KR20200059036A - Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent composition capable of realizing improved alignment and electrical properties while having excellent film strength, to a production method of a liquid crystal aligning film using the same, to a liquid crystal aligning film using the same, and to a liquid crystal display device. The liquid crystal aligning agent composition comprises: a polymer for a first liquid crystal aligning agent; a polymer for a second liquid crystal aligning agent; and a cross-linker compound.

Description

Liquid crystal aligning agent composition, manufacturing method of liquid crystal aligning film using same, liquid crystal aligning film and liquid crystal display device using same

The present invention is a liquid crystal aligning agent composition capable of realizing improved alignment properties and electrical properties while exhibiting high imidization conversion rate and excellent film strength when synthesizing a liquid crystal alignment film, a method for manufacturing a liquid crystal alignment film using the same, a liquid crystal alignment film and a liquid crystal display device using the same It is about.

In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning a liquid crystal in a constant direction. Specifically, 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, so that the liquid crystal alignment film has an appropriate direction. In order to obtain uniform brightness and high contrast ratio in the liquid crystal display device, it is essential to uniformly align the liquid crystal.

As one of the methods for aligning the liquid crystal, a rubbing method is used in which a polymer film such as polyimide is applied to a substrate such as glass and the surface is rubbed in a certain direction using fibers such as nylon or polyester. However, the rubbing method may cause fine dust or electrostatic discharge (ESD) when the fiber and the polymer film are rubbed, which may cause serious problems when manufacturing a liquid crystal panel.

In order to solve the problem of the rubbing method, recently, a photo-alignment method of inducing anisotropy (anisotropy) to a polymer film by irradiating light rather than friction and arranging liquid crystals using the same has been studied.

Various materials have been introduced as materials that can be used in the photo-alignment method, and among them, polyimide is mainly used for good overall performance of the liquid crystal alignment film. Accordingly, after coating in the form of a precursor such as polyamic acid or polyamic acid ester, a polyimide is formed through a heat treatment process at a temperature of 200 ° C to 230 ° C, and light irradiation is performed thereon to perform orientation treatment.

However, in order to obtain sufficient liquid crystal alignment by light irradiation on the polyimide film, not only is it difficult to secure actual productivity, but also an additional heat treatment process is required to secure alignment stability after light irradiation. Due to the large size of the manufacturing process, a scattering phenomenon of a column space (CS) occurs in the manufacturing process, and a haze occurs on the surface of the liquid crystal alignment layer, which causes a defect in the Milky Way, so that the performance of the panel is limited.

In addition, a high voltage holding ratio (VHR) must be exhibited for high-quality driving of the liquid crystal display device, and there is a limit in displaying this with only polyimide. In particular, as the demand for low-power displays has increased in recent years, the liquid crystal aligning agent may affect not only the basic characteristics of alignment of liquid crystals, but also electrical characteristics such as afterimages and voltage retention caused by DC / AC voltage. As a result, the need for development of a liquid crystal alignment material capable of simultaneously realizing excellent liquid crystal alignment and electrical characteristics is increasing.

Accordingly, a method of adding various crosslinking agents to the liquid crystal aligning agent composition has been proposed to produce a liquid crystal aligning film having a high film strength required in the display field, but electrical properties at high temperature and low frequency are reduced due to simple addition of the crosslinking agent compound. It was difficult to manufacture a liquid crystal alignment film applicable to a high performance / low power display.

Accordingly, there is a need to develop a composition capable of increasing the alignment characteristics and electrical properties of the alignment layer while manufacturing an alignment layer having a high film strength.

The present invention relates to a liquid crystal aligning agent composition capable of realizing improved alignment properties and electrical properties while having excellent film strength.

In addition, the present invention is to provide a method for producing a liquid crystal alignment film using the liquid crystal aligning agent composition.

In addition, the present specification is to provide a liquid crystal alignment film using the liquid crystal aligning agent composition and a liquid crystal display device including the same.

In the present specification, a polymer for a first liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2 and a repeating unit represented by the following Chemical Formula 3; A polymer for a second liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 4, a repeating unit represented by Formula 5 and a repeating unit represented by Formula 6; And it provides a liquid crystal aligning agent composition comprising a crosslinking agent compound represented by the formula (10).

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 1 to 6, at least one of R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, at least one of R ₃ and R ₄ is an alkyl group having 1 to 10 carbon atoms, and the rest is hydrogen. ,

X ₁ to X ₆ are each independently a tetravalent organic group represented by the following formula (7),

[Formula 7]

In Chemical Formula 7, R ₇ to R ₁₂ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and L ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , -CR ₁₃ R ₁₄ -,-(CH ₂ ) _Z- , -O (CH ₂ ) _Z O-, -COO (CH ₂ ) _Z OCO-, -CONH-, phenylene or combinations thereof Any one selected from the group consisting of, wherein L ₁ To R ₁₃ And R _{14 Are} each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and z in L ₁ is 1 to 10 Is an integer,

Y ₁ to Y ₃ are each independently a divalent organic group represented by the following formula (8),

[Formula 8]

In Chemical Formula 8, A is a group 15 element, R ^′ is hydrogen, or alkyl having 1 to 10 carbons, a is an integer of 1 to 3, at least one of Z ₁ to Z ₄ is nitrogen, and the rest is carbon. ego,

Y ₄ to Y ₆ are each independently a divalent organic group represented by the following formula (9),

[Formula 9]

In Chemical Formula 9, Ar ₁ , Ar ₂ are each independently a polycyclic arylene group having 10 or more carbon atoms, and L ₂ is a single bond, -O-, -CO-, -S-, -SO _2- , -C ( CH ₃ ) _2- , -C (CF ₃ ) _2- , -CONH-, -COO-,-(CH ₂ ) _y- , -O (CH ₂ ) _y O-, -O (CH ₂ ) _y- , -NH-, -NH (CH ₂ ) _y -NH-, -NH (CH ₂ ) _y O-, -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O-, -COO- (CH ₂ ) _y- OCO-, or -OCO- (CH ₂ ) _y -COO- is any one selected from the above, in L ₂ , y is an integer of 1 to 10, n is an integer of 1 to 5,

[Formula 10]

In Formula 10, A ₁ is a monovalent to tetravalent functional group, j is an integer from 1 to 4, L ₄ and L ₅ is the same or different from each other, and each independently is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R ₁₉ and R ₂₀ is a silicon-containing monovalent functional group each independently.

In addition, in the present specification, forming a coating film by applying the liquid crystal aligning agent composition to a substrate; Drying the coating film; Irradiating light to the coating film immediately after the drying step to perform alignment treatment; And curing the heat-treated coating film by heat treatment.

In addition, in the present specification, a liquid crystal alignment film including an alignment hardened product of the liquid crystal aligning agent composition and a liquid crystal display device including the same are provided.

Hereinafter, a liquid crystal aligning agent composition according to a specific embodiment of the present invention, a method of manufacturing a liquid crystal aligning film using the same, and a liquid crystal aligning film and a liquid crystal display device using the same will be described in more detail.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated otherwise.

In the present specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; Amino group; Carboxy group; Sulfonic acid group; Sulfonamide groups; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

Means a linkage to another substituent.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, the halo alkyl group means a functional group in which the halogen group is substituted with the aforementioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine or iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, and may be, for example, monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

Halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sn) or bismuth (Bi).

Nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are combined, and a nitrogen oxide functional group means a functional group containing nitrogen oxide in a functional group. As the nitrogen oxide functional group, a nitro group (-NO ₂ ) or the like can be used.

In the present specification, the alkylene group is a divalent functional group derived from alkane, and the number of carbon atoms is 1 to 20, or 1 to 10, or 1 to 5. For example, as a straight-chain, branched or cyclic, methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, and the like. One or more hydrogen atoms contained in the alkylene group may be substituted with substituents similar to those of the alkyl group.

In the present specification, the heteroalkylene group is an alkylene group containing oxygen (O), nitrogen (N) or sulfur (S) as a heteroatom, and has 1 to 10 carbon atoms or 1 to 5 carbon atoms. For example, it may be oxy alkylene. One or more hydrogen atoms contained in the heteroalkylene group may be substituted with substituents similar to those of the alkyl group.

