WO2018216940A1

WO2018216940A1 - Polymer for liquid crystal alignment agent, liquid crystal alignment agent comprising same, and liquid crystal alignment film and liquid crystal display element using same

Info

Publication number: WO2018216940A1
Application number: PCT/KR2018/005506
Authority: WO
Inventors: 권순호; 구기철; 조정호; 민성준; 이상미; 윤준영; 윤형석; 임윤빈
Original assignee: 주식회사 엘지화학
Priority date: 2017-05-22
Filing date: 2018-05-14
Publication date: 2018-11-29

Abstract

The present invention relates to: a polymer which has excellent liquid crystal alignment properties and electrical characteristics, thus being appropriate for use in a liquid crystal alignment agent; a liquid crystal alignment agent comprising same; a liquid crystal alignment film formed from the liquid crystal alignment agent; and a liquid crystal display element comprising the liquid crystal alignment film.

Description

[Explanation of invention]

[Name of invention]

Polymer for liquid crystal aligning agent, liquid crystal aligning agent comprising same, liquid crystal aligning film and liquid crystal display device using same

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0063089 dated May 22, 2017 and Korean Patent Application No. 10-2017-0150899 dated November 13, 2017. All content disclosed in the literature is included as part of this specification.

The present invention relates to a polymer suitable for use in a liquid crystal aligning agent having excellent liquid crystal alignment properties and electrical properties, a liquid crystal aligning agent comprising the same, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display device including the liquid crystal aligning film.

[Technique to become background of invention]

In the liquid crystal display device, in order to obtain uniform brightness and high contrast rat io, it is essential to orient the liquid crystal uniformly. The liquid crystal aligning agent acts as a dictor 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.

Conventionally, as the liquid crystal aligning agent, polyimide, polyamide, polyester, and the like are widely known, and among them, polyimide is particularly used in many liquid crystal display devices because of its excellent heat resistance, affinity with liquid crystal, mechanical strength, and the like.

However, in recent years, as the demand for low-power displays increases, liquid crystal alignment agents may affect not only the basic characteristics of liquid crystal alignment, but also electrical characteristics such as afterimage and voltage retention caused by DC / AC voltage. It has been found that the need for the development of a liquid crystal alignment material that can simultaneously realize excellent liquid crystal alignment and electrical properties is increasing.

To this end, the monomers used to prepare the liquid crystal alignment agent may be changed or Although various attempts have been made to improve the physical / chemical properties by changing the structure of the liquid crystal aligning agent through a method of combining a plurality of other monomers, the situation has not yet reached the groundbreaking improvement of physical properties.

Accordingly, there is a demand for development of a new liquid crystal aligning agent having excellent liquid crystal alignment and electrical properties.

[Content of invention]

Problem to be solved

The present invention is to provide a polymer suitable for use in a liquid crystal aligning agent because of excellent liquid crystal alignment and electrical properties.

The present invention also provides a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device using the polymer for liquid crystal aligning agent.

[Measures of problem]

In the present specification, a polymer for a liquid crystal aligning agent including one or more repeating units 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 is provided. do.

[Formula 1]

[Formula 3]

In Formulas 1 to 3, at least one of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X ¹ to X ³ are each independently a tetravalent organic group, Y ¹ to Y ³ is Each independently represent a divalent organic group represented by Formula 4,

[Formula 4]

In Formula 4, A is a group 16 element, ¾ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 3, at least one of Z ₄ is nitrogen, the rest is carbon.

Hereinafter, a polymer for a liquid crystal aligning agent according to a specific embodiment of the present invention, and a manufacturing method thereof will be described in more detail. In the present specification, when a part "includes" a certain component, this means that it may further include other components, except to exclude other components unless specifically stated otherwise.

In the present specification, the term "substitution" means that another functional group is bonded to the hydrogen atom in the compound, and the position to be substituted is not limited to the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other. As used herein, the term " substituted or unsubstituted " refers to deuterium; halogen groups; cyano groups; nitro groups; hydroxy groups; carbonyl groups; ester groups; imide groups; amide groups; amino groups; carboxy groups; sulfonic acid groups; sulfonamide groups; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, 0 and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "the substituent to which two or more substituents are linked" 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 linked.

In the present specification, +, or —— * means a bond connected to another substituent, and a direct bond means a case where no separate atom is present in a portion represented by L.

In the present specification, the alkyl group may be straight or branched chain, carbon number is not particularly limited, but is preferably 1 to 10. According to another chassis state, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include 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, nuclear chamber, n-nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethtalbutyl, heptyl , N-heptyl, 1-methylnucleus, cyclopentylmethyl, cyclonuxylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylnuclear, 2-propylpentyl, n-nonyl, 2, 2 -Dimethylheptyl, 1-ethyl-propyl, 1, 1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl, 4-methylnuclear chamber, 5-methylnuclear chamber, and the like, but is not limited thereto.

The fluoroalkyl group having 1 to 10 carbon atoms may have one or more hydrogens of the alkyl group having 1 to 10 carbon atoms substituted with fluorine, and the fluoroalkoxy group having 1 to 10 carbon atoms may have at least one hydrogen of the alkoxy group having 1 to 10 carbon atoms. May be substituted with fluorine.

Halogen may be fluorine (F), chlorine (C1), bromine (Br) or iodine (I).

Group 15 elements are nitrogen (N), phosphorus (P), arsenic (As), tin (Sb) or Bismuth (Bi).

Nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and a nitrogen oxide functional group means a functional group including nitrogen oxide in a functional group. Examples of the nitrogen oxide functional group include nitro group (-N0 ₂ ) and the like. Therefore, the present inventors have a high voltage retention at high temperatures by using a polymer for a liquid crystal aligning agent comprising the repeating units of Formulas 1 to 3 prepared from a diamine compound having a specific structure asymmetric with respect to a center point or a center line through experiments. It was confirmed that the reduction of the contrast ratio and the afterimage phenomenon can be improved and completed the invention.

Specifically, according to one embodiment of the invention liquid crystal comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 Polymers for the alignment agent may be provided.

Specifically, the polymer according to one embodiment includes the repeating unit of Formula 1 to 3 above. In the repeating units of Chemical Formulas 1 to 3, X ¹ to X ³ may be various tetravalent organic groups as described above, and Y ¹ to Y ³ may be various divalent organic groups as described above.

Y ¹ to Y ³ may be defined by a divalent organic group represented by the formula (4) can provide a polymer for a liquid crystal aligning agent having a variety of structures that can express the above-described effect.

[Formula 4]

In Formula 4, A is a Group 16 element, ¾ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 3, at least one of Z ₄ , that is, at least one is nitrogen, the rest is Carbon.

The Group 16 element may be oxygen (0), sulfur (S), selenium (Se), tellurium (Te), or polonium (Po). Wherein R ₃ is a three to _a functional group bonded to the A The number of displayed numbers can be combined with element A. Preferably, in Formula 4, A is oxygen, and a may be an ether functional group of 0.

Meanwhile, in Chemical Formula 4, at least one of Z ₄ is nitrogen, and as the remainder satisfies carbon, the Chemical Formula 4 may have an asymmetric structure not symmetrical with respect to the center point or the center line by the nitrogen atom. . Formula 4 is a repeating unit derived from diamine which is a precursor used to form a polymer for a liquid crystal aligning agent, and may be due to the use of an asymmetric diamine as described below.

