular orientation of the liquid crystal can be induced in one direction. This is different from the conventional method of inducing liquid crystal alignment by rubbing and patterning.

Thus, when such an epoxy compound is used in the liquid crystal aligning agent, it is possible to achieve a better transmittance and brightness than a panel using a conventional vertically aligned liquid crystal aligning agent, it is possible to shorten the process by not performing the ITO patterning process have. In addition, the alignment characteristics, the electrical properties, the afterimage characteristics, the liquid crystal alignment and chemical resistance can be improved, and the pretilt angle can be easily adjusted.

Specifically, the compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 1-1, but is not limited thereto.

[Formula 1-1]

In Formula 1-1,

A ¹ , A ² , A ³ , n ¹ , R ¹ , R ^2, and n ² are the same as defined in Chemical Formula 1.

More specifically, the compound represented by Chemical Formula 1 may include one selected from compounds represented by the following Chemical Formulas 2-1 to 2-10 and a combination thereof, but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

.

.

For example, the epoxy compound may be prepared by the following process, but is not limited thereto.

After dissolving the compound represented by the following Chemical Formula 1-A in ethanol, the compound represented by the following Chemical Formula 1-B is dissolved in ethanol and added and reacted thereto. Subsequently, the aqueous solution of sodium hydroxide is slowly added thereto, followed by filtration to prepare a compound represented by the following Chemical Formula 1-C.

[Chemical Formula 1-A]

[Chemical Formula 1-B]

[Chemical Formula 1-C]

In Formulas 1-A and 1-C, A ¹ , R ^2, and n ² are the same as defined in Formula 1 above.

The reaction molar ratio of the compound represented by Formula 1-A and the compound represented by Formula 1-B may be about 1: 2.

Subsequently, the compound represented by Chemical Formula 1-C is dissolved in methylene chloride (MC), and 4-dimethylaminopyridine (DMAP) and N, N'-diisopropyl carbodiimide After (N, N'-diisopropyl carbodiimide, DIC) was added, the compound represented by Chemical Formula 1-D was slowly added and reacted to prepare the compound represented by Chemical Formula 1-1.

[Chemical Formula 1-D]

In Formula 1-D, A ² , A ³ , R ¹ and n ¹ are the same as defined in Formula 1 above.

Once the reaction in each step is complete, the general purification process of washing, filtering and drying the reaction product of each step can be further carried out.

Liquid crystal aligning agent according to another embodiment includes an epoxy compound comprising a compound represented by Formula 1; And polymers including one selected from polyamic acid, polyimide, and combinations thereof.

Hereinafter, each component will be described in detail.

(A) epoxy compound

Epoxy compound includes a compound represented by the formula (1). The liquid crystal aligning agent used as an additive for mixing such epoxy compound with a polymer including one selected from polyamic acid, polyimide, and a combination thereof has excellent transmittance and brightness, and has alignment characteristics, reliability, electro-optical characteristics, afterimage characteristics, Liquid crystal alignment and chemical resistance can be improved, and the pretilt angle can be easily adjusted.

The liquid crystal aligning agent may include 0.01 parts by weight to 50 parts by weight based on 100 parts by weight of the solid compound (in the liquid crystal aligning agent, which is an epoxy compound and a polymer). When the content of the epoxy compound is within the above range, it is possible to effectively induce the molecular orientation of the liquid crystal in one direction by light irradiation in a voltage applied state, without lowering the printability and flatness at the time of coating on the substrate, as a liquid crystal aligning agent It can be useful. As a result, it is possible to improve transmittance and response speed, improve electrical characteristics such as voltage retention and residual DC, and easily control wire blind spots. Moreover, it has the outstanding chemical resistance, and has chemical resistance with respect to the washing | cleaning solvent in a panel manufacturing process, and the liquid-crystal orientation after washing may not fall. Specifically, the liquid crystal aligning agent may include the epoxy compound in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the solid content.

Specifically, the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1-1, but is not limited thereto.

More specifically, the compound represented by Chemical Formula 1 may include one selected from the compounds represented by Chemical Formulas 2-1 to 2-10 and a combination thereof, but is not limited thereto.

The said epoxy compound may further contain the epoxy compound conventionally used as an additive to a liquid crystal aligning agent.

Specific examples of the epoxy compound used conventionally include N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylmethane (TGDDM), N, N, N', N'-tetragly Cydyl-4,4'-diaminophenylethane, N, N, N ', N'-tetraglycidyl-4,4'-diaminophenylpropane, N, N, N', N'-tetragly Cydyl-4,4'-diaminophenylbutane, N, N, N ', N'-tetraglycidyl-4,4'-diaminobenzene, ethylene glycol diglycidyl ether, polyethylene glycol diglyci Dil 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, 2,2-dibromoneopentyl glycol 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'-te Traglycidyl-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.