In the present specification, the cycloalkylene group is a divalent functional group derived from cycloalkane, and has 3 to 20 carbon atoms or 3 to 10 carbon atoms. For example, cyclopropylene, cyclobutylene, cyclopentylene, 3-methylcyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 3-methylcyclohexylene, 4-methylcyclohexylene, 2 , 3-dimethylcyclohexylene, 3,4,5-trimethylcyclohexylene, 4-tert-butylcyclohexylene, cycloheptylene, cyclooctylene, and the like. The cycloalkylene group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and may be monocyclic or polycyclic, and has 6 to 20 carbon atoms or 6 to 10 carbon atoms. For example, it may be a phenylene group, biphenylene group, terphenylene group, stilbenylene group, naphthylenyl group, but is not limited thereto. Each of the at least one hydrogen atom contained in the arylene group may be substituted with a substituent similar to that of the alkyl group.

In this specification, the heteroarylene group has 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or 6 to 20 carbon atoms. The heteroatom is an arylene group containing O, N or S, and one or more hydrogen atoms contained in the heteroarylene group can be substituted with the same substituents as the alkyl group.

In this specification, the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, detectors and analytical columns, such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied. Conditions, solvents, and flow rates can be applied. As a specific example of the measurement conditions, using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column, the evaluation temperature is 160 ° C., dimethylformamide (DMF) and tetrahydrofuran (THF). Was mixed at a weight ratio of 50wt%: 50wt% and used as a solvent. The flow rate was 1mL / min, the sample was prepared at a concentration of 10mg / 10mL, and then supplied in an amount of 200 μL, and the assay formed using a polystyrene standard The value of Mw can be obtained using the curve. The molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In the present specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bound to an arbitrary compound are removed, for example, a divalent functional group, a trivalent functional group, and a tetravalent functional group. For example, a tetravalent functional group derived from cyclobutane refers to a residue in which any 4 hydrogen atoms attached to cyclobutane are removed.

In the present specification, a direct bond or a single bond means that there is no atom or atomic group at the corresponding position, and is connected by a bond line. Specifically, it means that a separate atom is not present in a portion represented by L ₁ and L ₂ in the chemical formula.

The liquid crystal aligning agent composition according to the present invention is a polymer for a first liquid crystal aligning agent, which is a polyimide precursor derived from diamine having an asymmetric pyridine structure, and a polymer for a second liquid crystal aligning agent, which is a polyimide precursor derived from diamine containing a polycyclic arylene group. The main feature is to include.

In the present invention, by including the polymer for the first liquid crystal aligning agent prepared from a diamine compound having an asymmetric pyridine structure containing a nitrogen atom, the liquid crystal aligning film has a high voltage retention even at high temperatures, and thus electrical properties and stability can be greatly improved. Not only can the contrast ratio be reduced or the afterimage phenomenon improved, but also the orientation stability due to thermal stress and the mechanical strength of the alignment layer may be improved.

And, in the present invention, it was confirmed that it is possible to maximize the electrical properties and alignment performance of the liquid crystal display device to which the liquid crystal alignment layer is applied, including a polymer for a second liquid crystal aligning agent, which is a polyimide precursor derived from a diamine containing a polycyclic arylene group. .

In addition, in the liquid crystal aligning agent composition of the above embodiment, the crosslinking agent compound added together with the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent, as shown in Chemical Formula 10, ends of the hydroxy group (-OH), which is a crosslinkable functional group. R ₁₉ and The R ₂₀ functional group acted as a protecting group to improve the dispersibility in the liquid crystal aligning agent composition, thereby confirming through experiments that the alignment characteristics and alignment stability of the finally obtained alignment film were improved, and the invention was completed.

In addition, the inventors of the cross-linking functional group hydroxy group (-OH) terminal R ₁₉ and When substituted with a silicon-containing functional group of R ₂₀ , the reactivity of the cross-linking agent in the initial drying process is reduced compared to the existing hydroxy group (-OH) terminal crosslinking agent as it contains the silicon-containing functional group, and the crosslinking reaction starts after the exposure process for orientation. It was confirmed that the decrease in the initial orientation by the crosslinking agent was reduced. In addition, it was confirmed through experiments that the technical effect of increasing the degree of alignment by increasing the imidization conversion rate and increasing the rearrangement rate in the process of imidization after exposure for orientation was increased, and the invention was completed.

R ₁₉ introduced at the end of the crosslinkable functional group of the crosslinker compound, and The functional group of R ₂₀ can improve the stability and reliability of the composition by minimizing the formation of unnecessary cross-linking structures by inhibiting the cross-linking reaction by the cross-linking functional group in the liquid crystal alignment agent composition, and for heat treatment during drying or firing of the liquid crystal alignment layer. By desorption and removal at a temperature of about 80 ° C. or higher, the hydroxyl group at the end of the crosslinkable functional group is recovered, and a smooth crosslinking reaction can be performed to improve the mechanical properties of the alignment layer.

That is, in the liquid crystal aligning agent composition, the structure of the crosslinker compound represented by the formula (10) is maintained, so that the crosslinking reaction between the polyimide or precursor polymer thereof and the crosslinker compound represented by the formula (10) can be suppressed. In addition, after passing through a drying process, an exposure process, a curing process, etc. for preparing a liquid crystal alignment film from a liquid crystal aligning agent composition, when the temperature increases by heat treatment, R ₁₉ in the crosslinking agent compound represented by Chemical Formula 10 and As the functional group of R ₂₀ is substituted with a hydrogen atom, a crosslinking reaction between the polyimide or its precursor polymer and the crosslinking agent compound represented by Chemical Formula 12 described below may proceed.

Therefore, the liquid crystal aligning agent composition of the above embodiment can sufficiently improve the dispersibility of the crosslinking agent compound and the polyimide or precursor polymer thereof by inhibiting the crosslinking reactivity of the crosslinking agent compound added in the composition, and the liquid crystal aligning film to other embodiments described below. During the manufacturing process, the crosslinking reaction between the crosslinking agent compound and the polyimide or precursor polymer in the composition improves the strength of the alignment layer, and it is possible to realize excellent alignment characteristics and electrical characteristics in the final produced liquid crystal alignment cell.

1. Liquid crystal aligning agent composition

According to one embodiment of the invention, the first liquid crystal alignment including at least one repeating unit selected from the group consisting of the repeating unit represented by Formula 1, the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 Medicinal polymers; A second liquid crystal aligning polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 4, a repeating unit represented by Formula 5 and a repeating unit represented by Formula 6; And it may be provided with a liquid crystal aligning agent composition comprising a crosslinking agent compound represented by the formula (10).

Specifically, the polymer for the first liquid crystal aligning agent is a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, a repeating unit represented by Formula 3, or a mixture of two of them, or Mixtures of all three may be included.

In addition, the polymer for the second liquid crystal aligning agent is a repeating unit represented by the formula (4), a repeating unit represented by the formula (5), one of the repeating units represented by the formula (6), or a mixture of two of them, or these Mixtures of all three may be included.

Specifically, in the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent in the liquid crystal aligning agent composition according to the one embodiment, X ₁ to X ₆ may each independently be a tetravalent organic group represented by Chemical Formula 7 above. have. The X ₁ to X ₆ may be a functional group derived from a polyamic acid, polyamic acid ester, or tetracarboxylic dianhydride compound used in the synthesis of polyimide.

In Chemical Formula 7, R ₇ to R ₁₂ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and L ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , -CR ₁₃ R ₁₄ -,-(CH ₂ ) _Z- , -O (CH ₂ ) _Z O-, -COO (CH ₂ ) _Z OCO-, -CONH-, or phenylene One, R ₁₃ and R ₁₄ in L ₁ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and z in L ₁ is an integer of 1 to 10.

More preferably, X ₁ to X ₆ are each independently an organic group represented by the following Chemical Formula 7-1 derived from cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,3-dimethylcyclobutane- Tetrahydro- [3,3'-bifuran] -2,2 ', 5,5'-tetraone, an organic group represented by the following formula 7-2 derived from 1,2,3,4-tetracarboxylic dihydrate The organic group represented by the following formula 7-3 derived from, the organic group represented by the following formula 7-4 derived from the 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, the following formula 7- derived from pyromellitic acid dihydrate The organic group of 5 or 3,3 ', 4,4'-biphenyltetracarboxylic acid dihydrate may be derived from an organic group of the formula 7-6.