In the known polymer for liquid crystal aligning agent, since the structure and effects thereof are not recognized at all in the asymmetric diamine or the repeating unit derived therefrom, the repeating unit of Formula 4 and the diamine compound as a precursor thereof are novel. .

More specifically, in Chemical Formula 4, one of 1 to Z ₄ may be nitrogen and the other may be carbon. In Chemical Formula 4, one of or may be nitrogen, the others may be carbon, and Z ₄ may be carbon. That is, in Chemical Formula 4, the aromatic ring including Z ₄ may have a pyr i dine structure. Accordingly, the liquid crystal display device to which the polymer for liquid crystal aligning agent of the above embodiment is applied may implement high voltage retention and liquid crystal alignment.

On the other hand, the functional group represented by the formula (4) is characterized in that only the amine group and hydrogen are bonded to each of the two aromatic ring compounds, preferably heteroaromatic ring compound and aromatic ring compound, characterized in that no other substituents are introduced. In addition, when a substituent, for example, a fluoroalkyl group, is introduced into the heteroaromatic ring compound or the aromatic ring compound, there may be a technical problem that the afterimage property is poor due to an increase in luminance fluctuation rate and the voltage retention rate is significantly reduced.

In addition, Chemical Formula 4 may include one or more functional groups selected from the group consisting of Chemical Formulas 4-1, 4-2, and 4-3.

[Formula 4-1]

[Formula 4—2]

[Formula 4-3]

A, A, χ,,, ₃ , Ζ ₄ , described in Addition Formula 4-1, Formula 4-2, and Formula 4-3 include the above-mentioned contents in Formula 4.

As such, the functional group 4 may include one or more repeating units selected from the group consisting of Chemical Formula 4-1, Chemical Formula 4-2, and Chemical Formula 4-3, thereby achieving better liquid crystal alignment.

On the other hand, X ¹ to X ³ may each independently include a tetravalent organic group described in formula (5). That is, X ¹ to X ³ may each independently correspond to any one of the tetravalent organic groups described in the following Formula 5.

[Formula 5]

or

In Formula 5, to R ₉ are each independently hydrogen, or an alkyl group having 1 to 10 carbon atoms, L ₂ is a single bond,-, -CO-, -S-, -S0-, -S0 ₂ -,- C ₁₀ Rn-, -C0NH-, -C00-,-(CH ₂ ) _b- , -0 (C¾) _b 0—, -C00- (CH ₂ ) _b -0C0-, phenylene or combinations thereof Any one selected from the group, R ₁₀ and R _u are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, b is an integer of 1 to 10.

More preferably, X ¹ to X ³ are each independently an organic group of formula 5-1 derived from pyromel l it ic di anhydride (PMDA); An organic group represented by the following Chemical Formula 5-2 derived from 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyltetracarboxylic acid dihydride, BPDA); Organic groups represented by the following Chemical Formula 5-3 derived from 1,2,4,5-cyclotetracarboxylic acid tetraanhydride (l, 2,4,5-Cyclohexanetetracarboxylic anhydride, HPMDA); Or 1,3-dimethyl-cyclobutane—1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA). It may be 5-4 organic group.

[Formula 5-1]

The polymer is 0 mol% to 80 mol% of the repeating units represented by the formula (1), which is an imide repeating unit, among the repeating units represented by the formulas (1), (2) and (3), preferably 0. It may include 1 mol% to 65 mol%.

As described above, when using a polymer containing a specific content of the imide repeating unit represented by the formula (1), since the polymer contains a predetermined amount of imide repeating unit already imidized, a high temperature heat treatment step is omitted, Even if light is irradiated immediately, the liquid crystal aligning film excellent in the orientation and stability can be manufactured.

If the repeating unit represented by the formula (1) is included less than the content range does not exhibit a sufficient orientation characteristics, the orientation stability may be lowered, and if the content of the repeating unit represented by the formula (1) exceeds the range solubility Difficult to produce stable alignment liquids that can be coated Problems may appear. Accordingly, it is preferable to include the repeating unit represented by Chemical Formula 1 in the above-described content range because it is possible to provide a polymer for a liquid crystal aligning agent having excellent storage stability, electrical characteristics, orientation characteristics, and orientation stability.

In addition, the repeating unit represented by Formula 2 or the repeating unit represented by Formula 3 may be included in an appropriate content according to the desired properties.

Specifically, the repeating unit represented by Formula 2 may include 0 mol% to 50 mol¾, preferably 0.01 mol% to 30 mol% based on the total repeating units represented by Chemical Formulas 1 to 3. Since the repeating unit represented by the formula (2) has a low rate of conversion to imide during the high temperature heat treatment process after light irradiation, when it exceeds the above range, the overall imidation ratio may be insufficient and the orientation stability may be lowered. Accordingly, the repeating unit represented by Formula 2 may provide a polymer for a liquid crystal aligning agent that exhibits proper solubility within the above-described range and may realize excellent imidation ratio while having excellent process characteristics.

In addition, the repeating unit represented by Formula 3 may include 10 mol% to 100 mol%, preferably 30 mol% to 99.8 mol% based on the total repeating units represented by Formulas 1 to 3. It is possible to provide a polymer for a liquid crystal aligning agent that exhibits excellent coating properties within these ranges and can realize high imidation ratio while having excellent process characteristics.

On the other hand, the polymer for a liquid crystal aligning agent of one embodiment further comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (11), a repeating unit represented by the following formula (12) and a repeating unit represented by the following formula (13) can do.

[Formula 11]

[Formula 12]

[Formula 13]

In Chemical Formulas 11 to 13,

At least one of R ³ and R ⁴ is an alkyl group having 1 to 10 carbon atoms, and the rest are hydrogen;

X ⁴ to X ⁶ are each independently a tetravalent organic group,

Y ⁴ to Y ⁶ are each independently a divalent organic group represented by Formula 14,

[Formula 14]

In Chemical Formula 14,

5 and R ⁶ are each independently hydrogen, halogen, cyano, - ₁₀ alkyl, C ₂ - ₁₀ Alkenyl, Cwo alkoxy, _-10 fluoroalkyl, or fluoroalkoxy, p and q are each independently an integer from 0 to 4,

L ¹ is a single bond, ᅳ 0— ， —CO—, -S-, -S0 _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -C0NH-, -C00-, _ _{((¾) ζ -, -0} (CH 2) z 0-, -0 (CH 2) z -, - NH -, -NH (CH 2) z -NH-, -NH (CH 2) z 0- , ᅳ 0CH ₂ -C (CH ₃ ) ₂ -CH ₂ 0-, -C00- (CH ₂ ) _z -0C0-, or -0C ()-(CH ₂ ) _z -C00-,

z is an integer from 1 to 10,

k and m are each independently an integer of 0-3, or 1-3, and n is an integer of 0-3.

Hydrogen may be bonded to carbon which is not substituted with R ⁵ or R ⁶ in Formula 14, and 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 ⁵ or R ⁶ may be the same or different substituents.

In addition, in Formula 4, k and m may be each independently an integer of 0 to 3, or 1 to 3, n may be an integer of 0 to 3, or 1 to 3.

More specifically, Formula 14 may be Formula 15 or Formula 16 below.

[Formula 15]

[Formula 16]

In Formula 16, D is a direct bond, -0-, -S0 ₂ -or -C (R ₇ ) (¾)-, wherein R ₇ and ¾ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms to be.

Preferably, Formula 15 may be the following Formula 17.