(B) polymer

The polymer may include one selected from polyamic acid, polyimide, and combinations thereof. In addition, when the polyamic acid and the polyimide are used in a mixture, it may be used by mixing in a ratio of 1 to 99% by weight and 99 to 1% by weight.

(B-1) polyamic acid

In the liquid crystal aligning agent, as the polyamic acid, any polyamic acid synthesized from an acid dianhydride and diamine may be used.

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

As the diamine, aromatic diamines or functional diamines may be used alone, or aromatic diamines and functional diamines may be mixed and used. In the case where a mixture of aromatic diamine and functional diamine is used, it is possible to easily adjust the pretilt angle of the liquid crystal molecules in the liquid crystal alignment film and to improve the orientation effectively.

The method of preparing the polyamic acid by copolymerizing the acid dianhydride and the diamine may be applied without being limited to a method known to be usable for the synthesis of polyamic acid.

Polyamic acid according to one embodiment may include a repeating unit represented by the following formula (3).

(3)

In Formula 3,

X ¹ is the same or different in each repeating unit and each independently is a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride,

Y ¹ is the same or different at each repeat unit and each independently a divalent organic group derived from diamine.

(B-1-1) Acid Anhydride

(B-1-1-1) Alicyclic Acid Anhydride

The alicyclic acid dianhydride includes 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene-1,2- Dicarboxylic anhydride (DOCDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA), 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride (CHDA), 1,2,4-tricarboxy-3-methylcarboxy cyclopentane dianhydride, 1,2,3,4-tetracarboxy cyclopentane dianhydride , 2,3,5-tricarboxycyclopentylacetic dianhydride, 4,10-dioxa-tricyclo [6.3.1.02,7] dodecane-3,5,9,11-tetraone or mixtures of one or more thereof However, the present invention is not limited thereto.

The tetravalent organic group derived from the alicyclic acid dianhydride may include at least one of functional groups represented by the following Chemical Formulas 5 to 9, but is not limited thereto.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

In the above formulas 5 to 9,

R ³ is 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,

n3 is an integer of 0 to 7,

R ⁴ to R ¹⁰ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.

When n3 is an integer of 2 or more, each of R ³ may be the same or different from each other.

(B-1-1-2) aromatic acid dianhydride

The aromatic acid dianhydrides include pyromellitic dianhydride (PMDA), nonphthalic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic acid. Anhydride (6-FDA), or may be used by mixing one or more thereof, but is not limited thereto.

The tetravalent organic group derived from the aromatic acid dianhydride may include at least one of a functional group represented by Formula 10 and a functional group represented by Formula 11, but is not limited thereto.

[Formula 10]

[Formula 11]

In Formula 10 and Formula 11,

R ¹¹ and R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

n4 and n5 are each independently an integer of 0 to 3,

T ¹ is a single bond, —O—, —CO—, a substituted or unsubstituted C1 to C6 alkylene group (eg C (CF ₃ ) ₂ ), a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substitution Or an unsubstituted C2 to C30 heterocycloalkylene group.

When n4 is an integer of 2 or more, R ¹³ may be the same or different from each other. Similarly, when n5 is an integer of 2 or more, each of R ¹⁴ may be the same or different from each other.

(B-1-2) diamine

(B-1-2-1) aromatic diamine

Examples of the aromatic diamine include para-phenylenediamine (p-PDA), 4,4-methylenedianiline (MDA), # 2,2'-dimethyl benzidine (DMBZ), 3,3'-dimethyl benzidine, 4,4- Oxydianiline (ODA), metabisaminophenoxydiphenylsulfone (m-BAPS), para-bisaminophenoxydiphenylsulfone (p-BAPS), 2,2-bisaminophenoxyphenylpropane (BAPP), 2, 2-bisaminophenoxyphenylhexafluoropropane (HF-BAPP), 1,4-diamino-2-methoxybenzene, or a mixture of one or more thereof may be used, but is not limited thereto.

The divalent organic group derived from the aromatic diamine may include at least one of functional groups represented by the following Chemical Formulas 12 to 15, but is not limited thereto. By the polyamic acid comprising a divalent organic group derived from the aromatic diamine, it is possible to improve the chemical resistance, thermal stability and mechanical properties of the liquid crystal aligning agent and the liquid crystal aligning film formed therefrom.

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

In Chemical Formulas 12 to 15,

R ¹⁵ to R ²⁴ are each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and the alkyl group and the aryl group And the heteroaryl group may further include one selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and a combination thereof.

T ² to T ⁷ are each independently a single bond, —O—, —SO ₂ — or —C (R ¹⁰³ ) (R ¹⁰⁴ ) — such as —C (CF ₃ ) ₂ —, wherein R ¹⁰³ and R ¹⁰⁴ is each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group,

n6 to n15 are each independently an integer of 0 to 4;

When n6 is an integer of 2 or more, R ¹⁵ may be the same or different from each other. Similarly, when n7 to n15 are each an integer of 2 or more, the R ¹⁶ to R ²⁴ may be the same or different from each other.

