KR20130002788A - Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device including the liquid crystal alignment film - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent is provided to improve response rate and transmittance, to improve electric performance and to easily control a pretilt angle. CONSTITUTION: A liquid crystal alignment agent comprises a polyamic acid which comprises a repeating unit represented by chemical formula 1, a polyimide which comprises a repeating unit indicated in chemical formula 2, and a polymer selected from combinations thereof. In chemical formula 1 and 2, each of X^1 and X^2 is independently quadrivalent organic groups derived from alicyclic dianhydride or aromatic dianhydride, and each of Y^1 and Y^2 is a divalent organic group derived from a diamine. The polyamic acid and polyimide has a weight average molecular weight of 10,000-300,000 g/mol.

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

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

With the recent growth of the liquid crystal display device market, the demand for high quality liquid crystal display devices is increasing, and as the size of the liquid crystal display devices increases, the demand for high productivity liquid crystal alignment films is increasing. Accordingly, studies have been made on liquid crystal aligning agents for producing high-performance liquid crystal display alignment films having a low defect rate in a liquid crystal display device production process and capable of expressing excellent electro-optical characteristics and reliability.

One embodiment includes a polymer synthesized using a diamine containing a functional group having reactivity to light irradiation, thereby improving transmittance and response speed, excellent electrical properties such as voltage retention and residual DC, and wire diameter Provided is a liquid crystal aligning agent that can easily control blind spots.

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.

According to one embodiment, 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 Chemical Formula 1, a polyimide comprising a repeating unit represented by the following Chemical Formula 2, and a combination thereof To provide.

[Formula 1]

[Formula 2]

In the above Formulas 1 and 2,

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

Y ¹ and Y ² are each independently a divalent organic group derived from a diamine, and the diamine includes a diamine represented by the following formula (3) and a functional diamine represented by the following formula (4).

(3)

In Formula 3,

R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group, and specifically, may be hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group.

n ₁ is an integer of 0-3.

A ¹ is a substituted or unsubstituted C1 to C20 alkylene group, specifically, may be a substituted or unsubstituted C1 to C10 alkylene group.

A ² 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, a single bond, a substituted or unsubstituted divalent C1 to C15 aliphatic organic group, a substituted or unsubstituted divalent C2 to C15 aromatic organic group, or a substituted or unsubstituted divalent C3 to C15 alicyclic organic group Can be.

Z ¹ is a single bond, oxygen (O), 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 It is an alicyclic organic group, Specifically, a single bond, oxygen (O), a substituted or unsubstituted bivalent C1-C15 aliphatic organic group, a substituted or unsubstituted divalent C2-C15 aromatic organic group, or a substituted or unsubstituted Divalent C3 to C15 alicyclic organic group.

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

[Formula 4]

In Chemical Formula 4,

A ¹⁰ is -O-, -CO-, -COO-, -NH-, -NHCO-, -CONH-, -S- or -OCO-, specifically -O-, -CO-, -COO- Or -OCO-.

R ²⁵ is a substituted or unsubstituted C1 to C40 aliphatic organic group, or a substituted or unsubstituted C3 to C40 alicyclic organic group, specifically, a substituted or unsubstituted C4 to C40 aliphatic organic group, or a substituted or unsubstituted group C4 to C40 alicyclic organic group, the alicyclic organic group may be a fused two or more rings.

Specifically, the diamine represented by Chemical Formula 3 may include at least one selected from the group consisting of a compound represented by the following Chemical Formulas 5 to 9 and a combination thereof.

[Formula 5] [Formula 6] [Formula 7] [Formula 8] [Formula 9]

.

.

Specifically, the functional diamine represented by Chemical Formula 4 may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 10 to 13 and combinations thereof.

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

.

.

In the liquid crystal aligning agent, the diamine may include a diamine represented by Chemical Formula 3 and a functional diamine represented by Chemical Formula 4 in a molar ratio of 1:70 to 99: 1.

Meanwhile, in the liquid crystal aligning agent, the diamine may further include an aromatic diamine represented by the following Chemical Formulas 21 to 24 or a combination thereof.

[Chemical Formula 21]

[Formula 22]

(23)

≪ EMI ID =

In Chemical Formulas 21 to 24,

R ¹⁵ to R ²⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group are -O-, It may further comprise selected from the group consisting of -COO-, -CONH-, -OCO- and combinations thereof,

A ⁴ to A ⁹ are each independently a single bond, O, SO ₂ or C (R ¹⁰³ ) (R ¹⁰⁴ ), wherein R ¹⁰³ and R ¹⁰⁴ are each independently hydrogen or substituted or unsubstituted C1 to C6 An alkyl group,

n ₅ to n ₁₄ are each independently an integer of 0 to 4;

When the diamine includes both the diamine represented by the formula (3), the functional diamine represented by the formula (4) and the aromatic diamine, the diamine is 1 mol% to 1% by weight of the diamine represented by the formula (3) based on the total amount of the diamine. 95 mol%, 1 to 70 mol% of the functional diamine represented by the formula (4), and may include 3 to 80 mol% of the aromatic diamine.