[Formula 17]

In addition, Chemical Formula 16 may be Chemical Formula 18.

[Formula 18]

In Formula 18, D is-or -CH _2- .

X ⁴ to X ⁶ may each independently include a tetravalent organic group described in Formula 5 below.

[Formula 5]

In Formula 5, R ₉ to R ₁₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and L ₂ is a direct bond, -0-, -CO-, -S-, -S0-, -S0 ₂ -, -CRisRie-, -C0NH-, -C00-,-(CH ₂ ) _b - ₍ -0 (CH ₂ ) _b 0-, — C0 (HCH ₂ ) _b — 0C0-, phenylene or combinations thereof Any one selected from the group consisting of, R ₁₅ and R ₁₆ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, b is an integer of 1 to 10.

In this case, at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3, and a repeating unit represented by Formula 11, The molar ratio between one or more repeating units selected from the group consisting of a repeating unit represented by 12 and a repeating unit represented by Formula 13 may be 1: 100 to 100: 1.

In addition, the polymer for a liquid crystal aligning agent of the embodiment further comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (21), a repeating unit represented by the following formula (22) and a repeating unit represented by the following formula (23) can do.

[Formula 21]

[Formula 22]

[Formula 23]

In Formulas 21 to 23, at least one of R ₂₁ and R ₂₂ is an alkyl group having 1 to 10 carbon atoms, the remainder is hydrogen, X ₂₁ to ¾ ₃ is different from X ¹ to X ³ of the formula 1 to 3, Different from X ⁴ to X ⁶ of Formula 11 to 13, or different from X ¹ to X ³ of Formula 1 to ³ and X ⁴ to X ⁶ of Formula 11 to 13, each independently represented by Formula 5 Y ₂₁ to Y ₂₃ are each independently a divalent organic group represented by Formula 4 or a divalent organic group represented by Formula 14. The weight average molecular weight of the polymer for liquid crystal aligning agent may be 1000 g / mol to 200, 000 g / il. 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 of the polystyrene conversion measured by the GPC method, a detector and an analytical column, such as a commonly known analytical device and a differential refractive index detector (Refract ive Index Detector), can be used, and are commonly applied. Temperature conditions, solvent, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ^° C, a chloroform solvent (Chloroform) and f low rate of 1 mL / min.

Such a polymer may be used as a liquid crystal aligning agent to provide a liquid crystal alignment layer that realizes excellent stability and reliability.

Examples of the method for producing the polymer for liquid crystal aligning agent are greatly limited It is not, for example, reacting with a compound of formula (7) to prepare a compound of formula (8); Reducing the compound of Formula 8 to prepare a diamine of Formula 9; Reacting the diamine of Chemical Formula 9 with tetracarboxylic acid or anhydride thereof; And the tetracarboxylic acid black may be provided a method for producing a polymer for a liquid crystal aligning agent comprising the step of imidizing the resulting reaction with its anhydride.

[Formula 6]

In Formula 6, R ₂₁ is a halogen element,! ½ is a nitrogen functional group,

At least one of Zi to Z ₄ is nitrogen, the rest is carbon,

[Formula 7]

In Formula 7, A is a group 16 element, R ₃ is hydrogen, and

Is an alkyl group of 10 to 10, q is an integer of 1 to 4, ₂ is

It is a functional group

[Formula 8]

[Formula 9]

Preferably, in Chemical Formula 6, R ₂₁ is a chlorine element, R ₂₂ is a nitro group,

One of Zi or ¾ is nitrogen, the other is carbon, and ¾ and Z ₄ may be carbon. That is, preferred examples of the formula (6) include 2-chloro-5-nitropyridine, 2-chloro-4-nitropyridine and the like.

Also preferably, in Formula 7, A is an oxygen element, R ₃ is hydrogen, q is 1, and ₃ may be a nitro group. That is, 4-nitrophenol, 3-nitrophenol, etc. are mentioned as a preferable example of the said General formula (7).

Specifically, in the preparing of the compound of Formula 8, the compound of Formula 8 may be prepared by reacting the heteroaromatic compound of Formula 6 with the compound of Formula 7. Specifically, a reaction in which the halogen element of R ₂₁ included in the heteroaromatic compound of Formula 6 is replaced with the Group 16 element of A included in the compound of Formula 7 may be performed.

In the compound of Formula 7, the reaction property of the A (R ₃ ) q functional group is higher than that of the R ₂₂ functional group. Accordingly, in the substitution reaction of the halogen element of ¾ι included in the heteroaromatic compound of Chemical Formula 6, the R ₂₂ functional group of the compound of Chemical Formula 7 may not be substituted, and the A (R ₃ ) q functional group may be substituted.

The reaction can be carried out in a high yield of 50% or more under mild conditions that proceed for 6 to 15 hours at room temperature by an inorganic catalyst such as potassium carbonate. The reaction may be carried out in the presence of various conventionally known organic solvents, and specific examples of the organic solvent include ethyl acetate, tetrahydrofuran, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2- Pyridone, Ν-methylcaprolactam, 2-pyrrolidone, Ν-ethylpyrrolidone, Ν-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea pyridine, dimethyl sulfone, nuxamethyl sulfoxide, butyrolactone , 3-methoxy-N, N-dimethylpropanamide, 3 'ethoxy-N, N-dimethylpropanamide, 3-Boroxy-N, N-dimethylpropanamide, 1,3- Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme or 4-hydroxy-4 Methyl-2-pentanone etc. are mentioned. These may be used alone or in combination. In Chemical Formula 6, R ₂₁ is a halogen element, R ₂₂ is a nitrogen oxide functional group, at least one of Λ to Ζ ₄ may be nitrogen, and the rest may be carbon. More specifically, in Formula 4, one of 1 _Λ to Ζ ₄ is nitrogen, the rest may be carbon, in Formula 4, or one of ¾ is nitrogen and the rest is carbon, ¾ and Ζ ₄ is carbon Can be. Also preferably, in Chemical Formula 6, 1½ may be chlorine, and R ₂₂ may be a nitro group. In Formula 7, A is a group 16 element, R ₃ is hydrogen, or an alkyl group having 1 to 10 carbon atoms, q is an integer of 1 to 4, R ₂₂ may be a nitrogen oxide functional group. Preferably, in Formula 7, A is oxygen, ¾ is hydrogen, q is 1, R ₂₂ may be a nitro group.

In the nitrogen oxide functional group, nitrogen oxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and the nitrogen oxide functional group means a functional group including nitrogen oxide in the functional group. As the nitrogen oxide functional group, for example, a nitro group (-N02) or the like can be used.

The Group 16 element may be oxygen (0), sulfur (S), selenium (Se), tellurium (Te), or polonium (Po). ¾ is a functional group that binds to A, and may bind to element A as many as the number represented by q.

The compound of Formula 8 thus prepared may prepare a diamine compound of Formula 9 through reduction reaction. Specifically, as the nitrogen oxide functional group of ₂ contained in the compound of Formula 8 is reduced under reducing conditions to be reduced to the primary amino group, a diamine compound may be synthesized.