(B-1-2-2) Functional Diamine

The functional diamine may include at least one of the compounds represented by the following Chemical Formulas 16 to 18, but is not limited thereto. In this case, the polyamic acid may include a divalent organic group derived from the functional diamine, thereby improving liquid crystal alignment, chemical resistance, and electro-optical properties, easily adjusting the pretilt angle, and expressing a high pretilt angle. have.

[Chemical Formula 16]

In Formula 16,

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

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

n16 is an integer of 0-3.

When n16 is an integer of 2 or more, each of R ²⁶ may be the same or different from each other.

[Chemical Formula 17]

In Formula 17,

R ²⁷ , R ²⁸ and R ²⁹ are the same or different and each independently represent 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 ego,

T ⁸ is a single bond, -O-, -COO-, -CONH-, -OCO-, or a substituted or unsubstituted C1 to C10 alkylene group,

R ³⁰ is hydrogen, a substituted or unsubstituted C1 to C30 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 selected from the group consisting of -O-, -COO-, -CONH-, -OCO-, and combinations thereof,

n17 is an integer of 0 to 3,

n18 and n19 are each independently an integer of 0-4.

When n17 is an integer of 2 or more, R ²⁷ may be the same or different from each other. Similarly, when n18 and n19 are each an integer of 2 or more, R ²⁸ and R ²⁹ may be the same or different from each other.

[Chemical Formula 18]

In Chemical Formula 18,

R ³¹ and R ³² are the same or different from each other, and each independently represent 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,

n20 and n21 are each independently an integer of 0 to 4,

R ³³ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

T ⁹ and T ¹⁰ are the same or different and are each independently a single bond, -O- or -COO-,

T ¹¹ is a single bond, -O-, -COO-, -CONH- or -OCO-.

When n20 is an integer of 2 or more, R ³¹ may be the same or different from each other. Similarly, when n21 is an integer of 2 or more, each of R ³² may be the same or different from each other.

When functional diamines are used in combination with aromatic diamines, some of the polyamic acids produced comprise divalent organic groups derived from aromatic diamines, and some comprise divalent organic groups derived from functional diamines.

When the diamine includes the aromatic diamine and the functional diamine, the aromatic diamine and the functional diamine may be included in a molar ratio of 5:95 Pa to 95: 5. When the aromatic diamine and the functional diamine are used within the above ranges, the pretilt angle of the liquid crystal molecules in the liquid crystal alignment layer can be easily adjusted, and the orientation can be effectively improved. In addition, the liquid crystal aligning agent and the liquid crystal aligning film prepared using the same may have excellent chemical resistance, electro-optical properties, thermal stability, and mechanical properties. Specifically, the aromatic diamine and the functional diamine may be included in a molar ratio of 10:90 Pa to 90:10.

(B-2) polyimide

Any of polyimide obtained by imidating the polyamic acid synthesize | combined from an acid dianhydride and diamine can be used for the said polyimide.

Unless otherwise described below, the description of the acid dianhydride and diamine is as described above.

The polyimide may be prepared by imidizing the polyamic acid represented by Chemical Formula 3.

Since a method of preparing polyimide by imidating polyamic acid is well known in the art, detailed description thereof will be omitted.

Polyimide according to one embodiment may include a repeating unit represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

X ² is the same or different at each repeating unit and is independently a tetravalent organic group derived from an alicyclic acid dianhydride or aromatic acid dianhydride,

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

(B-2-1) Acid dianhydride

The acid dianhydrides used to prepare the polyimide may be alicyclic acid dianhydrides, aromatic acid dianhydrides, or mixtures of one or more thereof, as described above in the polyamic acid.

(B-2-2) diamine

The diamine used to prepare the polyimide may be used as an aromatic diamine, a functional diamine or a mixture of one or more thereof, as described above in the polyamic acid.

(C) Solvent

According to one embodiment, the liquid crystal aligning agent includes a solvent.

As the solvent, any polymer capable of dissolving the polymer and the epoxy compound can be used.

As the solvent, N-methyl-2-pyrrolidone; N, N-dimethyl acetamide; N, N-dimethyl formamide; Dimethyl sulfoxide; ? -butyrolactone; Tetrahydrofuran (THF); And petroleum solvents such as meta cresol, phenol, halogenated phenols, and the like, but are not limited thereto.

The solvent may further include 2-butyl cellosolve (2-BC), thereby improving printability. In this case, the 2-butyl cellosolve may be included in an amount of 1 wt% to 60 wt% based on the total amount of the solvent including 2-butyl cellosolve. When 2-butyl cellosolve is included in the above range, the printability can be easily improved. Specifically, the 2-butyl cellosolve may be included in the amount of # 10% by weight to 60% by weight based on the total amount of the solvent including the 2-butyl cellosolve.