The polyamic acid and the polyimide may each have a weight average molecular weight of 10,000 g / mol to 300,000 g / mol.

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

The liquid crystal aligning agent may have a solid content of 1 wt% to 25 wt%, and may have a viscosity of 3 cps to 30 cps.

According to another embodiment provides a liquid crystal alignment film prepared by applying the liquid crystal 향 alignment agent to a substrate.

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

Specific details of other embodiments are included in the following detailed description.

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

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

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group (NH ₂ , NH (R ¹⁰⁰ ) or N (R ¹⁰¹ ) (R ¹⁰² ), wherein R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² are each independently a C1 to C10 alkyl group), an amidino group, a hydrazine group, a hydra Substituted, unsubstituted alkyl groups, substituted or unsubstituted haloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alicyclic organic groups, substituted or unsubstituted aryl groups, substituted or unsubstituted groups It means substituted with one or more substituents selected from the group consisting of an alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocycloalkyl group.

Unless stated otherwise in the present specification, "alkyl group" means a C1 to C40 alkyl group, specifically, a C1 to C20 alkyl group, and "cycloalkyl group" means a C3 to C40 cycloalkyl group, specifically C3 To C20 cycloalkyl group, "heterocycloalkyl group" means C2 to C40 heterocycloalkyl group, specifically C2 to C20 heterocycloalkyl group, "alkylene group" means C1 to C40 alkylene group , Specifically, a C1 to C20 alkylene group, "alkoxy group" refers to a C1 to C40 alkoxy group, specifically a C1 to C20 alkoxy group, "cycloalkylene group" refers to a C3 to C40 cycloalkylene group Meaning, specifically, a C3 to C20 cycloalkylene group, and a "heterocycloalkylene group" means a C2 to C40 heterocycloalkylene group It means, specifically, C2 to C20 heterocycloalkylene group, "aryl group" means C6 to C40 aryl group, specifically C6 to C20 aryl group, "heteroaryl group" means C2 to C40 It means a heteroaryl group, specifically means a C2 to C18 heteroaryl group, "arylene" group means a C6 to C40 arylene group, specifically means a C6 to C20 arylene group, "heteroarylene group" Means a C2 to C40 heteroarylene group, specifically means a C2 to C20 heteroarylene group, "alkylaryl group" means a C7 to C40 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 C40 alkyl, C2 to C40 alkenyl, C2 to C40 alkynyl, C1 to C40 alkylene, C2 to C40 alkenylene, or C2 to C40 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 C40 cycloalkyl, C3 to C40 cycloalkenyl, C3 to C40 cycloalkynyl, C3 to C40 cycloalkylene, C3 to C40 cycloalkenylene, or C3 to C40 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 C40 aryl, C2 to C40 heteroaryl, C6 to C40 arylene or C2 to C40 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 or graft copolymerization, and "copolymer" means block copolymer, random copolymer or graft copolymer.

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

The liquid crystal aligning agent according to one embodiment includes a polymer selected from the group consisting of a polyamic acid including a repeating unit represented by Formula 1, a polyimide including a repeating unit represented by the following Formula 2, and a combination thereof .

[Formula 1]

[Formula 2]

In the above Formulas 1 and 2,

X ¹ and X ² 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 each independently a divalent organic group derived from a diamine, and the diamine includes a diamine represented by the following formula (3) and a functional diamine represented by the following formula (4). The Y ¹ may be the same or different from each repeating unit, and the Y ² may be the same or different from each other.

(3)

In Formula 3,

R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group, and specifically, may be hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group.

n ₁ is an integer of 0-3.

A ¹ is a substituted or unsubstituted C1 to C20 alkylene group, specifically, may be a substituted or unsubstituted C1 to C10 alkylene group, and more specifically, may be a substituted or unsubstituted C1 to C5 alkylene group.

A ² 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, a single bond, a substituted or unsubstituted divalent C1 to C15 aliphatic organic group, a substituted or unsubstituted divalent C2 to C15 aromatic organic group, or a substituted or unsubstituted divalent C3 to C15 alicyclic organic group And more specifically, a substituted or unsubstituted C1 to C15 alkylene group, a substituted or unsubstituted C6 to C15 arylene group, or a substituted or unsubstituted C3 to C15 cycloalkylene group.

Z ¹ is a single bond, oxygen (O), 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, a single bond, oxygen, a substituted or unsubstituted divalent C1 to C15 aliphatic organic group, a substituted or unsubstituted divalent C2 to C15 aromatic organic group, or a substituted or unsubstituted divalent C3 to C15 alicyclic organic group, more specifically, a single bond, oxygen, substituted or unsubstituted C1 to C15 alkylene group, substituted or unsubstituted C6 to C15 arylene group, or substituted or unsubstituted C3 to C15 It may be a cycloalkylene group, more specifically oxygen.