The reduction reaction may be carried out in a high yield of 80% or more under mild conditions that proceed for 10 to 15 hours at room temperature by a palladium / carbon catalyst. The reaction can be carried out in the presence of various conventionally known organic solvents, and specific examples of the organic solvent include ethyl acetate, tetrahydrofuran, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν- Methyl-2-pyrrolidone, N—methylcaprolactam, 2 ᅳ pyridone, N-ethylpyridone, N-vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide ， Butyrolactone, 3-methoxy-N, N-dimethylpropanamide ， 3-Ethoxy-N, N-dimethylpropanamide ， 3'butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imi Dazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, cyclonucleanone, ethylene carbonane propylene carbonate, diglyme or 4-hydroxy-4-methyl- 2-pentanone etc. are mentioned. These may be used alone or in combination. The contents of A, R ₃ , q, ZZ ₂ , Z ₃ , Z ₄ , and R ₂₂ described in Chemical Formulas 8 and 9 include those described in Chemical Formulas 6 and 7.

The diamine of formula 9 prepared through the above steps may be used for the tetracarboxylic acid or its anhydride, for example pyromellitic di anhydride (PMDA), 3,3 ', 4, 4'-Biphenyltetracarboxylic acid anhydride (3,3 ', 4,4'-Biphenyl Tetracarboxylic Acid Dihydride, BPDA), 1,2,4,5-cyclonucleic acid tetracarboxylic acid anhydride (1,2,4 , 5-Cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethyl-cyclobutane— 1,2,3,4-tetracarboxylic acid anhydride (DMCBDA) or a mixture of two or more thereof to form amic acid, amic acid It is possible to prepare polymers consisting of esters, or mixtures thereof.

Or if necessary, in addition to the diamine of the general formula (9) prepared through the above steps, various kinds of diamine compounds well known in the art of liquid crystal aligning agent, for example, P-phenylenediamine, 4,4-oxydianiline, Amic acid, amic acid ester, or a mixture thereof can be prepared by mixing 4,4'-methylenedianiline or the like.

The reaction conditions may be appropriately adjusted with reference to the preparation conditions of the polyamic acid known in the art. Then, the obtained amic acid, amic acid ester, or a mixture thereof can be imidized to prepare a polymer having the above-described repeating units of the formulas (1) to (3). On the other hand, according to another embodiment of the invention, comprising the polymer A liquid crystal aligning agent is provided.

Because the liquid crystal aligning agent includes the polymer described above, the liquid crystal aligning agent effectively suppresses deterioration in stability and reliability due to polymer degradation reaction during the firing process and storage, and exhibits excellent coating properties and at the same time excellent imide conversion rate.

This liquid crystal aligning agent may be provided through a variety of methods known in the art that the present ^■ invention, except that it contains the above-described polymer.

As a non-limiting example, the above-described polymer may be dissolved or dispersed in an organic solvent to provide a liquid crystal aligning agent.

Specific examples of the organic solvent include Ν, Ν-dimethylformamide Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone, Ν-methylcaprolactam, 2-pyridone, Ν-ethylpyrrolidone , the blood Ν- vinyl pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethyl sulfone eu, hex-methyl sulfoxide, Υ-to-dimethylpropanamide, 3-hydroxy-butyrolactone, _3-meteuk when - _Ν, _Ν- Ν, Ν-dimethylpropanamide, 3-Buroxy-Ν, Ν-dimethylpropanamide, 1, 3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, Methyl isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy- 4-methyl- 2-pentanone, etc. are mentioned. These may be used alone or in combination.

In addition, the liquid crystal aligning agent may further include other components in addition to the polymer and the organic solvent. As a non-limiting example, when the liquid crystal aligning agent is applied, it improves the uniformity and surface smoothness of the film thickness, improves the adhesion between the liquid crystal aligning film and the substrate, or changes the dielectric constant or conductivity of the liquid crystal aligning film. Or, an additive which may increase the compactness of the liquid crystal alignment layer may be further included. Such additives may be exemplified by various solvents, surfactants, silane compounds, dielectrics or crosslinkable compounds. On the other hand, according to another embodiment of the invention, a liquid crystal aligning film including the liquid crystal aligning agent described above is provided.

In the above, the liquid crystal aligning film contains a liquid crystal aligning agent. It means that the alignment film contains the liquid crystal aligning agent itself, or that the liquid crystal aligning film contains a product (for example, a cured product) obtained through chemical reaction of the liquid crystal aligning agent.

The liquid crystal alignment layer may be formed through various methods known in the art to which the present invention belongs, except that the liquid crystal alignment agent described above is used.

For example, the step (step 1) which forms the coating film by apply | coating the liquid crystal aligning agent mentioned above to a board | substrate; Drying the coating film (step 2); Irradiating or rubbing the light onto the coating film immediately after the drying step (step 3); And a step (step 4) of curing the alignment-treated coating film (step 4).

Step 1 is a step of applying the above-described liquid crystal aligning agent to a substrate to form a coating film.

The method of applying the liquid crystal aligning agent to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, inkjet, or the like may be used.

In addition, the liquid crystal alignment agent may be ^dissolved, or dispersed in an organic solvent. Specific examples of the organic solvent include Ν, Ν—dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone, Ν-methylcaprolactam, 2-pyridone and Ν-ethylpyri. Lidon, N-vinylpyridone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, nuxamethyl sulfoxide, _γ -butyrolactone, 3-methoxy-Ν, Ν-dimethylpropanamide, 3 ethoxy -Ν, Ν-dimethylpropanamide, 3-subspecialty -Ν, Ν-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone ， Methyl isopropyl ketone, cyclonucleanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl on Le, 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, and the like. These may be used alone or in combination. In addition, the liquid crystal aligning agent may further include other components in addition to the organic solvent. Non-limiting examples, when the liquid crystal aligning agent is applied, to the film improve the thickness uniformity and surface smoothness, or, or to improve the adhesion of the liquid crystal alignment layer and the substrate, or black has a liquid crystal alignment film ^dielectric, changing the rate or conductive Or an additive capable of increasing the compactness of the liquid crystal alignment layer may be further included. Such additives may be exemplified by various solvents, surfactants, silane compounds, dielectrics or crosslinkable compounds.

The said step 2 is a step of drying the coating film formed by apply | coating the said liquid crystal aligning agent to a board | substrate.

Drying the coating film may be a method such as heating the coating film, vacuum evaporation, it is preferably carried out at 50 ^° C to 150 ^° C, or 60 t to 140 ^° C.

Step 3 is a step of performing alignment treatment by irradiating light or rubbing the coating film immediately after the drying step.

In the present specification, "the coating film ¹ " immediately after the drying step means light irradiation immediately without the progress of the heat treatment step after the drying step at a temperature higher than the drying step, and other steps other than the heat treatment may be added.

More specifically, when manufacturing a liquid crystal aligning film using a conventional liquid crystal aligning agent containing a polyamic acid or polyamic acid ester, the step of irradiating light after performing a high temperature heat treatment essentially for the imidization of the polyamic acid However, when the liquid crystal aligning film is manufactured using the liquid crystal aligning agent of the above-described embodiment, it does not include the heat treatment step, and is directly irradiated with light, followed by alignment treatment. It can manufacture.