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

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

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

The content of the solvent in the liquid crystal aligning agent is not particularly limited, but may be used so that the content of solid content in the liquid crystal aligning agent is from 1% by weight to 25% by weight. When the content of solids is within the above range, the uniformity of the film can be properly maintained and the appropriate viscosity can be maintained by being less affected by the contamination of the substrate surface at the time of printing, thereby preventing the uniformity of the film due to the high viscosity at the time of printing. Can exhibit an appropriate transmittance. Specifically, the solid content may be 1 wt% to 20 wt%.

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

(D) Other additives

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

For example, suitable surfactants or coupling agents can be used as additives to improve printability.

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

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

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

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

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

The liquid crystal alignment film formed by the above-described method is used in a liquid crystal display without performing a uniaxial alignment treatment by light irradiation in a state where a voltage is applied or in some applications such as a vertical alignment film.

The liquid crystal photoalignment film according to the embodiment may be subjected to uniaxial alignment treatment by exposing for 10 seconds to 10 minutes at an energy of 5mJ to 1000mJ while a voltage of 5V to 50V is applied.

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

Example

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

Synthetic example  1: 2- ( Methacryloyloxy ) Ethyl 4- ( Bis (oxirane-2-ylmethyl) amino ) Benzoate (2-( methacryloyloxy ) ethyl  4-( bis ( oxirane -2- ylmethyl ) amino) benzoate Manufacturing

2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate was prepared as shown in Scheme 1 below.

[Reaction Scheme 1]

Step 1: 2-hydroxyethyl methacrylate (2- hydroxyethylmethacrylate Manufacturing

In a nitrogen atmosphere, 800 ml of methylene chloride was added to a 2 L flask, and 35.3 g (0.57 mol) of 1,2-ethanediol was dissolved at room temperature, followed by pyridine. Add 90 g (1.14 mol).

Subsequently, 60 g (0.57 mol) of methacryloyl chloride is slowly added dropwise and refrigerated after completion of the reaction. After cooling for 24 hours, the filtrate obtained by filtration of the resulting solid was neutralized with 1N HCl and separated. Subsequently, after the organic layer was concentrated, 2-hydroxyethylmethacrylate represented by the following Formula 20 was obtained through a column in about 82% yield.

[Chemical Formula 20]

Step 2: Ethyl 4- ( Bis (oxirane-2-ylmethyl) amino Benzoic acid ( ethyl  4- (bis ( oxirane -2-ylmethyl) amino) benzoic acid Manufacturing

In a nitrogen atmosphere, 400 mL of ethanol was added to a 1 L flask, and 100 g (0.60 mol) of benzocaine was dissolved at room temperature, and the temperature was raised to 70 ° C. Subsequently, 279 g (0.30 mol) of epichlorohydrin was dissolved in 100 mL of ethanol and added thereto. After completion of the reaction, 250g (0.30mol) of 50% aqueous NaOH solution was slowly added at 0 ° C.

The resulting solid is then filtered and the solvent in the filtrate is removed. After extraction with toluene, the organic layer was concentrated, and then, through a column, 4- (bis (oxirane-2-ylmethyl) amino) benzoic acid (4- (bis (oxiran-2) represented by Formula 21 below. -ylmethyl) amino) benzoic acid) was obtained in about 52% yield.

[Chemical Formula 21]

Step 3: 2- ( methacryloyloxy ) ethyl  4- (bis ( oxirane Preparation of -2-ylmethyl) amino) benzoate

In a nitrogen atmosphere, 400 ml of methylene chloride (MC) was added to a 1 L flask, and ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoic acid (ethyl 4- (bis (oxiran-2-ylmethyl) amino Add 200 g (0.88 mol) of benzoic acid and dissolve it.

Subsequently, 4- (dimethylamino) pyridine (DMAP) '107.5 g (0.88 mol) and N, N'-diisopropylcarbodiimide (DIC)' 111.1 After g (0.88 mol) was added, 114.5 g (0.88 mol) of 2-hydroxyethyl methacrylate was added slowly. After completion of the reaction, the organic layer was concentrated and then, through a column, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by the following Chemical Formula 2-1. (2- (methacryloyloxy) ethyl 4- (bis (oxiran-2-ylmethyl) amino) benzoate) was obtained in about 66% yield.