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

[Formula 4]

In Chemical Formula 4,

A ¹⁰ is -O-, -CO-, -COO-, -NH-, -NHCO-, -CONH-, -S- or -OCO-, specifically -O-, -CO-, -COO- Or -OCO-.

R ²⁵ is a substituted or unsubstituted C1 to C40 aliphatic organic group, or a substituted or unsubstituted C3 to C40 alicyclic organic group, specifically, a substituted or unsubstituted C4 to C40 aliphatic organic group, or a substituted or unsubstituted group It may be a C4 to C40 alicyclic organic group. The alicyclic organic group may be a fused two or more rings, more specifically, may have a steroid skeleton. Here, some of the hydrogen atoms of the aliphatic organic group and the alicyclic organic group, specifically 1 to 15 hydrogen atoms may be substituted with halogen, specifically fluorine (F), but is not limited thereto.

The diamine represented by Formula 3 includes residues derived from acrylates or methacrylates at the terminals, and residues derived from acrylates or residues derived from methacrylates react to light irradiation. Therefore, when the liquid crystal aligning agent is prepared using the diamine represented by Chemical Formula 3, the molecular shape of the liquid crystal can be induced in one direction when light irradiation is applied to the liquid crystal aligning agent, and thus the alignment can be effectively improved. have.

Specifically, the diamine represented by Chemical Formula 3 may include at least one selected from the group consisting of a compound represented by the following Chemical Formulas 5 to 9 and a combination thereof, but is not limited thereto.

[Formula 5] [Formula 6] [Formula 7] [Formula 8] [Formula 9]

Functional diamine represented by the formula (4) has an excellent structural structure of the interaction with the liquid crystal. Therefore, when the liquid crystal aligning agent is prepared using the functional diamine represented by Chemical Formula 4, the liquid crystal alignment, chemical resistance and electro-optical characteristics of the liquid crystal aligning agent can be improved, and the pretilt angle can be easily adjusted. A high pretilt angle can be expressed and the said liquid crystal aligning agent can be used in order to manufacture a vertical alignment type liquid crystal aligning film and a twisted nematic type liquid crystal aligning film.

Specifically, the functional diamine represented by Chemical Formula 4 may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 10 to 13 and combinations thereof, but is not limited thereto.

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

.

.

In the liquid crystal aligning agent, the diamine may include a diamine represented by Chemical Formula 3 and a functional diamine represented by Chemical Formula 4 in a molar ratio of 1:70 to 99: 1. In this case, it can have excellent vertical alignment force, and the pretilt angle can be easily adjusted. Specifically, the diamine may include a diamine represented by Chemical Formula 3 and a functional diamine represented by Chemical Formula 4 in a molar ratio of 10:50 to 90:10.

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

Hereinafter, each component will be described in detail.

Polymer

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

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

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

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

As the diamine, a diamine represented by the formula (3) and a functional diamine represented by the formula (4) may be used, and at least one of predetermined aromatic diamines may be further mixed and used therein.

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

The tetravalent organic group derived from the cycloaliphatic acid dianhydride may include at least one of the functional groups represented by the following Chemical Formulas 14 to 18, but is not limited thereto.

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In Chemical Formulas 14 to 18,

R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₂ is an integer of 0 to 3,

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

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

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

The tetravalent organic group derived from the aromatic acid dianhydride may include at least one of a functional group represented by Formula 19 and a functional group represented by Formula 20, but is not limited thereto.

[Formula 19]

[Chemical Formula 20]

In Chemical Formulas 19 and 20,

R ¹¹ and R ¹² are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

n ₃ and n ₄ are each independently an integer of 0 to 3,

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

When n ₃ is an integer of 2 or more, R ¹³ may be the same or different from each other. Similarly, when n ₄ is an integer of 2 or more, R ¹⁴ may be the same or different from each other.

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

The aromatic diamine may include at least one of the compounds represented by the following Chemical Formulas 21 to 24, but is not limited thereto. In this case, the polyamic acid and the polyimide may include a divalent organic group derived from the aromatic diamine. By the polyamic acid and the polyimide containing a divalent organic group derived from the aromatic diamine, it is possible to improve the chemical resistance, thermal stability and mechanical properties of the liquid crystal aligning agent and the liquid crystal aligning film formed therefrom.

[Chemical Formula 21]

[Formula 22]

(23)

≪ EMI ID =

In Chemical Formulas 21 to 24,

R ¹⁵ to R ²⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group are -O-, It may further comprise selected from the group consisting of -COO-, -CONH-, -OCO- and combinations thereof,

A ⁴ to A ⁹ are each independently a single bond, O, SO ₂ or C (R ¹⁰³ ) (R ¹⁰⁴ ), such as C (CF ₃ ) ₂ , wherein R ¹⁰³ and R ¹⁰⁴ are each independently hydrogen, or A substituted or unsubstituted C1 to C6 alkyl group,

n ₅ to n ₁₄ are each independently an integer of 0 to 4;

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

The diamine may be a diamine represented by the formula (3) and a functional diamine represented by the formula (4), may be used in combination with the aromatic diamine in addition to the diamine represented by the formula (3) and the functional diamine represented by the formula (4). .