 [Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Formula 7-4]

[Formula 7-5]

[Formula 7-6]

Meanwhile, the polymer for the first liquid crystal aligning agent in the liquid crystal aligning agent composition according to the embodiment may be a divalent organic group in which Y ₁ to Y ₃ are independently represented by Formula 8 in the repeating units of Formulas 1 to 3. The Y ₁ , Y ₂ , and Y ₃ are defined as a divalent organic group represented by Chemical Formula 8, and may provide a polymer for a liquid crystal aligning agent having various structures capable of expressing the above-described effects.

As described above, as the polymer for the first liquid crystal aligning agent is synthesized from a diamine containing a specific organic functional group represented by Chemical Formula 8, it can have a high voltage retention even in a high temperature environment, and improve the electrical conductivity by decreasing the contrast ratio or afterimage phenomenon. It has features that improve properties.

In Chemical Formula 8, A is a group 15 element, and the group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sn), or bismuth (Bi). The R ^' is a functional group that binds to the A, and can bind to the A element as many as the number represented by a. Preferably, in Formula 12, A is nitrogen, R ^' is hydrogen, and a may be 1.

On the other hand, in the formula (8), at least one of Z ₁ to Z ₄ is nitrogen, the rest of the carbon satisfying the carbon, the formula (12) by the nitrogen atom to achieve an asymmetric structure that is not symmetrical about the center point or the center line Can be. The formula (12) is a repeating unit derived from a diamine having a specific structure containing a nitrogen atom or the like, which is a precursor used for forming a polymer for a liquid crystal aligning agent, and appears to be due to the use of an asymmetric diamine as described below.

The functional group represented by Formula 8 has a structural characteristic in which two aromatic ring compounds, preferably a heteroaromatic ring compound and an aromatic ring compound, are bonded through a secondary amine group or a tertiary amine group. Accordingly, while the alignment property or the afterimage property as a liquid crystal alignment agent satisfies an equal level or higher, the voltage retention is improved, and thus excellent electrical properties can be realized.

On the other hand, when two aromatic cyclic compounds are combined by a single bond without a secondary amine group or a tertiary amine group, a technical problem may occur in that the alignment characteristics of the liquid crystal aligning agent are poor and the voltage retention is significantly reduced.

In addition, when each of the two aromatic cyclic compounds bound through a secondary amine group or a tertiary amine group does not contain a nitrogen atom, an imidization reaction is performed on a polyamic acid or a polyamic acid ester formed by the reaction of an amine and an acid anhydride. Even if it proceeds, there is a limit in that the imidation rate in the final liquid crystal alignment film decreases, as a sufficient imidization reaction (eg, through a heat treatment at 230 ° C.) fails to proceed.

In addition, the functional group represented by Formula 8 is characterized in that only two amine groups and hydrogen are bonded to each of the two aromatic ring compounds, preferably the heteroaromatic ring compound and the aromatic ring compound, and no other substituents are introduced. When a substituent, for example, a fluoroalkyl group, is introduced into the heteroaromatic ring compound or the aromatic ring compound, a technical problem may occur in that the alignment characteristics of the liquid crystal aligning agent are poor and the voltage retention is significantly reduced.

More specifically, in Formula 8, one of Z ₁ to Z ₄ is nitrogen, the other may be carbon, and in Formula 8, one of Z ₁ or Z ₃ is nitrogen and the other is carbon, Z ₂ and Z ₄ may be carbon. That is, in Formula 8, the aromatic ring containing Z ₁ to Z ₄ may have a pyridine structure. Accordingly, the liquid crystal display device to which the polymer for liquid crystal aligning agent of one embodiment is applied can realize high voltage retention and liquid crystal alignment.

In addition, the Chemical Formula 8 may include one or more repeating units selected from the group consisting of the following Chemical Formulas 8-1, 8-2, and 8-3.

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

In the above Chemical Formulas 8-1 to 8-3, the contents of A, Z ₁ to Z ₄ , R ^' and a include the contents described above in Chemical Formula 8.

As described above, as the repeating unit represented by Chemical Formula 8 includes one or more repeating units selected from the group consisting of Chemical Formula 8-1, Chemical Formula 8-2, and Chemical Formula 8-3, superior liquid crystal alignment can be realized. .

More specifically, the example of the organic group represented by Chemical Formula 8 is not particularly limited, but may be, for example, one or more functional groups selected from the group consisting of the following Chemical Formulas 8-4, 8-5, and 8-6. .

[Formula 8-4]

[Formula 8-5]

[Formula 8-6]

On the other hand, the polymer for the second liquid crystal aligning agent in the liquid crystal aligning agent composition according to the above embodiment is a divalent organic group in which the formulas 4 to 6, Y ₄ to Y ₆ are each independently represented by the formula (9). By including the polymer for the second liquid crystal aligning agent containing the organic group represented by the formula (9), it is possible to greatly improve the electrical properties of the alignment film such as voltage holding ratio (Voltage Holding Ratio), amplify the alignment of the liquid crystal alignment film, By improving the mechanical properties, it is possible to secure the durability of the alignment layer.

In Chemical Formula 9, Ar ₁ , Ar ₂ are each independently a polycyclic arylene group having 10 or more carbon atoms, and L ₂ is a single bond, -O-, -CO-, -S-, -SO _2- , -C ( CH ₃ ) _2- , -C (CF ₃ ) _2- , -CONH-, -COO-,-(CH ₂ ) _y- , -O (CH ₂ ) _y O-, -O (CH ₂ ) _y- , -NH-, -NH (CH ₂ ) _y -NH-, -NH (CH ₂ ) _y O-, -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O-, -COO- (CH ₂ ) _y- OCO-, or -OCO- (CH ₂ ) _y -COO-, and in L ₂ , y is an integer of 1 to 10, n is an integer of 1 to 5.

In Chemical Formula 9, the polycyclic arylene group having 10 or more carbon atoms or 10 to 30 carbon atoms corresponding to Ar ₁ and Ar ₂ is a polycyclic arylene group containing 2 or more benzene rings having 6 carbon atoms, and the carbon number 10 The two or more benzene rings contained in the above polycyclic arylene group may be fused to each other, bonded to each other, or both fused and bonded.

Specific examples of the polycyclic arylene group having 10 or more carbon atoms or 10 to 30 carbon atoms may be a biphenylene group, a terphenylene group, a stilbenylene group, or a naphthylenyl group, but is not limited thereto. Biphenylene groups in which benzene rings are bonded to each other can be used.

In Chemical Formula 9, L ₂ may be preferably -O (CH ₂ ) _y O-, where y may be an integer from 1 to 3.

More specifically, the example of the repeating unit represented by Chemical Formula 9 is not particularly limited, but may be, for example, a functional group represented by Chemical Formula 9-1.

[Formula 9-1]

The polymer for the second liquid crystal aligning agent may further include at least one repeating unit selected from the group consisting of a repeating unit represented by Chemical Formula 21, a repeating unit represented by Chemical Formula 22, and a repeating unit represented by Chemical Formula 23: .

[Formula 21]

[Formula 22]

[Formula 23]

In the above formulas 21 to 23,

At least one of R ₃₁ and R ₃₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, X ₂₁ to X ₂₃ are each independently a tetravalent organic group, and Y ₂₁ to Y ₂₃ are each independently represented by the following Chemical Formula 24 It may be either a divalent organic group represented or a divalent organic group represented by Formula 25 below.

[Formula 24]

In Chemical Formula 24,

R ₃₃ and R ₃₄ are each independently hydrogen, halogen, cyano, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, haloalkyl having 1 to 10 carbons, or 1 to 10 carbons. Haloalkoxy of 10, p and q are each independently an integer of 0 to 4, L ₁₁ is a single bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) ₂ -, -C (CF ₃ ) _2- , -CONH-, -COO-,-(CH ₂ ) _z- , -O (CH ₂ ) _z O-, -O (CH ₂ ) _z- , -NH-, -NH (CH ₂ ) _z -NH-, -NH (CH ₂ ) _z O-, -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O-, -COO- (CH ₂ ) _z -OCO-, or -OCO- (CH ₂ ) _z -COO-, z is an integer from 1 to 10, k and m are each independently an integer from 0 to 3, preferably 0 to 1, and n is an integer from 0 to 3 to be.

In Formula 24, carbon not substituted with R ₃₃ or R ₃₄ may be hydrogen, p and q are each independently an integer of 0 to 4, or 1 to 4, or 2 to 4, and p or q is When an integer of 2 to 4, a plurality of R ₃₃ or R ₃₄ may be the same or different substituents.