[Formula 2-1]

¹ H NMR (600 MHz, CDCl ₃ ) Calcd .: δ H 7.72 ppm (d, ArH, 2H), 6.87 ppm (d, ArH, 2H), 6.48 ppm (m, CH 2, 1H), 6.40 ppm (m, CH 2 , 1H), 4.56ppm (m, CH2, 2H), 4.48ppm (m, CH2, 2H), 3.61ppm (q, CH2, 2H), 3.36ppm (q, CH2, 2H), 2.77ppm (m, CH , 2H), 2.63ppm (q, CH2, 2H), 2.38ppm (q, CH2, 2H), 2.01ppm (t, CH3, 3H)

Manufacturing example One: Of polyamic acid (PAA-1)  Produce

0.7 moles of p-phenylenediamine and 3,5-diaminophenyldecyl represented by the following formula (23) while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler. 0.3 mmol of succinimide (3,5-diaminophenyldecyl succinimide) was added, and N-methyl-2-pyrrolidone (NMP) was added thereto to prepare a mixed solution.

(23)

1.0 mmol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in solid state was added to the mixed solution, followed by vigorous stirring. Solid content at this time is 20% by weight, the reaction was carried out for 10 hours while maintaining the temperature at 30 ℃ 50 50 ℃. A mixed organic solvent (mixing ratio (volume ratio) = 55: 45) of N-methyl-2-pyrrolidone and? -Butyrolactone was added thereto, followed by stirring at room temperature for 24 hours to give a polyamic acid (PAA-1) solution. Was prepared.

Manufacturing example 2: polyimide ( SPI -1)

0.8 mol of para-phenylenediamine and 0.2 mol of 3,5-diaminophenyldecyl succinimide represented by the formula (23) while passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injector, and a cooler. To this was added, N-methyl-2-pyrrolidone was added to prepare a mixed solution.

1.0 mmol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in solid state was added to the mixed solution, followed by vigorous stirring. Solid content at this time is 20% by weight, the reaction was carried out for 10 hours while maintaining the temperature at 30 ℃ 50 50 ℃. A mixed organic solvent (mixing ratio (volume ratio) = 55: 45) of N-methyl-2-pyrrolidone and? -Butyrolactone was added thereto, followed by stirring at room temperature for 24 hours to prepare a polyamic acid solution.

3.0 mol of acetic anhydride and 5.0 mol of pyridine were added to the “polyamic acid” solution prepared above, heated to 80 ° C., reacted for 6 hours, and the catalyst and solvent were removed by vacuum distillation to obtain a polyimide resin having a solid content of 20%. Prepared.

A mixed organic solvent (mixing ratio (volume ratio) = 55: 45) of N-methyl-2-pyrrolidone 부 and γ-butyrolactone was added to the prepared polyimide resin, and the mixture was stirred at room temperature for 24 hours for polyimide (SPI). -1) A solution was prepared.

Example  1: Preparation of liquid crystal aligning agent

80 g of the polyamic acid (PAA-1) solution of 8 wt% solids obtained in Preparation Example 1 and 20 g of the polyimide (SPI-1) solution of 8w% of solids obtained in Preparation Example 2 were mixed.

Subsequently, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Chemical Formula 2-1 obtained in Synthesis Example 1 was used as the epoxy compound. 100 parts by weight of the solid content of the liquid crystal aligning agent containing the compound (epoxy compound and polymer) was added to 0.01 part by weight, stirred for 24 hours while passing nitrogen, and then filtered through a filter having a particle size of 0.1 μm to give a liquid crystal orientation of 8 wt% of solid content. (SPVA-1) was obtained.

Example  2: Preparation of liquid crystal aligning agent

As the epoxy compound, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 containing the epoxy compound A liquid crystal aligning agent (SPVA-2) having a solid content of 8 wt% was obtained in the same manner as in Example 1, except that 30 parts by weight of the solid content (epoxy compound and polymer) of the liquid crystal aligning agent was added.

Example 3: Preparation of liquid crystal aligning agent

As the epoxy compound, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 containing the epoxy compound A liquid crystal aligning agent (SPVA-3) having a solid content of 8 wt% was obtained in the same manner as in Example 1, except that 50 parts by weight of the solid content (epoxy compound and polymer) of the liquid crystal aligning agent was added.

Example  4: Preparation of liquid crystal aligning agent

80 g of the polyamic acid (PAA-1) solution of 8 wt% solids obtained in Preparation Example 1 and 20 g of the polyimide (SPI-1) solution of 8w% of solids obtained in Preparation Example 2 were mixed.

Subsequently, the compound represented by the following Chemical Formula 2-3 as an epoxy compound was added to 0.01 part by weight based on 100 parts by weight of the solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound, and passed through nitrogen while 24 After stirring for some time, the liquid crystal aligning agent (SPVA-4) of 8 wt% of solid content was obtained by filtering by the filter of 0.1 micrometer of particle diameters.

[Formula 2-3]

Example  5: Preparation of liquid crystal aligning agent

The same method as in Example 4, except that the compound represented by Formula 2-3 as an epoxy compound was added to 30 parts by weight based on 100 parts by weight of solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound. It carried out by and obtained the liquid crystal aligning agent (SPVA-5) of 8 weight% of solid content.