When the diamine includes the aromatic diamine in addition to the diamine represented by the formula (3) and the functional diamine represented by the formula (4), 1 mol% to 95 mol% of the diamine represented by the formula (3) relative to the total amount of the diamine, A functional diamine represented by Formula 4 may be included in 1 mol% to 70 mol%, and the aromatic diamine may be included in 3 mol% to 80 mol%. When the amount of each diamine is in the above range, it is possible to effectively control the pretilt angle and the expression of the high pretilt angle, and also to effectively improve the liquid crystal alignment property, chemical resistance, electro-optical properties, thermal stability and mechanical properties. In addition, the processability can be improved by increasing the solubility.

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

When the liquid crystal aligning agent includes both the polyamic acid and the polyimide, the polyamic acid and the polyimide may be included in a weight ratio of 1:99 to 50:50. When the polyamic acid and the polyimide are included in the above range, the orientation stability can be improved. Specifically, the polyamic acid and the polyimide may be included in a weight ratio of 10:90 to 50:50.

In the liquid crystal aligning agent, the polymer may be included in an amount of 1 wt% to 25 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 according to one embodiment includes a solvent suitable for dissolving the polymer.

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

The solvent may further include 2-butyl cellosolve (2-BC), thereby improving printability. In this case, the 2-butyl cellosolve may be included in an amount of 1 wt% to 60 wt% based on the total amount of the solvent including 2-butyl cellosolve. When 2-butyl cellosolve is included in the above range, the printability can be easily improved. 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 a poor solvent alcohols, ketones, esters, ethers, hydrocarbons, or halogenated hydrocarbons in an appropriate ratio within the limit of the precipitation of the soluble polyimide polymer. The poor solvents may lower the surface energy of the liquid crystal aligning agent to improve spreadability and flatness during application.

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

Specific examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl Acetate, diethyl oxalate, malonic ester, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenylmethyl ether, ethylene glycol phenylethyl ether, di Ethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl 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.

Other additives

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

Examples of the epoxy compound may include a compound represented by the following Formula 25, but is not limited thereto.

(25)

In Formula 25,

A ¹⁴ is a substituted or unsubstituted C6 to C12 aromatic organic group, or a substituted or unsubstituted divalent C6 to C12 alicyclic organic group, or a substituted or unsubstituted divalent C6 to C12 aliphatic organic group, specifically It may be a substituted or unsubstituted C1 to C6 alkylene group.

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

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

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

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

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

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

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

According to 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: 4- (3,5- Diaminobenzyloxy ) Phenyl  Methacrylate (4- (3,5-diaminobenzyloxy) phenyl 메록acrylate Manufacturing

Step 1: 1- ( Bromomethyl ) -3,5-dinitrobenzene (1- ( bromomethyl ) -3,5-dinitrobenzene) and 4- ( tert - Butyldimethylsilyloxy ) Phenol (4- ( tert - butyldimethylsilyloxy ) phenol Manufacturing

In a nitrogen atmosphere, 350 g (1.8 mmol) of (3,5-dinitrophenyl) methanol) and 6 L of dichloromethane were added to a 10 L flask, and triphenylphosphine at room temperature was added thereto. 555 g (2.2 mmol) of (triphenyl phophine, PPh ₃ ) was added dropwise, and 377 g (2.2 mmol) of N-bromo succinimide (NBS) was slowly added dropwise, followed by stirring for 2 hours. After the reaction was completed, 4L of water and the reaction product were added and worked up. The organic layer was then washed with 4 L saturated aqueous NaCl solution, filtered and concentrated under reduced pressure to yield 1- (bromomethyl) -3,5-dinitrobenzene (1- (bromomethyl) -3 in about 76% yield. , 5-dinitrobenzene) was obtained.

Meanwhile, 200 g (1.8 mmol) of hydroquinone and tetrahydrofuran (THF) hydro 2 L were added to a 5 L flask under nitrogen atmosphere, and 87 g (3.0 mmol) of sodium hydride (NaH) was added thereto at room temperature. Add slowly Subsequently, a solution of 273 g (3.0 mmol) of tert-butyldimethylsilylchloride in 1.2 L of tetrahydrofuran (THF) was slowly added dropwise thereto, followed by stirring at room temperature for 4 hours. After the reaction was completed, 7 L of water and 1 L of ethylacetate were added to the reaction product and worked up. Subsequently, the organic layer was washed with saturated aqueous NaCl solution 4 L, and concentrated under reduced pressure to obtain 4- (tert-butyldimethylsilyloxy) phenol (4- (tert-butyldimethylsilyloxy) phenol) in a yield of about 80%.