And, the light irradiation in the alignment process may be to irradiate polarized ultraviolet rays of 150 nm to 450 ran wavelength. At this time, the intensity of exposure Depends on the kind of liquid crystal aligning jeyong polymer, you can check out of 10 mJ / cin ² to 10 J / crf energy, preferably _{30 m} j / _cl) of f to 2 J / cirf energy. As the ultraviolet rays, a polarizer using a substrate coated with a dielectric anisotropic substance on a transparent substrate surface such as quartz glass, soda lime glass, soda lime free glass, a polarizing plate on which fine aluminum or metal wires are deposited, or quartz glass An orientation treatment is performed by irradiating polarized ultraviolet rays selected from polarized ultraviolet rays by a method of passing or reflecting through a Brewster polarizer by reflection or the like. In this case, the polarized ultraviolet rays may be irradiated perpendicularly to the substrate surface, or may be irradiated at an inclined angle at a specific angle. In this way, the alignment ability of the liquid crystal molecules is imparted to the coating film.

In addition, the rubbing treatment in the alignment treatment 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 with the cloth of rubbing cloth attached to the metal ruler.

Step 4 is a step of curing the alignment-treated coating film by heat treatment.

The curing of the alignment-treated coating film may be performed after irradiation with light even in a method of manufacturing a liquid crystal alignment film using a polymer for liquid crystal aligning agent including polyamic acid or polyamic acid ester. It is distinguished from the heat treatment step applied to the substrate and irradiated with light, or performed to imidize the liquid crystal aligning agent while irradiating light.

At this time, the heat treatment may be carried out by a heating means such as a hot plate, hot air circulation furnace, infrared furnace, it is preferable to be carried out at 150 t to 300 ° C, or 180 ^° C to 250 ^° C.

On the other hand, after the step of drying the coating film (step 2), if necessary, the coating film immediately after the drying step may further comprise the step of heat treatment at a temperature above the drying step. The heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and is preferably performed ^at 150 ^° C to 250 ^° C. In this process, the liquid crystal aligning agent can be imidated. That is, the manufacturing method of the liquid crystal aligning film includes the steps of applying the above-mentioned liquid crystal aligning 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); Irradiating or rubbing the light on the heat-treated coating film may comprise a step (step 4) and the step of the heat-treated hardened coating film (step 5). On the other hand, according to another embodiment of the invention, there is provided a liquid crystal display device comprising the liquid crystal alignment film described above.

The liquid crystal alignment layer may be introduced into the liquid crystal cell by a known method, and the liquid crystal cell may likewise be introduced into the liquid crystal display by a known method. The liquid crystal alignment layer may include repeating units of Chemical Formulas 1 to 3. It can be prepared from the polymer to realize excellent stability with excellent physical properties. Accordingly, a liquid crystal display device capable of exhibiting high reliability is provided.

【Effects of the Invention】

According to the present invention, a polymer for a liquid crystal aligning agent excellent in liquid crystal alignment and electrical properties, and a method of manufacturing the same can be provided.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Preparation Examples 1 to 3: Preparation of Diamine

17. 2-chloro-5-nitropyridine of lg (100 隱 01) (2-chl or 0-5-ni tropyr idine, compound 1), 4-nitrophenol of 12.5 (98.6 讓 01) , Compound 2) was completely dissolved in 200 mL of dimethylsulfoxide (Dimethylsulfoxide, DMS0), and then 27.2 g (200 Pa ol) of potassium carbonate (K ₂ CO ₃ ) was added and stirred at room temperature for 16 hours. When the reaction was finished, the reaction product was added to a vessel containing 500 mL of water and stirred for 1 hour. The solid obtained by filtration was washed with 200 mL of water and 200 mL of ethanol to synthesize 16 g (61.3 μL) of Compound 3. (Yield: 57%)

Compound 3 was dissolved in 200 mL solution of ethyl acetate (EA) and THF in a 1: 1 mixture, 0.8 g of palladium (Pd) / carbon (C) was added thereto, and the mixture was stirred under a hydrogen environment for 12 hours. . After completion of reaction, the filtrate was concentrated in a celite pad to prepare llg compound 4 diamine. (Yield: 89%)

1 H NMR (500 MHz, DMS0-d6) δ 7.48 (dd, J = 3.0, 0.7 Hz, 1H), 7.01 (dd, J = 8.6, 3.0 Hz, 1H), 6.70-6.66 (m, 2H), 6.58 ( dd, J = 8.6 0.6 Hz, 1H), 6.65-6.50 (m, 2H), 4.92 (s, 2H), 4.85 (s, 2H). Preparation Example 2

Diamine of Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that 3-nitrophenol (3_nitrophenol) was used instead of 4-nitrophenol (4-nitrophenol, Compound 2). Preparation Example 3

Preparation Example 1 except that 2-chloro-4-nitropyridine was used instead of 2-chloro-5-nitropyridine (2-chlor 5-nitropyridine, Compound 1). In the same manner as in the diamine of Preparation Example 3 was prepared.

Synthesis Example and Comparative Synthesis Example: Synthesis of Polymer for Liquid Crystal Alignment

Synthesis Example 1 Polymer P-1 for Liquid Crystal Alignment

19.840 g (0.099 隱₀ 1) of diamine prepared in Preparation Example 1 was completely dissolved in 225.761 g of anhydrous N—methyl pyrrol i done (NMP).

Then, 20.0 g (0.092 mmol) of pyromellitic dianhydride (PMDA) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-1 for liquid crystal alignment. As a result of confirming the molecular weight of the additive polymer P-1 through GPC, the weight average molecular weight (Mw) was 25,000 g / irol.

Synthesis Example 2 Polymer P-2 for Liquid Crystal Alignment

14.708 g (0.073 隱₀ 1) of diamine prepared in Preparation Example 1 was completely dissolved in 196.681 g of anhydrous N-methyl pyrrol i done (NMP).

And 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Dihydride, BPDA) 20.Og (0.068 隱 ol) It was added to the solution and stirred for 16 hours at room temperature to prepare a liquid crystal alignment polymer P-2. As a result of checking the molecular weight of the polymer P-2 through GPC, the weight average molecular weight (Mw) is 23,000 g / mc) l.

Synthesis Example 3 Polymer P-3 for Liquid Crystal Alignment

19.305 g (0.096 μl) of the diamine prepared in Preparation Example 1 was completely dissolved in 222.726 g of anhydrous N-methyl pyrrol i done (NMP).

And, . 1,2,4,5—cyclohexanetetracarboxylic acid anhydride (l, 2,4,5-Cyclohexanetetracarboxylic dianhydride, HPMDA) 20.Og (0.089 腿 ol) is added to the solution for 16 hours at room temperature Stirring for a while to prepare polymer P-3 for liquid crystal alignment. As a result of checking the molecular weight of the polymer P-3 through GPC, the weight average molecular weight (Mw) is

25,500 g / m.

Synthesis Example 4 Polymer P-4 for liquid crystal alignment

1.984 g (0.01 μl ol) of diamine prepared in Preparation Example 1 and 9.596 g (0.089 μl ol) of p-phenylenediamine (p-PDA) were dissolved in anhydrous N-methyl pyridone (anhydr ous N -methyl pyrrol i done: NMP) was completely dissolved in 178.952g.

Then, pyromel litic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred for 16 hours at room temperature to prepare a liquid crystal alignment polymer P-4. . When the molecular weight of the polymer P-4 was confirmed through GPC, the weight average molecular weight (Mw) was 24,000 g / ii) l.

Synthesis Example 5 Polymer P-5 for liquid crystal alignment

9.920 g (0.049 μl ol) of p-phenylenediamine (p-PDA) 5.331 g (0.049 μl ol) of diamine prepared in Preparation Example 1 was anhydrous N-methyl pyridone (anhydrous N-methyl). pyrrol i done: NMP) 199.756g completely dissolved.

Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 瞧 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare a liquid crystal alignment polymer P-5. . As a result of checking the molecular weight of the polymer P-5 through GPC, the weight average molecular weight (Mw) is 27,000 g / mc) l.

Synthesis Example 6 Polymer P-6 for Liquid Crystal Alignment

1.984 g (0.01 μl ol) of diamine and 4,4′-oxydianiline (ODA) 17.768 g (0.089 μl ol) prepared in Preparation Example 1 were dried with anhydrous N-methylpyridone. (anhydrous N-methyl pyrrol idone: 匪 P) was completely dissolved in 225.263 g.

Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred for 16 hours in phase silver to prepare a polymer P-6 for liquid crystal alignment. When the molecular weight of the polymer P-6 was confirmed through GPC, the weight average molecular weight (Mw) was 27,000 g / mol.

Synthesis Example 7 Polymer P-7 for Liquid Crystal Alignment

9.920 g (0.049 瞧 ol) of diamine prepared in Preparation Example 1, 9.871 g (0.049 9.8 ol) of 4,4'-oxydianiline (0DA) was dissolved in anhydrous N_methylpyrrolidone (anhydrous). N-methyl pyrrol idone: NMP) was completely dissolved in 225.484 g.

Then, trimellitic anhydride, lactic acid-di (1 pyromel itic di anhydride, PMDA) fatigue under ice bath 20. Og (0.092隱ol ) to the to the added to the solution stirred at room temperature for 16 hours mekjeong oriented polymer P-7 for the ^" Was done. The molecular weight of the polymer P-7 was confirmed by GPC. The weight average molecular weight (Mw) was 27,500 g / irol.

Synthesis Example 8 Polymer P-8 for Liquid Crystal Alignment

1.984 g (0.01 μl ol) of diamine prepared in Preparation Example 1,

17.593 g (0.089 mmol) of 4,4'-methylenedianiline (MDA) was completely dissolved in 224.272 g of anhydrous N-methyl pyrrol idone (NMP).

Then, pyromel 1 itic di anhydride (PMDA) 20. Og (0.092 醒 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-8 for liquid crystal orientation. Prepared. The molecular weight of the polymer P-8 was confirmed by GPC. The weight average molecular weight (Mw) was 28,500 g / mol.

Synthesis Example 9 ： P-9 for Liquid Crystal Alignment

9.920 g (0.049 μl ol) of diamine prepared in Preparation Example 1 was added 9.774 g (0.049 μl ol) of 4,4′-Methylenedianiline (MDA) to anhydrous N-methylpyridone (anhydrous). N-methyl pyrrol i done: NMP) was completely dissolved in 224.934 g.

Then, pyromel Htic di anhydride (PMDA) 20. Og (0.092 mmol) was added to the solution under an ice bath, and stirred for 16 hours at room temperature to prepare Polymer P-9 for liquid crystal orientation. When the molecular weight of the solution was confirmed through GPC, the weight average molecular weight (Mw) was ² 8,500 g / iTOl.

Synthesis Example 10 ： Polymer P-10 for liquid crystal alignment

1.471 g (0.007 mmol) of diamine prepared in Preparation Example 1 and 7.114 g (0.066 μl ol) of p-phenylenediamine (p-PDA) were anhydrous N-methyl pyrrol. i done: NMP) It was completely dissolved in 161.980g.

And 20. Og (0.068 隱 ol) was added to the solution in a 3,3 ', 4,4' ᅳ biphenyltetracarboxylic acid anhydride (BPDA) in an ice bath. Stirring at room temperature for 16 hours to prepare a polymer P- ₁₀ for liquid crystal alignment. When the molecular weight of the polymer P-10 was confirmed through GPC, the weight average molecular weight (Mw) was ² 5,500 g / nK) l.

Synthesis Example 11 Polymer P-11 for liquid crystal alignment

1.471 g (0.007 μl ol) of diamine prepared in Preparation Example 1,

13.172 g (0.066 μl ol) of 4,4'-oxydianiline (0DA) was completely dissolved in 196.312 g of anhydrous N-methyl pyrrol i done (NMP).

And 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Dihydride, BPDA) under ice bath. 20. Og (0.068 隱 ol) was added to the solution, followed by stirring at room temperature for 16 hours to prepare polymer P-11 for liquid crystal alignment. As a result of checking the molecular weight of the polymer P-11 through GPC, the weight average molecular weight (Mw) is

² 5,000 g / mol.

Synthesis Example 12 ： Polymer P-12 for liquid crystal alignment

1.471 g (0.007 μl ol) of diamine, 4,4′-methylenedianiline (MDA) prepared in Preparation Example 1, 13.043 g (0.066 μl ol) was dissolved in anhydrous N-methylpyrrolidone ( anhydrous N-methyl pyrrol i done: NMP) was completely dissolved in 195.578g.

And 20, Og (0.068 mmol) was added to the 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (3,3', 4,4'-Biphenyl Tetracarboxylic Acid Di anhydride, BPDA) under an ice bath. The solution was added to the solution and stirred for 16 hours at phase silver to prepare Polymer P-12 for liquid crystal alignment. When the molecular weight of the polymer P-12 was confirmed through GPC, the weight average molecular weight (Mw) was 26,000 g / m.

Synthesis Example 13 Polymer P-13 for Liquid Crystal Alignment

1.930 g (0.01 μl ol) of diamine prepared in Preparation Example 1 and 9.337 g (0.086 μl ol) of P-phenylenediamine (p—PDA) were anhydrous N-methyl pyrrolidone (anhydr ous N-methyl pyrrol i done: NMP) was completely dissolved in 177.181 g.

Then, 10.0,4,5-cyclotetracarboxylic acid dianhydride (1,2,4,5-0 (: 101 311 6 ^ 3130 1 Di anhydride, HPMDA) 20.0 g (0.089 隱 ol) in an ice bath The solution was added to the solution and stirred at room temperature for 16 hours to prepare a liquid crystal alignment polymer P-13. As a result of checking the molecular weight of the polymer P-13 through GPC, the weight average molecular weight (Mw) was

25,500 g / iiK) l.

Synthesis Example 14 Polymer P-14 for Liquid Crystal Alignment

1.930 g (0.01 mmol) of diamine prepared in Preparation Example 1, 17.289 g (0.086 mmol) of 4,4'-oxydianiline (0DA), and anhydrous N-methylpyrrolidone (anhydrous) were prepared. N-methyl pyrrol i done: NMP) Completely dissolved in 222.242 g.

Then, 20, Og (0.089 誦 ol) was added to the solution at room temperature in an ice bath to add 1,2,4,5-cyclotetracarboxylic acid anhydride (l, 2,4,5-Cyclohexanetetracarboxylic dianhydride, HPMDA). Stirring for 16 hours to prepare a polymer P-14 for liquid crystal alignment. As a result of checking the molecular weight of the polymer P-14 through GPC, the weight average molecular weight (Mw) is

26,500 g / iTK) l.

Synthesis Example 15 Polymer P-15 for liquid crystal alignment

1.930 g (0.01 μl ol) of diamine, 4,4′-methylenedianiline (MDA) prepared in Preparation Example 1, and 17.119 g (0.086 μl ol) of anhydrous N-methyl pyrrolidone ( anhydrous N— methyl pyrrol i done: NMP) was completely dissolved in 221.278 g.