Example 6: Preparation of liquid crystal aligning agent

The same method as in Example 4, except that the compound represented by Formula 2-3 as the epoxy compound was added to 50 parts by weight based on 100 parts by weight of the solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound. It carried out by the above and obtained the liquid crystal aligning agent (SPVA-6) of solid content 8wt%.

Example  7: Preparation of liquid crystal aligning agent

80 g of the polyamic acid (PAA-1) solution of 8 wt% solids obtained in Preparation Example 1 and 20 g of the polyimide (SPI-1) solution of 8w% of solids obtained in Preparation Example 2 were mixed.

Subsequently, the compound represented by the following Chemical Formula 2-7 was added as an epoxy compound to 0.01 part by weight based on 100 parts by weight of the solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound, and passed through nitrogen while 24 After stirring for some time, it filtered by the filter of 0.1 micrometer of particle diameters, and obtained the liquid crystal aligning agent (SPVA-7) of 8 weight% of solid content.

[Chemical Formula 2-7]

Example  8: Preparation of liquid crystal aligning agent

The same method as in Example 7, except that the compound represented by the formula (2-7) as an epoxy compound was added to 30 parts by weight based on 100 parts by weight of solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound. It carried out by the above and obtained the liquid crystal aligning agent (SPVA-8) of 8 weight% of solid content.

Example 9: Preparation of liquid crystal aligning agent

The same method as in Example 7, except that the compound represented by the formula (2-7) as an epoxy compound was added to 50 parts by weight based on 100 parts by weight of solids (epoxy compound and polymer) of the liquid crystal aligning agent containing the epoxy compound. The obtained liquid crystal aligning agent (SPVA-9) of 8 wt% of solid content was obtained.

Example  10: Preparation of liquid crystal aligning agent

2- (methacryloyloxy) ethyl 4- (bis () represented by Chemical Formula 2-1 obtained in Synthesis Example 1 as an epoxy compound in 100 g of a polyamic acid (PAA-1) solution having a solid content of 8 wt% obtained in Preparation Example 1. Oxylan-2-ylmethyl) amino) benzoate was added in an amount of 0.01 parts by weight based on 100 parts by weight of the solids (the epoxy compound and the polymer) of the liquid crystal aligning agent containing the epoxy compound, followed by stirring for 24 hours while passing nitrogen. It filtered by the filter of 0.1 micrometer of particle diameters, and obtained the liquid crystal aligning agent (SPVA-10) of 8 wt% of solid content.

Example  11: Preparation of liquid crystal aligning agent

As the epoxy compound, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 containing the epoxy compound A liquid crystal aligning agent (SPVA-11) having a solid content of 8 wt% was obtained in the same manner as in Example 10, except that 30 parts by weight of the solid content (epoxy compound and polymer) of the liquid crystal aligning agent was added.

Example  12: Preparation of Liquid Crystal Alignment Agent

2- (methacryloyloxy) ethyl 4- (bis () represented by Chemical Formula 2-1 obtained in Synthesis Example 1 as an epoxy compound in 100 g of a polyimide (SPI-1) solution having a solid content of 8 w% obtained in Preparation Example 2. Oxylan-2-ylmethyl) amino) benzoate was added in an amount of 0.01 parts by weight based on 100 parts by weight of the solids (the epoxy compound and the polymer) of the liquid crystal aligning agent containing the epoxy compound, followed by stirring for 24 hours while passing nitrogen. It filtered by the filter of 0.1 micrometer of particle diameters, and obtained the liquid crystal aligning agent (SPVA-12) of 8 wt% of solid content.

Example  13: Manufacture of liquid crystal aligning agent

As the epoxy compound, 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 containing the epoxy compound A liquid crystal aligning agent (SPVA-13) having a solid content of 8 wt% was obtained in the same manner as in Example 12, except that 30 parts by weight of the solid content (epoxy compound and polymer) of the liquid crystal aligning agent was added.

Comparative example  1: Preparation of liquid crystal aligning agent

Except for not using 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 It carried out similarly to 1 and obtained the liquid crystal aligning agent (SPVA-14) of 8 wt% of solid content.

Comparative example  2: Preparation of liquid crystal aligning agent

Except for not using 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 It carried out similarly to 10 and obtained the liquid crystal aligning agent (SPVA-15) of 8 wt% of solid content.

Comparative example  3: Preparation of liquid crystal aligning agent

Except for not using 2- (methacryloyloxy) ethyl 4- (bis (oxirane-2-ylmethyl) amino) benzoate represented by Formula 2-1 obtained in Synthesis Example 1 It carried out similarly to 12 and obtained the liquid crystal aligning agent (SPVA-16) of solid content 8wt%.

Test Example  1: vertical of liquid crystal aligning film Orientation  Evaluation (with standard liquid crystal cell Square  Difference (△ pretilt ) Measure)

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

To remove other parts of the ITO, leaving only 7 cm × 7 cm square ITO shapes and electrode ITO shapes for voltage application on a glass substrate with standard sized indium-tin oxide (ITO). Patterned using a photolithography process.