Step 2: tert -Butyl (4- (3,5- Dinitrobenzyloxy ) Phenoxy ) Dimethylsilane Preparation of (tert-butyl (4- (3,5-dinitrobenzyloxy) phenoxy) dimethylsilane)

Under a nitrogen atmosphere, 345 g (1.321 mmol) of 1- (bromomethyl) -3,5-dinitrobenzene (1- (bromomethyl) -3,5-dinitrobenzene) and 4- (tert-butyldimethylsilyloxy in a 5 L flask ) 326 g (1.453 mmol) of 4- (tert-butyldimethylsilyloxy) phenol, 273.9 g (2.0 mmol) of potassium carbonate (K ₂ CO ₃ ), and 22 g (0.14 mmol) of potassium iodide (KI) were added thereto, followed by dimethylformamide. After adding 5.3 L (dimethyl formamide, DMF), the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, 4L of water and 5L of ethyl acetate were added to the reaction product and worked up. The organic layer was then washed twice with water, then with 4 L of saturated aqueous NaCl solution and concentrated under reduced pressure to yield tert-butyl (4- (3,5-dinitrobenzyloxy) phenoxy) dimethylsilane in a yield of about 71%. (tert-butyl (4- (3,5-dinitrobenzyloxy) phenoxy) dimethylsilane) was obtained.

STEP 3: tert -Butyl-5-((4- Hydroxyphenoxy ) methyl ) -1,3-phenylenedicarbamate ( tert - butyl -5-((4- hydroxyphenoxy ) methyl ) -1,3- phenylenedicarbamate Manufacturing

In a nitrogen atmosphere, 100 g (0.247 mmol) of tert-butyl (4- (3,5-dinitrobenzyloxy) phenoxy) dimethylsilane in a 5 L flask 502 g (2.3 mmol) of SnCl ₂ .2H ₂ O, 1 L of tetrahydrofuran (THF) and 1 L of water (H ₂ O) were added thereto, and the mixture was stirred at 60 ° C. under reflux for 6 hours. After the reaction was completed, 2 L of water, 1 L of ethyl acetate, and 2 kg of celite were added to the reaction product, and saturated sodium hydrogencarbonate (NaHCO ₃ ) was slowly added dropwise. The sodium hydrogen carbonate was added dropwise until the pH was 7 to 8, the celite was filtered, and the filtered solution was then worked up.

Then, the organic layer is concentrated under reduced pressure. Under a nitrogen atmosphere, 0.247 mmol of the concentrated compound was placed in a 5 L flask, to which 161.7 g of tetrahydrofuran (THF) 3L and di-tert-butoxypyrocarbonate (Boc) ₂ O) was added. 0.74mmol), and stirred at room temperature for 8 hours. After the reaction was completed, 2 L of water and 2 L of ethyl acetate were added to the reaction product, and the mixture was worked up. The organic layer was then washed twice with water, concentrated under reduced pressure and tert-butyl-5-((4-hydroxyphenoxy) methyl) -1,3-phenylenedicarbamate (tert) in about 90% yield. -butyl-5-((4-hydroxyphenoxy) methyl) -1,3-phenylenedicarbamate) was obtained.

Step 4: 4- (3,5- Bis (tert-butoxycarbonylamino) benzyloxy ) Phenyl  Methacrylate (4- (3,5-bis ( tert - butoxycarbonylamino ) benzyloxy) phenyl 메록acrylate Manufacturing

In a nitrogen atmosphere, tert-butyl-5-((4-hydroxyphenoxy) methyl) -1,3-phenylenedicarbamate (tert-butyl-5-((4-hydroxyphenoxy) methyl)- 106 g (0.25 mmol) of 1,3-phenylenedicarbamate), 1.5 L of tetrahydrofuran (THF), 106 ml of stabilizer, 35 g (0.3 mmol) of Hunig base, and 4-methylaminopyridine (DMAP) Add 3 g (0.024 mmol). Subsequently, 37.9 g (0.246 mmol) of methacrylic anhydride was slowly added dropwise thereto at 25 ° C. under a nitrogen atmosphere, followed by stirring at room temperature. 2L of water and 2L of ethyl acetate # 2 are put here, and it works up. The organic layer was then concentrated under reduced pressure to yield 4- (3,5-bis (tert-butoxycarbonylamino) benzyloxy) phenyl methacrylate (4- (3,5-bis (tert-butoxycarbonylamino) in about 80% yield. ) benzyloxy) phenyl methacrylate) was obtained.

Step 5: 4- (3,5- Diaminobenzyloxy ) Phenyl  Methacrylate (4- (3,5-diaminobenzyloxy) phenyl 메록acrylate Manufacturing

Under a nitrogen atmosphere, 4- (3,5-bis (tert-butoxycarbonylamino) benzyloxy) phenyl methacrylate (4- (3,5-bis (tert-butoxycarbonylamino) benzyloxy) phenyl methacrylate) in a 5L flask 103 g (0.206 mmol), 122 ml of stabilizer and 1.1 L of dichloromethane are added. Subsequently, 376.8 g (3.30 mmol) of trifluoroacetic acid (TFA) was slowly added dropwise thereto at 25 ° C, followed by stirring at room temperature. After the completion of the reaction, 4L of saturated sodium bicarbonate (NaHCO ₃ ) and 2L of ethyl acetate were added thereto and worked up. Subsequently, the organic layer was washed once more with water, concentrated under reduced pressure, recrystallized with ether and filtered to give 4- (3,5-diaminobenzyloxy) phenyl methacrylate represented by the following Formula 5 in about 50% yield: (4- (3,5-diaminobenzyloxy) phenyl methacrylate) was obtained.