In addition, in Chemical Formula 24, k and m may each independently be 0 to 3, preferably 0 to 1, and n may be an integer from 0 to 3, or 1 to 3.

Preferably, the formula 24 may be a functional group represented by the following formula 24-1.

[Formula 24-1]

In addition, Chemical Formula 24 may be a functional group represented by Chemical Formula 24-2.

[Formula 24-2]

In the above formula 24-2, D is O, or CH ₂ .

[Formula 25]

In Chemical Formula 25, T is a tetravalent organic group represented by the following Chemical Formula 26, and D ₁ and D ₂ are each independently an alkylene group having 1 to 20 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms, or 3 to 20 carbon atoms. Cycloalkylene group, an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms.

Each of X ₂₁ to X ₂₃ may be independently a tetravalent organic group represented by the following Chemical Formula 26.

[Formula 26]

In the above formula 26, R ₇ to R ₁₂ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, L ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , -CR ₁₃ R ₁₄ -,-(CH ₂ ) _Z- , -O (CH ₂ ) _Z O-, -COO (CH ₂ ) _Z OCO-, -CONH-, phenylene or combinations thereof Any one selected from the group consisting of, wherein L ₁ To R ₁₃ And R _{14 Are} each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and z in L ₁ is 1 to 10 It is an integer.

As a preferable example of the above formula (25), a functional group represented by the following formula (25-1) or a functional group represented by the formula (25-2) may be used.

[Formula 25-1]

[Formula 25-2]

At least one repeating unit selected from the group consisting of the repeating unit represented by Chemical Formula 4, the repeating unit represented by Chemical Formula 5 and the repeating unit represented by Chemical Formula 6, Y ₄ to Y ₆ are 2 represented by Chemical Formula 9 While a pseudo organic group, at least one repeating unit selected from the group consisting of the repeating unit represented by Chemical Formula 21, the repeating unit represented by Chemical Formula 22 and the repeating unit represented by Chemical Formula 23 has a structure of Y ₂₁ to Y ₂₃ Is a repeating unit different from the formula (9). That is, the polymer for the second liquid crystal aligning agent may be a copolymer synthesized from two or more types of diamines.

At this time, the first repeating unit including at least one selected from the group consisting of the repeating unit represented by Formula 4, the repeating unit represented by Formula 5 and the repeating unit represented by Formula 6, and represented by Formula 21 The molar ratio between the repeating unit, the repeating unit represented by Formula 22 and the second repeating unit including at least one selected from the group consisting of the repeating unit represented by Formula 23 is 1:99 to 99: 1, 5: 95 to 95: 5, or 10:90 to 90:10.

Meanwhile, the liquid crystal aligning agent composition according to an embodiment may have a polymer content for the second liquid crystal aligning agent of 10 parts by weight to 1000 parts by weight, or 15 parts by weight to 800 parts by weight based on 100 parts by weight of the polymer for the first liquid crystal aligning agent. have.

When the polymer for the first liquid crystal aligning agent having the above characteristics and the polymer for the second liquid crystal aligning agent are mixed and used in the weight ratio range, the excellent electrical properties of the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent have Since alignment and mechanical properties can be complemented with each other, a liquid crystal alignment film having excellent electrical properties such as an afterimage generated by direct current / AC voltage and voltage retention, and improved mechanical durability can be produced.

The weight average molecular weight (GPC measurement) of each of the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent is not particularly limited, but may be, for example, 10000 g / mol to 200000 g / mol.

The liquid crystal aligning agent composition of the above embodiment may include a crosslinking agent compound in addition to the polymer for the first liquid crystal aligning agent and the polymer for the second liquid crystal aligning agent, and the crosslinking agent compound may have a specific chemical structure represented by Chemical Formula 10 have. The physical / chemical properties of the crosslinker compound appear to be due to the specific structure of Formula 10 described above.

In Chemical Formula 10, A ₁ is a monovalent to tetravalent functional group, and j may be an integer from 1 to 4. The A ₁ is a functional group located in the center of the cross-linking agent compound, and the terminal functional groups contained in A ₁ may be bound to j groups of functional groups indicated by braces [[] ”in Chemical Formula 10.

That is, in the formula 10, when j is 1, A ₁ is a monovalent functional group. Moreover, when j is 2, A ₁ is a divalent functional group. Moreover, when j is 3, A ₁ is a trivalent functional group. Moreover, when j is 4, A ₁ is a tetravalent functional group. Preferably, in Chemical Formula 10, j is 2, and A ₁ may be an alkylene group having 1 to 10 carbon atoms, specifically, a butylene group.

In Formula 10, L ₄ And L ₅ is the same as or different from each other, and each independently is one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, preferably L ₄ and Each of L ₅ may independently be an alkylene group having 1 to 5 carbon atoms, for example, an ethylene group.

In Formula 10, R ₁₉ And R ₂₀ is a functional group substituted for a hydrogen atom at the terminal of a hydroxy group (-OH), which is a crosslinkable functional group of the crosslinking agent compound, wherein the polymer for the first liquid crystal aligning agent, the polymer for the second liquid crystal aligning agent and the formula (10) The crosslinking reaction between the crosslinking agent compounds can be suppressed.

As described later, the R ₁₉ and R ₂₀ undergoes a drying process, an exposure process, a curing process, and the like, in which a liquid crystal alignment layer is prepared from a liquid crystal aligning agent composition, and may be desorbed while being replaced with a hydrogen atom when elevated to a temperature of approximately 80 ° C. or higher.

R ₁₉ and R ₂₀ may each independently be a silicon-containing monovalent functional group.

Specifically, the silicon-containing monovalent functional group may be a functional group represented by Formula 11 below.

[Formula 11]

In Formula 11, R ₂₁ , R ₂₂ and R ₂₃ are each independently hydrogen or alkyl having 1 to 10 carbons. More specifically, in Formula 11, R ₂₁ , R ₂₂ and R ₂₃ may be a methyl group or an ethyl group.

In Chemical Formula 10, A ₁ is an alkylene group having 1 to 10 carbon atoms, and j may be 2. That is, the crosslinker compound represented by Chemical Formula 10 may include a compound represented by Chemical Formula 10-1.

[Formula 10-1]

In Formula 10-1, A 'is an alkylene group having 1 to 10 carbon atoms, and L ₆ to L ₉ is each independently an alkylene group having 1 to 5 carbon atoms, and R ₂₄ to R ₂₇ may each independently be a silicon-containing monovalent functional group

More specifically, as an example of the crosslinking agent compound represented by Formula 10-1, A 'is a butylene group having 4 carbon atoms, and L ₆ to L ₉ is all an ethylene group having 2 carbons, and R ₂₄ to R ₂₇ is a compound represented by the following Chemical Formula 10-2, which is a functional group represented by Chemical Formula 11 (R ₂₁ , R ₂₂ and R ₂₃ are methyl groups).

[Formula 10-2]

In addition, another example of the crosslinking agent compound represented by Chemical Formula 10-1, A 'is a butylene group having 4 carbon atoms, and L ₆ to L ₉ is all an ethylene group having 2 carbons, and R ₂₄ to R ₂₇ is a compound represented by the following Chemical Formula 10-3, which is a functional group represented by Chemical Formula 11 (R ₂₁ , R ₂₂ and R ₂₃ are ethyl groups).

[Formula 10-3]

The crosslinking agent compound represented by the formula (10) is 0.1 wt% to 30 wt%, or 2 wt% to 25 wt%, or 10 wt% to 25 wt%, or 10 wt% based on the total weight of the liquid crystal aligning agent composition. More than 25% by weight. When the content of the crosslinking agent compound is too large, the flexibility of the polymer may decrease as the degree of crosslinking of the polymer for the liquid crystal aligning agent increases excessively.

On the other hand, if the content of the cross-linking agent compound is too small, it may be difficult to sufficiently implement the mechanical strength and electrical properties improvement effect by increasing the cross-linking degree of the polymer for the liquid crystal alignment agent.

2. Manufacturing method of liquid crystal alignment film

According to another embodiment of the invention, applying the liquid crystal aligning agent composition to a substrate to form a coating film (step 1); Drying the coating film (step 2); Orienting the coating film by irradiating light or rubbing (step 3); And it provides a method for producing a liquid crystal alignment film comprising a step (step 4) of curing by heat treatment of the alignment-treated coating film.