The liquid crystal aligning agent prepared in Examples 1 to 13 and Comparative Examples 1 to 3 was applied to the patterned ITO substrate, spin-coated to a thickness of 0.1 μm, and then subjected to a two-step curing process at temperatures of 80 ° C. and 220 ° C. After that, two substrates were prepared for each liquid crystal aligning agent.

The spacers are spread on one substrate, and the sealant is applied on the other substrate, followed by thermocompression bonding to assemble a cell gap of 3.25 mu m.

The liquid crystal for VA mode was inject | poured into the empty cell using the capillary phenomenon, and it sealed with the UV hardening bond for end sealing, and produced the liquid crystal cell for j test.

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

At this time, the vertical alignment evaluation criteria are as follows.

<Vertical Orientation Evaluation Criteria>

Good: When the difference of the pretilt angle from the standard liquid crystal cell is 0.3 ° to 4 °

Poor: If the difference of the pretilt angle from the standard liquid crystal cell is less than 0.3˚ or more than 4˚

Test Example  2: electrical characteristics evaluation

The voltage holding ratio (VHR) of each liquid crystal cell was measured according to the temperature by applying a voltage of 1V to the liquid crystal cell prepared in Test Example 1, and the residual DC of each liquid crystal cell by applying a voltage of -10V to + 10V. (RDC) voltage was measured.

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

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 measurement results are shown in Table 1 below.

Test Example  3: Light transmittance  evaluation

DC 30V is applied to each liquid crystal cell produced in Test Example 1 　 After applying a voltage, light is irradiated by energy of 20 J to align the liquid crystal alignment on the surface of the liquid crystal alignment film in a desired direction.

A voltage of AC 6.5V is applied to each of the liquid crystal cells to measure the amount of light transmitted through the liquid crystal cell. Prepared using the liquid crystal aligning agent of Examples 1-13 assuming 100% of the amount of transmitted light with respect to 400 nm-750 nm of light of the liquid crystal cell manufactured using the liquid crystal aligning agent of Comparative Examples 1-3 The amount of transmitted light for 400 nm to 750 nm of light of one liquid crystal cell was evaluated by comparing with the amount of transmitted light for 400 nm to 750 nm of light of the liquid crystal cell prepared using the liquid crystal aligning agent of Comparative Examples 1 to 3. .

The results are shown in Table 1 below.

Test Example  4: response speed evaluation

While applying alternating voltages of AC 6.5V and AC 0.1V to each of the liquid crystal cells fabricated in Test Example 1, the change of transmittance is recorded in real time using an oscilloscope (at the moment when the voltage of AC 6.5V is applied, Transmittance increases from 0% to 100%, and at the moment of applying a voltage of 0.1 V AC, transmittance decreases from 100% to 0%). The response rate is usually the sum of the time taken to reach from 10% to 90% of the transmission (rising time, T _on ) and the time of falling from 90% to 10% of the transmission (falling time, T _off ), where rising time (T _on ) was measured and compared.

The results are shown in Table 1 below.

Test Example  5: printability and End coating  Uniformity evaluation

On the cleaned glass substrate with a 7 cm × 7 cm square ITO, the liquid crystal aligning agent prepared in Examples 1 to 13 and Comparative Examples 1 to 3 was used an alignment film printer (CZ 200 ^® Nakan Corporation). After flexographic printing, the printed substrate was left to stand on a hot plate at 50 ° C to 90 ° C for 2 to 5 minutes to temporarily dry the coating film.

After the substrate was temporarily dried, the substrate was baked on a hot plate at 200 ° C. to 230 ° C. for 10 minutes to 30 minutes to prepare a substrate with a liquid crystal alignment film.

The film surface of the liquid crystal aligning film was measured by visual and electron microscopy (MX50 ^® Olympus Co., Ltd.) and the printability (pinhole and stain) and the film thickness change of the coating film were measured over the entire surface of the substrate (center and end). The results are shown in Table 1 below.

In Table 1 below, the printability on the 7 cm × 7 cm square ITO glass substrate was marked as good when the pinhole is 0 to 3, normal when 3 to 5, and more than 6 cases as poor, The unevenness is marked as good when not occurring and when it is defective. The coating film uniformity is regarded as good when the thickness variation is less than 0.005 μm, and the case where 0.005 μm to 0.01 μm is normal, and when it exceeds 0.01 μm is marked as bad. .