And 20. Og (0.089 隱 ol) was added to the solution at room temperature under ice bath. Stirring for 16 hours to prepare a polymer P-15 for liquid crystal alignment. As a result of checking the molecular weight of the polymer P-15 through GPC, the weight average molecular weight (Mw) is

25,500 g / nK) l.

Synthesis Example 16 Polymer P-16 for liquid crystal alignment

1.984 g (0.01 mmol) of diamine prepared in Preparation Example 2 and 9.596 g (0.089 μl) of p-phenylenediamine (p-PDA) were dried using anhydrous N-methyl anhydrous N-methyl. pyrrol i done: NMP) completely dissolved in 178.952g.

Then, pyromellitic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-16 for liquid crystal orientation. When the molecular weight of the polymer P-16 was confirmed through GPC, the weight average molecular weight (Mw) was 22, 000 g / mo 1.

Synthesis Example 17 Polymer P-17 for Liquid Crystal Alignment 1.984 g (0.01 μl ol) of diamine, 4,4′-oxydianiline (0DA) prepared in Preparation Example 2, and 17.768 g (0.089 μl ol) of anhydrous N-methylpyrrolidone ( anhydrous N-methyl pyrrol i done: completely dissolved in 225.263 g of P).

Then, 20.0 g (0.092 물 ol) of pyromellitic di anhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer P-17 for liquid crystal alignment. The molecular weight of the polymer P-17 was confirmed by GPC, and a weight average molecular weight (Mw) was 26,500 g / irol.

Synthesis Example 18 ： Polymer P-18 for liquid crystal alignment

1.984 g (0.01 mmol) of diamine prepared in Preparation Example 2 and 17.593 g (0.089 μl ol) of 4 ′ 4′-methylenedianiline (MDA) were dissolved in anhydrous N-methylpyrrolidone (anhydrous). N-methyl pyrrol i done: NMP) was completely dissolved in 224.272g.

Then, pyromeltic dianhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer P-18. It was. The molecular weight of the polymer P-18 was confirmed by GPC. The weight average molecular weight (Mw) was 24,500 g / mol.

Synthesis Example 19 ： Polymer P-19 for liquid crystal orientation

1.984 g (0.01 μl ol) of diamine prepared in Preparation Example 3 and 9.596 g (0.089 μl ol) of p-phenylenediamine (p-PDA) were added to anhydrous N-methyl pyridone (anhydrous N- methyl pyrrol i done: NMP) completely dissolved in 178.952g.

Then, pyromelic acid dianhydride (pyromel 1 it ic di anhydride, PMDA) 20. Og (0.092 薩 ol) is added to the solution under an ice bath and stirred at room temperature for 16 hours to form a polymer for liquid crystal alignment. P-19 was prepared. The molecular weight of the polymer P-19 was confirmed by GPC, and a weight average molecular weight (Mw) was 22,500 g / mol.

Synthesis Example 20 ： Polymer P-20 for liquid crystal alignment 1.984 g (0.01 μl ol) of diamine, 4,4′-oxydianiline (0DA) prepared in Preparation Example 3, and 17.768 g (0.089 μl ol) of anhydrous N-methylpyrrolidone ( anhydrous N-methyl pyrrol i done: NMP) was completely dissolved in 225.263 g.

Then, 20.0 g (0.092 瞧 ol) of pyromellitic acid anhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare a liquid crystal alignment polymer P-20. . As a result of checking the molecular weight of the polymer P-20 through GPC, the weight average molecular weight (Mw) was 24,500 g / m.

Synthesis Example 21 Polymer P-21 for Liquid Crystal Alignment

1.984 g (0.01 隱 ol) of diamine and 4,4′-methylenedianiline (MDA) prepared in Preparation Example 3, 17.593 g (0.089 瞧) of anhydrous N—methylpyridone ( anhydrous N-methyl pyrrol i done: NMP) completely dissolved in 224.272g.

Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 隱 ol) was added to the solution under an ice bath, and stirred for 16 hours in phase silver to prepare a liquid crystal alignment polymer P ᅳ 21. It was. The molecular weight of the polymer P-21 was confirmed by GPC, and a weight average molecular weight (Mw) was 26,000 g / mol.

Synthesis Example 22 ： Polymer P-22 for Liquid Crystal Alignment

1.93 g (0.01 μl ol) of diamine prepared in Preparation Example 1 and 9.337 g (0.086 μl ol) of p-phenylenediamine (p-PDA) were added to anhydrous N-methylpyrrolidone (anhydrous N- Methyl pyrrol i done: NMP) was completely dissolved in 177.181 g.

Then, 20.0 g (0.089 隱 ol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) was added to the solution under an ice bath, and the mixture was stirred for 16 hours in phase silver liquid crystal. Orientation Polymer P-22 was prepared. The molecular weight of the polymer P-22 was confirmed by GPC. As a result, the weight average molecular weight (Mw) was 21,000 g / mol.

Synthesis Example 23 Polymer P-23 for Liquid Crystal Alignment 19.305 g (0.096 μl) of the diamine prepared in Preparation Example 1 were completely dissolved in 222.726 g of anhydrous N-methyl pyrrol i done (NMP).

And under an ice bath _. 1, 3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) 20. Og (0.089 隱 ol) was added to the solution and stirred for 16 hours at room temperature to give a liquid crystal alignment polymer P -23 was prepared. The molecular weight of the polymer P-23 was confirmed by GPC, and a weight average molecular weight (Mw) was 23,500 g / mol.

Synthesis Example 24 Polymer P-24 for Liquid Crystal Alignment

1.93 g (0.01 μl ol) of diamine, 4,4′-methylenedianiline (4,4′—Methylenedianiline, MDA) prepared in Preparation Example 1, and 17.119 g (0.086 μl ol) of anhydrous N-methylpyrrolidone ( anhydrous N-methyl pyrrol i done: NMP) was completely dissolved in 221.278g.

Then, 20.0 g (0.089 瞧 ol) of 1, 3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to give a liquid crystal. Orientation Polymer P-24 was prepared. When the molecular weight of the polymer P-24 was confirmed through GPC, the weight average molecular weight (Mw) was 22,500 g / m.

Synthesis Example 25 ： Polymer P-25 for liquid crystal alignment

1.93 g (0.01 隱 ol) of diamine prepared in Preparation Example 1, and 17.119 g (0.086 mmol) of 4,4 ′ ᅳ methylenedianiline (J-Methylenedianiline Jffl) were added to anhydrous N—methylpyrrolidone (anhydrous N-methyl pyrrol i done: NMP) completely dissolved in 219.749 g.

And 10.0 g (0.045 醒 ol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA) and pyromellitic di anhydride (PMDA) 9.73 g (0.045 μl) was added to the solution, followed by stirring at room temperature for 16 hours to prepare polymer P-25 for liquid crystal alignment. The molecular weight of the polymer P-25 was confirmed by GPC. The weight average molecular weight (Mw) was 22,000 g / ii l. Comparative Synthesis Example 1 Polymer R-1 for Liquid Crystal Alignment

26.852 g (0.099 隱 ol) of p-phenylenediamine (p-PDA) was completely dissolved in 265.496 g of anhydrous N-methyl pyrrolidone (NMP).

Then, pyromel 1 itic di anhydride (PMDA) 20. Og (0.092 醒 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare polymer R-1 for liquid crystal orientation. Through the GPC confirmed the molecular weight of the polymer R-1 results, a weight average molecular weight (Mw) of ² 6,000g / n) was l.