[Chemical Formula 5]

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

0.79 mole of para-phenylenediamine while passing through nitrogen in a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler, 0.2 0.2 mole of functional diamine represented by the following formula (10), and the above formula 0.01 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate represented by 5 was added thereto, and N-methyl-2-pyrrolidone (NMP) was added thereto to prepare a mixed solution.

[Formula 10]

1.0 mol of 2,3,5-tricarboxycyclopentylacetic 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 ℃. N-methyl-2-pyrrolidone was added thereto and stirred at room temperature for 24 hours to prepare a polyamic acid solution.

3.0 mol of acetic anhydride and 5.0 mol of pyridine were added to the prepared polyamic acid solution, and the temperature was raised to 80 ° C., followed by reaction for 6 hours. The solution was prepared. N-methyl-2-pyrrolidone, γ-butyrolactone, and a mixed organic solvent (volume ratio = 50: 40: 10) were added thereto, followed by stirring at room temperature for 24 hours for polyimide. The liquid crystal aligning agent containing (PSPI-1) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-1) was 200,000.

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

A liquid crystal aligning agent including polyimide (PSPI-2) was prepared in the same manner as in Example 1 except for using the functional diamine represented by the following Formula 11 instead of the functional diamine represented by the Formula 10. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-2) was 190,000.

[Formula 11]

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

A liquid crystal aligning agent including polyimide (PSPI-3) was prepared in the same manner as in Example 1 except that the functional diamine represented by the following Chemical Formula 12 was used instead of the functional diamine represented by the Chemical Formula 10. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-3) was 190,000.

[Chemical Formula 12]

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

A liquid crystal aligning agent including polyimide (PSPI-4) was prepared in the same manner as in Example 1 except that the functional diamine represented by the following Chemical Formula 13 was used instead of the functional diamine represented by the Chemical Formula 10. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-4) was 190,000.

[Chemical Formula 13]

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

The same method as in Example 1, except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 10, and 0.3 mole of 4- (3,5-diaminobenzyloxy) phenyl methacrylate The liquid crystal aligning agent containing polyimide (PSPI-5) was manufactured by this. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-5) was 200,000.

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

The same method as in Example 2, except that 0.5 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 11, and 0.3 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-6) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-6) was 210,000.

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

The same method as in Example 3, except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 12, and 0.3 mole of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-7) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-7) was 190,000.

Example 8: polyimide ( PSPI -8) Preparation of Liquid Crystal Aligner

The same method as in Example 4, except that 0.5 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by Formula 13, and 0.3 mole of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-8) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-8) was 190,000.

Example 9: polyimide ( PSPI -9) Preparation of Liquid Crystal Aligner

The same method as in Example 1, except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 10, and 0.7 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-9) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-9) was 180,000.

Example 10: polyimide ( PSPI Preparation of a liquid crystal aligning agent containing -10)

0.1 mole of para-phenylenediamine, 0.2 mole of functional diamine represented by the above formula (11), and 4- (3,5-diaminobenzyloxy) phenyl methacrylate 0.7 mole were used in the same manner as in Example 2. The liquid crystal aligning agent containing the rho polyimide (PSPI-10) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-10) was 200,000.

Example 11: polyimide ( PSPI (11) Preparation of Liquid Crystal Aligner

The same method as in Example 3, except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 12, and 0.7 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-11) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-11) was 190,000.

Example 12: polyimide ( PSPI Preparation of the liquid crystal aligning agent containing -12)

The same method as in Example 4, except that 0.1 mol of para-phenylenediamine, 0.2 mol of the functional diamine represented by Formula 13, and 0.7 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the Rheopolyimide (PSPI-12) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-12) was 190,000.

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

The same method as in Example 1, except that 0.05 mol of para-phenylenediamine, 0.05 mol of the functional diamine represented by Formula 10, and 0.9 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-13) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-13) was 200,000.

Example 14: polyimide ( PSPI Preparation of the liquid crystal aligning agent containing -14)

The same method as in Example 2, except that 0.05 mol of para-phenylenediamine, 0.05 mol of the functional diamine represented by Formula 11, and 0.9 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-14) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-14) was 190,000.

Example 15: polyimide ( PSPI Preparation of liquid crystal aligning agent containing -15)

The same method as in Example 3, except that 0.05 mol of para-phenylenediamine, 0.05 mol of the functional diamine represented by Formula 12, and 0.9 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-15) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-15) was 210,000.