sample Perpendicular
Orientation Voltage retention rate (%) Residual DC
(mV) △ pretilt
(˚) Light transmittance
(%) Response speed
(rising, ms) Printability Example 1 Good 99.0 39 0.64 108 14 Good Example 2 Good 99.1 41 0.68 107 13 Good Example 3 Good 99.1 45 0.59 104 16 Good Example 4 Good 99.2 39 0.66 106 14 Good Example 5 Good 98.9 40 0.78 114 13 Good Example 6 Good 99.0 45 0.72 110 14 Good Example 7 Good 98.9 37 0.73 109 13 Good Example 8 Good 98.8 48 0.74 110 11 Good Example 9 Good 98.9 48 0.95 115 9 Good Example 10 Good 99.1 46 0.94 111 11 Good Example 11 Good 98.9 38 0.92 112 10 Good Example 12 Good 99.1 46 0.94 114 9 Good Example 13 Good 99.2 42 1.03 120 7 Good Comparative Example 1 Bad 98.8 43 0.0 100 43 Good Comparative Example 2 Bad 98.9 39 0.0 100 43 Good Comparative Example 3 Bad 98.9 50 0.0 100 43 Good

As shown in Table 1, the liquid crystal locator prepared in Examples 1 to 13 is excellent in the vertical alignment, electrical properties, light transmittance, response speed and printability, it can be confirmed that can be effectively used in the preparation of the liquid crystal alignment film have.

On the other hand, the liquid crystal aligning agent prepared in Comparative Examples 1 to 3 has good electrical characteristics and printability, but its vertical alignment, light transmittance, and response speed are poor, and thus the use of the liquid crystal alignment layer may be limited.

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 (10)

Epoxy compound containing a compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
A ¹ is a single bond, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, -COO-, or a substituted or unsubstituted C1 to C20 alkylene group,
A ² is a single bond, a substituted or unsubstituted divalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,
A ³ is a single bond, a substituted or unsubstituted divalent C1 to C20 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,
n1 is an integer of 0 or 1,
R ¹ is hydrogen or a methyl group,
R ² is hydrogen or a substituted or unsubstituted C 1 to C 10 alkyl group,
n2 is an integer of 0-4.
The method of claim 1,
The compound represented by Formula 1 is an epoxy compound comprising a compound represented by the formula 1-1:
[Formula 1-1]

In Chemical Formula 1-1,
A ¹ , A ² , A ³ , n ¹ , R ¹ , R ^2, and n ² are the same as defined in Chemical Formula 1.
The method of claim 1,
The compound represented by Formula 1 is an epoxy compound comprising one selected from compounds represented by the following formulas 2-1 to 2-10 and combinations thereof:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Formula 2-9]

[Formula 2-10]

.
Epoxy compound containing a compound represented by the formula (1); And
A polymer comprising one selected from polyamic acid, polyimide, and combinations thereof
Liquid crystal aligning agent containing:
[Formula 1]

In Chemical Formula 1,
A ¹ is a single bond, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, -COO-, or a substituted or unsubstituted C1 to C20 alkylene group,
A ² is a single bond, a substituted or unsubstituted divalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,
A ³ is a single bond, a substituted or unsubstituted divalent C1 to C20 aliphatic organic group, a substituted or unsubstituted divalent C2 to C30 aromatic organic group, or a substituted or unsubstituted divalent C3 to C30 alicyclic organic group ,
n1 is an integer of 0 or 1,
R ¹ is hydrogen or a methyl group,
R ² is hydrogen or a substituted or unsubstituted C 1 to C 10 alkyl group,
n2 is an integer of 0-4.
5. The method of claim 4,
The compound represented by Formula 1 is a liquid crystal aligning agent comprising a compound represented by the formula (1-1):
[Formula 1-1]

In Chemical Formula 1-1,
A ¹ , A ² , A ³ , n ¹ , R ¹ , R ^2, and n ² are the same as defined in Chemical Formula 1.
5. The method of claim 4,
The compound represented by Formula 1 is a liquid crystal aligning agent comprising one selected from compounds represented by the following formulas 2-1 to 2-10 and combinations thereof:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Formula 2-9]

[Formula 2-10]

.
5. The method of claim 4,
The epoxy compound is a liquid crystal aligning agent is contained in 0.01 to 50 parts by weight based on 100 parts by weight of the total of the epoxy compound and the polymer.
5. The method of claim 4,
Wherein the polyamic acid includes a repeating unit represented by the following Chemical Formula 3, and the polyimide includes a repeating unit represented by the following Chemical Formula 4:
(3)

In Formula 3,
X ¹ is the same or different in each repeating unit and each independently is a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride,
Y ¹ is the same or different at each repeating unit and each independently is a divalent organic group derived from diamine,
[Chemical Formula 4]

In Chemical Formula 4,
X ² is the same or different at each repeating unit and is independently a tetravalent organic group derived from an alicyclic acid dianhydride or aromatic acid dianhydride,
Y ² is the same or different from each other and is a divalent organic group independently derived from diamine.
The liquid crystal aligning film manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 4-8 to a board | substrate.
A liquid crystal display device comprising the liquid crystal display alignment film according to claim 9.