Step 1 is a step of forming a coating film by applying the above-described liquid crystal aligning agent composition to a substrate. The contents of the liquid crystal aligning agent composition include all of the contents described above in one embodiment.

The method of applying the liquid crystal aligning agent composition to the substrate is not particularly limited, and for example, methods such as screen printing, offset printing, flexo printing, and inkjet may be used.

Further, the liquid crystal aligning agent composition may be dissolved or dispersed in an organic solvent. Specific examples of the organic solvent are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolid Don, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone , Methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, etc. Can be heard. These may be used alone or in combination.

In addition, the liquid crystal aligning agent composition may further include other components in addition to the organic solvent. As a non-limiting example, when the liquid crystal aligning agent composition is applied, the film thickness uniformity or surface smoothness is improved, or the adhesion between the liquid crystal alignment film and the substrate is improved, or the dielectric constant or conductivity of the liquid crystal alignment film is changed. Alternatively, an additive that can increase the density of the liquid crystal alignment layer may be further included. Examples of such additives include various solvents, surfactants, silane-based compounds, dielectric or crosslinkable compounds, and the like.

Step 2 is a step of drying the coating film formed by applying the liquid crystal aligning agent composition to a substrate.

The step of drying the coating film may use a method such as heating or vacuum evaporation of the coating film, and is preferably performed at 50 ° C to 150 ° C or 60 ° C to 140 ° C.

In the step 3, the coating film is irradiated with light to perform alignment treatment.

The coating film in the alignment treatment step may mean a coating film immediately after the drying step, or may be a coating film after heat treatment after the drying step. The "coating film immediately after the drying step" means that light is irradiated immediately without proceeding to the heat treatment at a temperature higher than the drying step after the drying step, and other steps other than the heat treatment can be added.

More specifically, in the case of manufacturing a liquid crystal alignment film using a liquid crystal aligning agent containing a polyamic acid or a polyamic acid ester, a step of irradiating light after essentially performing a high temperature heat treatment for imidization of the polyamic acid is performed. In the case of manufacturing a liquid crystal alignment film using the liquid crystal aligning agent of the above-described one embodiment, the alignment layer is formed by heat-curing the alignment-treated coating film immediately after irradiating the light without directing the heat treatment step. Can be produced.

In addition, in the step of the alignment treatment, light irradiation may be to irradiate polarized ultraviolet light having a wavelength of 150 nm to 450 nm. At this time, the intensity of the exposure depends on the type of the polymer for the liquid crystal aligning agent, and energy of 10 mJ / cm 2 to 10 J / cm 2, preferably energy of 30 mJ / cm 2 to 2 J / cm 2 can be irradiated.

As the ultraviolet light, a polarizing device using a substrate coated with a dielectric anisotropic material on a transparent substrate surface such as quartz glass, soda lime glass, soda lime free glass, or a polarizing plate on which aluminum or metal wires are deposited, or quartz glass Orientation is performed by irradiating polarized ultraviolet rays selected from polarized ultraviolet rays by passing or reflecting a Brewster polarizer or the like by reflection. At this time, the polarized ultraviolet light may be irradiated perpendicularly to the substrate surface, or may be irradiated by tilting the incident angle at a specific angle. By this method, the alignment ability of the liquid crystal molecules is imparted to the coating film.

In addition, the rubbing treatment in the alignment treatment step may use a method using a rubbing cloth. More specifically, the rubbing treatment may rub the surface of the coating film after the heat treatment step in one direction while rotating the rubbing roller having a cloth of rubbing cloth attached to the metal roller.

The step 4 is a step of curing by heat-treating the alignment-treated coating film.

In the step of heat-treating and curing the alignment-treated coating film, R ₁₉ of the crosslinking agent compound represented by Chemical Formula 10 in the alignment-treated coating film and R ₂₀ functional group can be desorbed while being substituted with a hydrogen atom, a polymer for a first liquid crystal aligning agent; Alternatively, a crosslinking reaction between the polymers for the second liquid crystal aligning agent may proceed.

Specifically, in the step of heat-treating and curing the alignment-treated coating film, a crosslinking agent compound represented by Chemical Formula 12 may be included in the alignment-treated coating film.

[Formula 12]

In Chemical Formula 12, A ₁ , j, L ₄ and L ₅ is as defined in Chemical Formula 10 of the above embodiment.

When the liquid crystal aligning agent composition of the above embodiment includes the crosslinking agent compound represented by Chemical Formula 12, it is difficult to evenly disperse the crosslinking agent compound in the composition as some crosslinking reaction proceeds from within the composition.

On the other hand, the present invention suppresses the crosslinking reaction in the composition by adding the crosslinking agent compound represented by the formula (10) in the liquid crystal aligning agent composition, and is represented by the formula (10) in the step of heat-treating the hardened coating film to cure Can be induced to be converted to a crosslinker compound represented by the formula (12). Accordingly, in the composition, the dispersibility and stability of the crosslinking agent compound can be increased, and in the alignment film, an effect of improving the film strength can be realized through the formation of a crosslinked structure.

The step of heat-treating and curing the alignment-treated coating film is a step performed after irradiation with light in the method of manufacturing a liquid crystal alignment film using a polymer for a liquid crystal aligning agent containing a polyamic acid or a polyamic acid ester. It is distinguished from the heat treatment step applied to the substrate and prior to irradiating light or imidizing the liquid crystal aligning agent while irradiating light.

At this time, the heat treatment may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and is preferably performed at 150 ° C to 300 ° C, or 200 ° C to 250 ° C.

On the other hand, after the step of drying the coating film (step 2), if necessary, may further include the step of heat-treating the coating film immediately after the drying step at a temperature equal to or higher than the drying step. The heat treatment may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and is preferably performed at 150 ° C to 250 ° C. In this process, the liquid crystal aligning agent can be imidized.

That is, the method of manufacturing the liquid crystal alignment film includes the steps of applying the above-described liquid crystal alignment agent to a substrate to form a coating film (step 1); Drying the coating film (step 2); Heat-treating the coating film immediately after the drying step at a temperature equal to or higher than the drying step (step 3); The heat-treated coating film may be irradiated with light or subjected to rubbing treatment to perform alignment treatment (step 4) and heat-curing the orientation-treated coating film (step 5).

3. Liquid crystal alignment film

In addition, the present invention provides a liquid crystal alignment film prepared according to the method for manufacturing a liquid crystal alignment film described above. Specifically, the liquid crystal alignment layer may include an alignment cured product of the liquid crystal aligning agent composition of the embodiment. The alignment cured product means a material obtained through an alignment process and a curing process of the liquid crystal aligning agent composition of the above embodiment.

As described above, the polymer for the first liquid crystal aligning agent, the polymer for the second liquid crystal aligning agent; And when using a liquid crystal aligning agent composition comprising a crosslinking agent compound represented by the formula (10), stability is enhanced, it is possible to manufacture a liquid crystal alignment film exhibiting excellent electrical properties.

Although the thickness of the liquid crystal alignment layer is not particularly limited, for example, it can be freely adjusted within a range of 0.01 μm to 1000 μm. When the thickness of the liquid crystal alignment layer is increased or decreased by a specific value, physical properties measured in the liquid crystal alignment layer may also be changed by a certain value.

Specifically, the liquid crystal alignment layer may have a film strength of 0.5% or less, or 0.01% to 0.5%, 0.01% to 0.05%, or 0.01% to 0.04%, or 0.01% to 0.03%, calculated by Equation 1 below. .

[Equation 1]

Film strength = haze of the liquid crystal aligning film after rubbing treatment-haze of the liquid crystal aligning film before rubbing treatment.

The rubbing treatment for the liquid crystal alignment layer may be performed using a rubbing treatment method while rotating the alignment layer surface at 1000 rpm using a sindo engineering rubbing machine, and a haze value may be measured using a hazemeter.

4. Liquid crystal display element

In addition, the present invention provides a liquid crystal display device comprising the above-described liquid crystal alignment film.

The liquid crystal alignment layer may be introduced into a liquid crystal cell by a known method, and the liquid crystal cell may be introduced into a liquid crystal display device by a known method. The liquid crystal alignment layer is manufactured from the liquid crystal alignment agent composition of the above embodiment, and can realize excellent stability along with excellent physical properties. Specifically, it can have a high voltage preservation rate at high temperatures and low frequencies, and thus has excellent electrical characteristics, reduced performance of contrast ratio or image sticking (image sticking), and excellent film strength. Can provide.