Example 16: polyimide ( PSPI Preparation of a liquid crystal aligning agent containing -16)

The same method as in Example 4, except that 0.05 mol of para-phenylenediamine, 0.05 mol of the functional diamine represented by Formula 13, and 0.9 mol of 4- (3,5-diaminobenzyloxy) phenyl methacrylate were used. The liquid crystal aligning agent containing the rho polyimide (PSPI-16) was manufactured. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-16) was 210,000.

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

Except that 0.8 moles of para-phenylenediamine and 0.2 moles of functional diamine represented by the above formula (10) were used as the diamine, and 4- (3,5-diaminobenzyloxy) phenyl methacrylate was not used. In the same manner as in 1, a liquid crystal aligning agent containing a polyimide (PSPI-17) was prepared. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-17) was 190,000.

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

As diamine, 0.8 mole of para-phenylenediamine and 0.2 mole of functional diamine represented by the above formula (11) were used, except that 4- (3,5-diaminobenzyloxy) phenyl methacrylate was not used. In the same manner as in Example 2, a liquid crystal aligning agent containing polyimide (PSPI-18) was prepared. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-18) was 200,000.

Comparative example 3: polyimide ( PSPI -19) Preparation of Liquid Crystal Aligner

Except that 0.8 moles of para-phenylenediamine and 0.2 moles of functional diamine represented by Formula 12 above were used as the diamine, and 4- (3,5-diaminobenzyloxy) phenyl methacrylate was not used. By the same method as 3, a liquid crystal aligning agent containing a polyimide (PSPI-19) was prepared. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-19) was 210,000.

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

Except that 0.8 moles of para-phenylenediamine and 0.2 moles of functional diamine represented by Formula 13 above were used as diamine, and 4- (3,5-diaminobenzyloxy) phenyl methacrylate was not used. In the same manner as in 4, a liquid crystal aligning agent containing polyimide (PSPI-20) was prepared. Solid content of the above-mentioned liquid crystal aligning agent was 10 weight%, and the viscosity was 25 cps. In addition, the weight average molecular weight of the said polyimide (PSPI-20) was 210,000.

Test Example  1: vertical of liquid crystal aligning film Orientation  Evaluation (with standard liquid crystal cell Pretilt  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 ITO from other parts, leaving only a 3 cm × 6 cm square ITO shape and an electrode ITO shape for voltage application on a glass substrate with standardized size of indium-tin oxide (ITO). Patterned using a photolithography process.

Applying the liquid crystal aligning agent prepared in Examples 1 to 16, and Comparative Examples 1 to 4 on the patterned ITO substrate to make a 0.1㎛ thickness, and then the two-step curing process at a temperature of 80 ℃ and 220 ℃ 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 then sealed with the UV hardening bond for end sealing, and the test liquid crystal cell was produced.

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

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. It manufactured using the liquid crystal aligning agent of Examples 1-16 on the assumption that the amount of transmitted light with respect to the light of 400 nm-750 nm of the liquid crystal cell manufactured using the liquid crystal aligning agent of Comparative Examples 1-4 was 100%. The amount of transmitted light for light of 400 nm to 750 nm of one liquid crystal cell was evaluated by comparing the amount of light transmitted for light of 400 nm to 750 nm of the liquid crystal cell prepared using the liquid crystal aligning agent of Comparative Examples 1 to 4 above. . 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.

sample Perpendicular
Orientation Voltage
Retention rate (%) Residual DC
(mV) △ pretilt
(˚) Light transmittance
(%) Response speed
(rising, ms) Example 1 Good 98.8 59 0.38 101 19 Example 2 Good 98.9 68 0.40 102 19 Example 3 Good 98.7 50 0.37 101 20 Example 4 Good 98.9 58 0.35 102 19 Example 5 Good 98.7 58 0.65 104 16 Example 6 Good 98.8 61 0.66 104 17 Example 7 Good 98.5 69 0.66 105 16 Example 8 Good 98.9 65 0.66 104 16 Example 9 Good 98.5 68 0.81 106 14 Example 10 Good 98.9 50 0.83 106 15 Example 11 Good 98.9 52 0.81 106 13 Example 12 Good 98.8 65 0.81 107 14 Example 13 Good 98.7 66 0.95 109 11 Example 14 Good 98.9 62 0.92 108 12 Example 15 Good 98.7 55 0.89 109 12 Example 16 Good 98.9 50 0.91 109 12 Comparative Example 1 Bad 98.8 69 0.0 100 25 Comparative Example 2 Bad 98.9 59 0.0 100 25 Comparative Example 3 Bad 98.7 68 0.0 100 25 Comparative Example 4 Bad 98.9 67 0.0 100 25

As shown in Table 1, the liquid crystal locator prepared in Examples 1 to 16 is excellent in the vertical alignment, electrical properties, light transmittance and response speed, it can be confirmed that can be effectively used in the preparation of the liquid crystal alignment film. On the other hand, the liquid crystal aligning agent prepared in Comparative Examples 1 to 4 has good electrical properties, but its vertical alignment, light transmittance, and response speed are poor, and thus the use of the liquid crystal aligning film 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 (14)

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 Chemical Formulas 1 and 2,
X ¹ and X ² are each independently a tetravalent organic group derived from an alicyclic acid dianhydride or an aromatic acid dianhydride,
Y ¹ and Y ² are each independently a divalent organic group derived from a diamine, the diamine includes a diamine represented by the following formula (3) and a functional diamine represented by the following formula (4),
(3)

In Chemical Formula 3,
R ¹ is hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, or a substituted or unsubstituted C2 to C30 aromatic organic group,
n ₁ is an integer of 0 to 3,
A ¹ is a substituted or unsubstituted C1 to C20 alkylene group,
A ² 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 ,
Z ¹ is a single bond, oxygen (O), 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,
R ² is hydrogen (H) or methyl group (CH ₃ ),
[Chemical Formula 4]

In Chemical Formula 4,
A ¹⁰ is -O-, -CO-, -COO-, -NH-, -NHCO-, -CONH-, -S- or -OCO-,
R ²⁵ is a substituted or unsubstituted C1 to C40 aliphatic organic group, or a substituted or unsubstituted C3 to C40 alicyclic organic group.
The method of claim 1,
In Chemical Formula 3,
R ¹ is hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
N ₁ is an integer of 0 to 3,
A ¹ is a substituted or unsubstituted C1 to C10 alkylene group,
A ² is a single bond, a substituted or unsubstituted divalent C 1 to C 15 aliphatic organic group, a substituted or unsubstituted divalent C 2 to C 15 aromatic organic group, or a substituted or unsubstituted divalent C 3 to C 15 alicyclic organic group ego,
Z ¹ is a single bond, oxygen (O), a substituted or unsubstituted divalent C1 to C15 aliphatic organic group, a substituted or unsubstituted divalent C2 to C15 aromatic organic group, or a substituted or unsubstituted divalent C3 to C15 alicyclic organic group,
R ² is hydrogen (H) or methyl group (CH ₃ ).
The method of claim 1,
The diamine represented by the formula (3) is a liquid crystal aligning agent comprising at least one selected from the group consisting of a compound represented by the following formula 5 to 9 and combinations thereof:
[Formula 5] [Formula 6] [Formula 7] [Formula 8] [Formula 9]

.
The method of claim 1,
In Chemical Formula 4,
A ¹⁰ is -O-, -CO-, -COO-, or -OCO-,
R ²⁵ is a substituted or unsubstituted C4 to C40 aliphatic organic group, or a substituted or unsubstituted C4 to C40 alicyclic organic group, wherein the alicyclic organic group has two or more rings fused to each other.
The method of claim 1,
Functional diamine represented by the formula (4) is a liquid crystal aligning agent comprising at least one selected from the group consisting of compounds represented by the following formulas 10 to 13 and combinations thereof:
[Formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

.
The method of claim 1,
The diamine is a liquid crystal aligning agent comprising a diamine represented by the formula (3) and a functional diamine represented by the formula (4) in a molar ratio of 1:70 to 99: 1.
The method of claim 1,
Wherein the diamine further comprises an aromatic diamine represented by the following Chemical Formulas 21 to 24 or a combination thereof:
[Chemical Formula 21]

[Chemical Formula 22]

(23)

[Formula 24]

In Chemical Formulas 21 to 24,
R ¹⁵ to R ²⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and the alkyl group, the aryl group and the heteroaryl group are -O-, It may further comprise selected from the group consisting of -COO-, -CONH-, -OCO- and combinations thereof,
A ⁴ to A ⁹ are each independently a single bond, O, SO ₂ or C (R ¹⁰³ ) (R ¹⁰⁴ ), wherein R ¹⁰³ and R ¹⁰⁴ are each independently hydrogen or substituted or unsubstituted C1 to C6 Alkyl group,
n ₅ to n ₁₄ are each independently an integer of 0 to 4;
The method of claim 7, wherein
The diamine is based on the total amount of the diamine, 1 mol% to 95 mol% of the diamine represented by the formula (3), 1 mol% to 70 mol% of the functional diamine represented by the formula (4), and 3 mol% to the aromatic diamine Liquid crystal aligning agent to contain in 80 mol%.
The method of claim 1,
Wherein said polyamic acid and said polyimide each have a weight average molecular weight of 10,000 g / mol to 300,000 g / mol.
The method of claim 1,
When the liquid crystal aligning agent includes the polyamic acid and the polyimide, the liquid crystal aligning agent containing the polyamic acid and the polyimide in a weight ratio of 1:99 to 50:50.
The method of claim 1,
Wherein the liquid crystal aligning agent has a solid content of 1% by weight to 25% by weight.
The method of claim 1,
The liquid crystal aligning agent having a viscosity of 3 cps to 30 cps.
The liquid crystal aligning film manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 1-12 to a board | substrate.
A liquid crystal display device comprising the liquid crystal alignment film according to claim 13.