Specifically, the liquid crystal display device has a voltage retention of 85% or more, or 85% to 99%, or 90% to 99%, or 95%, measured using TOYO corporation's 6254C equipment at a temperature of 1V, 1Hz, 60 ° C. To 99%, or 97% to 99%, or 97% to 99%. When the voltage retention rate measured using TOYO Corporation's 6254C equipment at a temperature of 1V, 1Hz, and 60 ° C of the liquid crystal alignment display device is excessively reduced, it may be difficult to implement a liquid crystal display device having high-quality driving characteristics at low power. .

In addition, the liquid crystal display device is attached to the upper and lower plates so that the polarizers are perpendicular to each other, and then attached to a backlight of 7,000 cd / m 2 and the initial luminance (L0), which is the luminance of the black state measured using PR-880 equipment, and room temperature. After driving for 120 hours at AC voltage of 7 V, the difference between the luminance of the black, the later luminance (L1), divided by the initial luminance (L0) value and multiplied by 100 is the luminance fluctuation factor of the liquid crystal display device. %.

According to the present invention, a liquid crystal aligning agent composition capable of realizing improved alignment properties and electrical properties while having excellent film strength, a method of manufacturing a liquid crystal aligning film using the same, and a liquid crystal aligning film and a liquid crystal display device using the same are provided.

The invention is described in more detail in the following examples. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example>

Preparation Example 1 Synthesis of Diamine DA1-1

18.3 g (100 mmol) of 2-chloro-5-nitropyridine (Compound 1), 12.5 g (98.6 mmol) of paraphenylenediamine (p-PDA, Compound 2) about 200 After completely dissolving in mL of Dimethylsulfoxide (DMSO), 23.4 g (200 mmol) of triethylamine (Trimethylamine, TEA) was added and stirred at room temperature for about 12 hours. When the reaction was completed, the reactant was added to a container containing about 500 mL of water and stirred for about 1 hour. The solid obtained by filtration was washed with about 200 mL of water and about 200 mL of ethanol to synthesize 16 g (61.3 mmol) of Compound 3 (yield: 60%).

After dissolving the compound 3 in an about 200 mL solution in which ethyl acetate (Ethyl acetate, EA) and THF are 1: 1 mixed, 0.8 g of palladium (Pd) / carbon (C) is added and about 12 hours in a hydrogen environment. While stirring. After the reaction was completed, the filtrate filtered on the celite pad was concentrated to prepare 11 g of diamine DA1-1 (yield: 89%).

Preparation Example 2: Synthesis of Diamine DA1-2

Diamine DA1-2 of Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that metaphenylenediamine (m-PDA, Compound 4) was used instead of the paraphenylenediamine (p-PDA, Compound 2). It was prepared.

Preparation Example 3: Synthesis of diamine DA1-3

The above except that 2-chloro-4-nitropyridine (Compound 5) was used instead of 2-chloro-5-nitropyridine (Compound 1). Diamine DA1-3 of Preparation Example 3 was manufactured in the same manner as in Preparation Example 1.

Preparation Example 4: Preparation of crosslinking agent

N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide (N, N, N', N'-Tetrakis (2-hydroxyethyl) adipamide) 5 g (15.6 mmol) and chlorotrimethyl After adding 10.2 g (94 mmol) of silane (Chlorotrimethylsilane) to 150 ml of chloroform, 17.3 g (125 mmol) of potassium carbonate (K ₂ CO ₃ ) was added and stirred for 10 hours under a nitrogen atmosphere at 0 ° C. After completion of the reaction, the filtrate was concentrated in a celite pad, and N1, N1, N6, N6-tetrakis (2- (trimethylsilyloxy) ethyl) adipamide (N1, N1, N6, N6-tetrakis (2- ( trimethylsilyloxy) ethyl) adipamide) 7.3 g (yield 77%) was prepared.

Comparative Production Example 1: Preparation of crosslinking agent

Compare the reactants of Preparation Example 4, N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide (N, N, N', N'-Tetrakis (2-hydroxyethyl) adipamide) It was used as a crosslinking agent in Preparation Example 1.

<Synthesis example>

The first polymer and the second polymer were synthesized using the reactants shown in Table 1 below. The specific synthesis conditions of each of Synthesis Examples 1 to 8 are listed in Table 1 or below.

First polymer Synthetic example Diamine Acid anhydride Synthesis Example 1 (Q-1) Preparation Example 1 (DA1-1) BT-100 Synthesis Example 2 (Q-2) Preparation Example 1 (DA1-1) CHDA Synthesis Example 3 (Q-3) Preparation Example 1 (DA1-1) PMDA Second polymer Synthetic example Diamine Acid anhydride Synthesis Example 4 (R-1) bp-EODA DMCBDA Synthesis Example 5 (R-2) bp-EODA + p-PDA DMCBDA Synthesis Example 6 (R-3) bp-EODA + MDA DMCBDA Synthesis Example 7 (R-4) bp-EODA + MDA DMCBDA + PMDA Synthesis Example 8 (R-5) bp-EODA + formula y DMCBDA Synthesis Example 9 (R-6) bp-EODA + formula y DMCBDA Synthesis Example 10 (R-7) bp-EODA + formula y DMCBDA

<Synthesis Examples 1 to 3: Synthesis of the first polymer>

Synthesis Example 1: Polymer Q-1 for liquid crystal aligning agent

21.735 g (0.109 mol) of diamine DA1-1 prepared in Preparation Example 1 was completely dissolved in 236.501 g of anhydrous N-methyl pyrrolidone (NMP).

And, tetrahydro- [3,3'-bifuran] -2,2 ', 5,5'-tetraone (tetrahydro- [3,3'-bifuran] -2,2', 5,5 under ice bath '-tetraone, BT100) 20.0 g (0.101 mol) was added to the solution and stirred at room temperature for about 16 hours to prepare polymer Q-1 for liquid crystal aligning agent. As a result of confirming the molecular weight of the polymer Q-1 through GPC, the weight average molecular weight (Mw) was 26,400 g / mol.

Synthesis Example 2: Preparation of polymer Q-2 for liquid crystal aligning agent

Diamine DA1-1 prepared in Preparation Example 1 19.211 g (0.096 mol) was completely dissolved in 222.194 g of anhydrous N-methyl pyrrolidone (NMP).

Then, under ice bath, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride (1,2,4,5-Cyclohexanetetracarboxylic Dianhydride, CHDA) 20.0 g (0.089 mol) was added to the solution for about 16 hours at room temperature. During stirring, a polymer Q-2 for liquid crystal aligning agent was prepared. As a result of confirming the molecular weight of the polymer Q-2 through GPC, the weight average molecular weight (Mw) was 24,000 g / mol.

Synthesis Example 3: Preparation of polymer Q-3 for liquid crystal aligning agent

Diamine DA1-1 prepared in Preparation Example 1 19.743 g (0.099 mol) was completely dissolved in 225.213 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 20.0 g (0.092 mol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath and stirred at room temperature for about 16 hours to prepare polymer Q-3 for liquid crystal aligning agent. As a result of confirming the molecular weight of the polymer Q-3 through GPC, the weight average molecular weight (Mw) was 27,000 g / mol.

<Synthesis Examples 4 to 10: second polymer synthesis>

Synthesis Example 4: Polymer R-1 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy) represented by the following formula x )) dibiphenyl-4-amine, bp-EODA) 38.062 g (0.096 mol) was completely dissolved in 222.194 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 20.0 g (0.089 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-1 was prepared.

[Formula x]

Synthesis Example 5: Polymer R-2 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- amine, bp-EODA) 3.965 g (0.010 mol) and p-phenylenediamine (p-PDA) 9.337 g (0.086 mol) anhydrous N-methyl pyrrolidone (NMP) Completely dissolved in 177.128 g.

Then, 20.0 g (0.089 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-2 was prepared.

Synthesis Example 6: Polymer R-3 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- amine, bp-EODA) 3.965 g (0.010 mol) and, 4'-methylenedianiline (4,4'-Methylenedianiline, MDA) 17.119 g (0.086 mol) anhydrous N-methyl pyrrolidone : NMP) Dissolved completely in 221.225 g.

Then, 20.0 g (0.089 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-3 was prepared.

Synthesis Example 7: Polymer R-4 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- amine, bp-EODA) 3.965 g (0.010 mol) and, 4'-methylenedianiline (4,4'-Methylenedianiline, MDA) 17.119 g (0.086 mol) anhydrous N-methyl pyrrolidone : NMP) It completely dissolved in 219.696 g.

Then, 10.0 g (0.045 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) and pyromellitic dianhydride (PMDA) 9.73 g (under ice bath) 0.045 mol) was added to the solution and stirred at room temperature for 16 hours to prepare polymer R-4 for liquid crystal alignment.

Synthesis Example 8: Polymer R-5 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- 3.965 g (0.010 mol) of amine, bp-EODA and 34.918 g (0.089 mol) of Preparation 2 diamine DA1-2 were completely dissolved in 322.091 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 20.0 g (0.089 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-5 was prepared.

Synthesis Example 9: Polymer R-6 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- 14.273 g (0.036 mol) of amine, bp-EODA and 14.549 g (0.036 mol) of Preparation 2 diamine DA1-2 were completely dissolved in 208.269 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 15.0 g (0.067 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-6 was prepared.

Synthesis Example 10: Polymer R-7 for liquid crystal aligning agent

4 ', 4 "-(ethane-1,2-diylbis (oxy)) dibiphenyl-4-amine (4', 4 ''-(ethane-1,2-diylbis (oxy)) dibiphenyl-4- 19.031 g (0.048 mol) of amine, bp-EODA and 19.399 g (0.048 mol) of diamine DA1-2 in Preparation Example 2 were completely dissolved in 276.163 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 10.0 g (0.045 mol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) was added to the solution under an ice bath and stirred at room temperature for 16 hours to align the liquid crystal. The polymer R-7 was prepared.

<Examples and Comparative Examples: Preparation of liquid crystal aligning agent composition, liquid crystal alignment film, and liquid crystal alignment cell>

Example 1

(1) Preparation of liquid crystal aligning agent composition

A solution obtained by dissolving the first polymer and the second polymer with a composition as shown in Table 2 below in a mixed solvent of NMP, GBL, and 2-butoxyethanol was obtained. Then, N1, N1, N6, N6-tetrakis (2- (trimethylsilyloxy) ethyl) adipamide obtained in Preparation Example 4 as a crosslinking agent was added to the solution at 3% by weight based on the total solution, followed by stirring at 25 ° C for 16 hours. . A liquid crystal aligning agent composition was prepared by pressure filtration through a filter having a pore size of 0.1 µm made of poly (tetrafluorene ethylene).

(2) Preparation of liquid crystal alignment film

Liquid crystal aligning agent by spin coating on the upper and lower substrates for voltage retention ratio (VHR) patterned with ITO electrodes with a thickness of 60 nm and an area of 1 cm X 1 cm on a rectangular glass substrate having a size of 2.5 cm X 2.7 cm The composition was applied. Subsequently, the substrate coated with the liquid crystal aligning agent was placed on a hot plate at about 70 ° C. and dried for 3 minutes to evaporate the solvent.

In order to orient the coating film thus obtained, ultraviolet rays at 254 nm were irradiated with an exposure amount of about 0.1 to 1 J / cm 2 using an exposure machine having a linear polarizer attached to each of the upper and lower plates. Thereafter, the alignment-treated upper / lower plates were fired (cured) in an oven at about 230 ° C. for 30 minutes to obtain a liquid crystal alignment film having a film thickness of 0.1 μm.

(3) Preparation of liquid crystal alignment cell

A sealing agent impregnated with a ball spacer having a size of 4.5 μm was applied to the edge of the top plate except for the liquid crystal injection hole. Then, after aligning the liquid crystal alignment films formed on the upper and lower plates so that the alignment directions were parallel to each other, an empty cell was manufactured by bonding the upper and lower plates and UV and heat curing the sealing agent. Then, the liquid crystal was injected into the empty cell and the injection hole was sealed with a sealing agent to prepare a liquid crystal alignment cell.

Example 2: Preparation of liquid crystal aligning agent composition

With the composition shown in Table 2, a liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as in Example 1, except that the total solution was added at 20% by weight based on the crosslinking agent.

Comparative Example 1

A liquid crystal aligning agent in the same manner as in Example 1, except that a solution obtained by dissolving the first polymer and the second polymer with a composition as shown in Table 2 below in a mixed solvent of NMP, GBL, and 2-butoxyethanol was used. A composition, a liquid crystal alignment film, and a liquid crystal alignment cell were prepared.

Comparative Example 2

A liquid crystal aligning agent composition, a liquid crystal aligning film, and a liquid crystal aligning cell were prepared in the same manner as in Example 1, except that the crosslinking agent of Preparation Example 4 was not added.

Comparative Example 3

Liquid crystal aligning agent composition in the same manner as in Example 1, except that N, N, N ', N'-Tetrakis (2-hydroxyethyl) adipamide of Comparative Preparation Example 1 was added instead of the crosslinking agent of Preparation Example 4, A liquid crystal alignment film and a liquid crystal alignment cell were prepared.

division First polymer Second polymer Polymer weight ratio
(First polymer: Second polymer) Crosslinker Kinds Input (% by weight) Example 1 Q-1 R-1 5: 5 Preparation Example 4 3 Example 2 Q-1 R-1 5: 5 Preparation Example 4 20 Comparative Example 1 - R-1 - Preparation Example 4 3 Comparative Example 2 Q-1 R-1 5: 5 - - Comparative Example 3 Q-1 R-1 5: 5 Comparative Production Example 1 3

<Experimental Example>

1) Evaluation of liquid crystal alignment

The polarizing plates were attached to the upper and lower plates of the prepared liquid crystal alignment cell to be perpendicular to each other. Then, a liquid crystal alignment cell with a polarizing plate was placed on a backlight having a brightness of 7,000 cd / m 2, and light leakage was observed with the naked eye. At this time, if the alignment characteristics of the liquid crystal alignment film are excellent and the liquid crystals are well arranged, light is not passed through the upper and lower flat plates attached vertically to each other, and dark without defects. The orientation characteristic in this case was evaluated as 'good', and when light leakage such as liquid crystal marks or bright spots was observed, it was evaluated as 'bad', and the results are shown in Table 3 below.

2) Voltage holding ratio (VHR) measurement

The voltage holding ratio (VHR), which is an electrical characteristic of the prepared liquid crystal alignment cell, was measured using TOYO corporation's 6254C equipment. The voltage retention (VHR) was measured at a temperature of 1 Hz and 60 ° C. (VHR 60 ° 1 Hz n-LC condition). The measurement results of the voltage retention (VHR) of the liquid crystal alignment cell are shown in Table 3 below.

3) Evaluation of orientation stability (AC afterimage)

The polarizing plates were attached to the upper and lower plates of the prepared liquid crystal alignment cell to be perpendicular to each other. The liquid crystal cell to which the polarizing plate was attached was attached to a backlight of 7,000 cd / m 2 and the luminance of the black state was measured using PR-788 equipment, which is a luminance brightness measuring device. Then, the liquid crystal cell was driven at room temperature for 5 hours with an AC voltage of 5 V. Subsequently, the luminance of the black state was measured in the same manner as described above while the voltage of the liquid crystal cell was turned off. The difference between the initial luminance (L0) measured before driving of the liquid crystal cell and the later luminance (L1) measured after driving was divided by the initial luminance (L0) value and multiplied by 100 to calculate the luminance fluctuation rate. The calculated luminance variation rate means that the closer to 0%, the better the orientation stability. The residual image level was evaluated under the following criteria through the measurement result of the luminance change rate. It is desirable to minimize the AC afterimage, and it was evaluated as 'good' when the luminance fluctuation rate is less than 10%, 'normal' when the luminance fluctuation rate is 10% to 20%, and 'bad' when the luminance fluctuation rate exceeds 20%. , The results are shown in Table 3 below.

4) Film strength

About the prepared liquid crystal alignment film, the surface of the liquid crystal alignment film was rubbed while rotating at 850 rpm using a rubbing machine manufactured by sindo engineering, and then a haze value was measured using a hazemeter, as shown in Equation 1 below. The film strength was evaluated by calculating the difference from the haze value before rubbing. When the haze change value is less than 1, the film strength is excellent.

[Equation 1]

Film strength = haze of the liquid crystal aligning film after rubbing treatment-haze of the liquid crystal aligning film before rubbing treatment.

5) Imidation conversion rate (%)

The FT-IR spectrum was measured by the ATR method for the prepared liquid crystal alignment film, and the ratio of the imide structure in the polymer molecules contained in the alignment film was measured.

6) Storage stability

For the prepared liquid crystal aligning agent composition, the initial viscosity and the viscosity after storage for 30 days at room temperature were measured, respectively, and the rate of change of viscosity was measured by Equation 2 below.

The viscosity of the liquid crystal aligning agent composition may be measured according to the torque at a temperature of 25 ° C., a rotation speed of 0.5 rpm, and a Brookfield viscometer on the RV-7 spindle.

[Equation 2]

Viscosity change rate (%) = (viscosity of liquid crystal aligning agent composition after storage for 30 days at room temperature-viscosity of initial liquid crystal aligning agent composition) / viscosity of initial liquid crystal aligning agent composition * 100.

Then, the storage stability level was evaluated under the following criteria.

Excellent: Viscosity change over 30 days is 8% or less

Poor: Viscosity change over 30 days exceeded 8%

division Liquid crystal orientation Orientation stability VHR (%) Film strength (%) Imidation conversion rate (%) Storage stability (%) Example 1 Good Great 98 0.03 95 1.24 Example 2 Good Great 97 0.03 94 1.21 Comparative Example 1 Bad Great 81 0.03 94 1.24 Comparative Example 2 Good usually 82 0.14 94 1.24 Comparative Example 3 Good usually 91 0.05 93 1.21

As shown in Table 3 above, from the liquid crystal aligning agent compositions of Examples 1 to 2 containing the crosslinking agent of Preparation Example 4 together with the polyimide-based polymer in which two types of polymers of the first polymer and the second polymer were mixed. It was confirmed that the obtained liquid crystal alignment film or liquid crystal alignment cell exhibited a high voltage retention rate of 97% to 98%, and a high imidization conversion rate of 94% to 95%, along with excellent liquid crystal alignment properties and alignment stability. In addition, it was confirmed that the haze change value before and after the rubbing treatment was very low at 0.03%, indicating excellent film strength.

On the other hand, in Comparative Example 1 using only one polymer of the second polymer except for the first polymer, the liquid crystal orientation was not only poor, but the voltage retention was 81%, indicating that the electrical properties were inferior to the above example. It was confirmed that it appeared.

In addition, the alignment layer obtained from the liquid crystal aligning agent composition of Comparative Example 2, which does not contain the crosslinking agent of Production Example 4, exhibited a luminance fluctuation rate of 10% to 20%, resulting in a decrease in orientation stability compared to Examples, and a haze change value before and after rubbing treatment. It was confirmed that the film strength was not only very poor due to the rapid increase to 0.14%, but also the electrical characteristics were poor because the voltage retention was rapidly decreased to 82%.

On the other hand, the alignment film obtained from the liquid crystal aligning agent composition of Comparative Example 3 containing the crosslinking agent of Comparative Preparation Example 1 instead of the crosslinking agent of Production Example 4, the luminance variation rate is 10% to 20%, and the alignment stability is reduced compared to the Example, and the voltage The retention rate was 91%, indicating that the electrical properties were inferior.

Claims (13)

A polymer for a first liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula 1, a repeating unit represented by the following formula 2 and a repeating unit represented by the following formula 3;
A polymer for a second liquid crystal aligning agent comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 4, a repeating unit represented by Formula 5 and a repeating unit represented by Formula 6; And
A liquid crystal aligning agent composition comprising a crosslinking agent compound represented by Chemical Formula 10:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 1 to 6,
At least one of R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen,
At least one of R ₃ and R ₄ is an alkyl group having 1 to 10 carbon atoms, and the rest is hydrogen,
X ₁ to X ₆ are each independently a tetravalent organic group represented by the following formula (7),
[Formula 7]

In Chemical Formula 7,
R ₇ to R ₁₂ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,
L ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , -CR ₁₃ R ₁₄ -,-(CH ₂ ) _Z- , -O (CH ₂ ) _Z O-, -COO (CH ₂ ) _Z OCO-, -CONH-, or any one selected from phenylene,
R ₁₃ and R ₁₄ in L ₁ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms,
L ₁ to z is an integer from 1 to 10,
Y ₁ to Y ₃ is a divalent organic group represented by the following formula (8),
[Formula 8]

In Chemical Formula 8,
A is a group 15 element,
R ^' is hydrogen or alkyl having 1 to 10 carbon atoms,
a is an integer from 1 to 3,
At least one of Z ₁ to Z ₄ is nitrogen, the other is carbon,
Y ₄ to Y ₆ are each independently a divalent organic group represented by the following formula (9),
[Formula 9]

In Chemical Formula 9,
Ar ₁ and Ar ₂ are each independently a polycyclic arylene group having 10 or more carbon atoms,
L ₂ is a single bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -CONH-, -COO-,- (CH ₂ ) _y- , -O (CH ₂ ) _y O-, -O (CH ₂ ) _y- , -NH-, -NH (CH ₂ ) _y -NH-, -NH (CH ₂ ) _y O- , -OCH ₂ -C (CH ₃ ) ₂ -CH ₂ O-, -COO- (CH ₂ ) _y -OCO-, or -OCO- (CH ₂ ) _y -COO-.
In L ₂ , y is an integer from 1 to 10,
n is an integer from 1 to 5,
[Formula 10]

In Chemical Formula 10,
A ₁ is a monovalent to tetravalent functional group,
j is an integer from 1 to 4,
L ₄ and L ₅ is the same as or different from each other, and each independently is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms,
R ₁₉ and R ₂₀ is a silicon-containing monovalent functional group each independently.
According to claim 1,
In Chemical Formula 8, one of Z ₁ to Z ₄ is nitrogen, and the other is carbon, the liquid crystal aligning agent composition.
According to claim 1,
In Chemical Formula 8, one of Z ₁ or Z ₃ is nitrogen, the other is carbon, and Z ₂ and Z ₄ are carbon.
According to claim 1,
In Chemical Formula 8, A is nitrogen, R ^' is hydrogen, and a is 1, the liquid crystal aligning agent composition.
According to claim 1,
The Chemical Formula 8 includes one or more functional groups selected from the group consisting of the following Chemical Formulas 8-1, 8-2, and 8-3:
[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

In Chemical Formulas 8-1 to 8-3,
A, Z ₁ to Z ₄ , R ^' , a are as defined in claim 1.
According to claim 1,
In Chemical Formula 9,
The benzene ring contained in the polycyclic arylene group having 10 or more carbon atoms is bonded to or bonded to each other, a liquid crystal aligning agent composition.
According to claim 1,
A liquid crystal aligning agent composition having a polymer content for a second liquid crystal aligning agent of 10 parts by weight to 1000 parts by weight based on 100 parts by weight of the polymer for the first liquid crystal aligning agent.
According to claim 1,
In Chemical Formula 10,
A ₁ is an alkylene group having 1 to 10 carbon atoms,
j is 2,
L ₄ and L ₅ are each independently an alkylene group having 1 to 5 carbon atoms,
R ₁₉ and Each of R ₂₀ is a silicon-containing monovalent functional group independently, a liquid crystal alignment agent composition.
According to claim 1,
The silicon-containing monovalent functional group is represented by the following formula (11), liquid crystal alignment agent composition:
[Formula 11]

In Formula 11, R ₂₁ , R ₂₂ and R ₂₃ are each independently hydrogen or alkyl having 1 to 10 carbons.
Forming a coating film by applying the liquid crystal aligning agent composition of claim 1 to a substrate;
Drying the coating film;
Orienting the coating film by irradiating light or rubbing treatment; And
And curing the heat-treated coating film by heat treatment.
The method of claim 10,
In the step of heat-treating and curing the alignment-treated coating film, the alignment-treated coating film includes a crosslinking agent compound represented by Chemical Formula 12, a method for producing a liquid crystal alignment film:
[Formula 12]

In Chemical Formula 12,
A ₁ , j, L ₄ and L ₅ is as defined in claim 1.
The liquid crystal aligning film containing the alignment hardened | cured material of the liquid crystal aligning agent composition of Claim 1.
A liquid crystal display device comprising the liquid crystal alignment film of claim 12.