Comparative Synthesis Example 2 Polymer R-2 for Liquid Crystal Alignment

19.743 g (0.099 mmol) of 4,4'-oxydianiline (4,4'-oxydianiline, 0DA) was completely dissolved in 225.208 g of anhydrous N-methyl pyrrolidone (NMP).

Then, 20.0 g (0.092 물 ol) of pyromellitic di anhydride (PMDA) was added to the solution under an ice bath, followed by stirring at room temperature for 16 hours to prepare polymer R-2 for liquid crystal alignment. When the molecular weight of the polymer R-2 was confirmed through GPC, the weight average molecular weight (Mw) was 21,000 g / nx) l.

Comparative Synthesis Example 3 Polymer for Liquid Crystal Alignment R-3

19.548 g (0.089 dl ol) of 4,4'-methylenedianiline (4,4'-Methylenedianiline DA) was completely dissolved in 224.218 g of anhydrous N-methyl pyrrolidone (XP).

Then, pyromel 1 it ic di anhydride (PMDA) 20. Og (0.092 匪 ol) was added to the solution under an ice bath, and stirred at room temperature for 16 hours to prepare a polymer for liquid crystal alignment R-3. It was. When the molecular weight of the polymer R-3 was confirmed through GPC, the weight average molecular weight (Mw) was 23,000 g / ii l.

Comparative Synthesis Example 4: Polymer R-4 for Liquid Crystal Alignment

Liquid crystal in the same manner as in Synthesis Example 1, except that the compound represented by the following Formula A was used instead of the diamine prepared in Preparation Example 1. Polymer R-4 for an alignment agent was prepared.

Example 1

20 g of the polymer for liquid crystal aligning agent of Synthesis Example 1 (Ρ-1) was dissolved in a mixed solvent of MP 8.65 g, GBL 19.95 g, and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-1.

Example 2

20 g of the liquid crystal aligning agent polymer (P-2) of Synthesis Example 2 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-2.

Example 3

20 g of the liquid crystal aligning agent polymer (P-3) of Synthesis Example 3 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2'butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent A-3.

Example 4

20 g of the liquid crystal aligning agent polymer (P-4) of Synthesis Example 4 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. And the pore size of the poly (tetrafluorene ethylene) material of the obtained solution is O. The liquid crystal aligning agent B-1 was manufactured by pressure filtration with the filter which is lizm.

Example 5

20 g of the liquid crystal aligning agent polymer (P # 5) of Synthesis Example 5 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. And the pore size of the poly (tetrafluorene ethylene) material

The liquid crystal aligning agent B-2 was manufactured by pressure filtration with the filter which is 0.01 / m.

Example 6

20 g of the liquid crystal aligning agent polymer (P-6) of Synthesis Example 6 was dissolved in P.65g, GBL 19.95g, and 2-butoxyethane in 11.4g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-3.

Example 7

20 g of the liquid crystal aligning agent polymer (P-7) of Synthesis Example 7 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-4.

. Example 8

20 g of the liquid crystal aligning agent polymer (P-8) of Synthesis Example 8 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (im / im) of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-5.

Example 9

20 g of the liquid crystal aligning agent polymer (P-9) of Synthesis Example 9 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent B-6.

Example 10

20 g of the liquid crystal aligning agent polymer (P-10) of Synthesis Example 10 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (pore size) made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent C-1.

Example 11

A 5 wt solution by dissolving a liquid crystal aligning jeyong polymer (P-11) 20 g of the above Synthesis Example 11 in 8.65 g heunhap solvent of NMP, GBL 19.95 g, 2 eu Appendix ethanol during 11 .4g ^' Got it. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (l / m) of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent C-2.

Example 12

20 g of the polymer (P-12) for liquid crystal aligning agent of Synthesis Example 12 was P 8.65 g, GBL 19.95 g,. 2-Buroxyethane was dissolved in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent C-3.

Example 13

20 g of the liquid crystal aligning agent polymer (P-13) of Synthesis Example 13 was dissolved in NMP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.1 / Λπ of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent D-1.

Example 14

20 g of the liquid crystal aligning agent polymer (P-14) of Synthesis Example 14 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. And the obtained solution was filtered under pressure with the filter whose pore size of the poly (tetrafluoreneethylene) material is 0.01 / (La), and the liquid crystal aligning agent D-2 was manufactured.

Example 15

20 g of the liquid crystal aligning agent polymer (P-15) of Synthesis Example 15 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (m / m) made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent D-3.

Example 16

20 g of the liquid crystal aligning agent polymer (P-16) of Synthesis Example 16 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 zm of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent E-1.

Example 17

20 g of the liquid crystal aligning agent polymer (Ρ-Γ7) of Synthesis Example 17 was dissolved in NMP 8.65 g, GBL 19.95 g, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt solution. Got it. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent E-2.

Example 18

20 g of the liquid crystal aligning agent polymer (P-18) of Synthesis Example 18 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.1 (Λ Π) of poly (tetrapuloene ethylene) material to prepare a liquid crystal aligning agent E-3.

Example 19

20 g of the liquid crystal aligning agent polymer (P—19) of Synthesis Example 19 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-1.

Example 20

20 g of the liquid crystal aligning agent polymer (P # 20) of Synthesis Example 20 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2'butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-2.

Example 21

20 g of the liquid crystal aligning agent polymer (P-21) of Synthesis Example 21 was dissolved in a mixed solvent of P 8.65 g, GBL 19.95 g, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 m of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent F-3.

Example 22

20 g of the liquid crystal aligning agent polymer (P-22) of Synthesis Example 22 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution has a pore size of poly (tetrafluoreneethylene). The liquid crystal aligning agent G-1 was manufactured by pressure filtration with the filter of (beta) (eta).

Example 23

20 g of the liquid crystal aligning agent polymer (Ρ-23) of Synthesis Example 23 was dissolved in a mixed solvent of NMP 8.65 g, GBL 19.95 g, and 2—butoxyethanol 11.4 g to obtain a 5 wt solution. Got it. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent G-2.

Example 24

20 g of the liquid crystal aligning agent polymer (P-24) of Synthesis Example 24 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent G-3.

Example 25

20 g of the liquid crystal aligning agent polymer (P-25) of Synthesis Example 25 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2'butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 (Λ ΛΠ) made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent G-4.

Comparative Example 1

20 g of the liquid crystal aligning agent polymer (R-1) of Comparative Synthesis Example 1 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent R'-1.

Comparative Example 2

20 g of the polymer for liquid crystal aligning agent of Comparative Synthesis Example 2 (R-2) was dissolved in 8.65 g of NMP, 19.95 g of GBL, and 2-butoxyethane in 11.4 g of a mixed solvent to obtain a 5 wt% solution. And the pore size of the poly (tetrafluorene ethylene) material of the obtained solution is O. The liquid crystal aligning agent R'_2 was produced by pressure filtration with the filter which is IJI.

Comparative Example 3

20 g of the liquid crystal aligning agent polymer (R'3) of Comparative Synthesis Example 3 was dissolved in a mixed solvent of 8.65 g of NMP, 19.95 g of GBL, and 11.4 g of 2-butthoethanol to obtain a 5 wt% solution. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.01 / Λπ of poly (tetrafluoreneethylene) material to prepare a liquid crystal aligning agent R'-3.

Comparative Example 4

20 g of the liquid crystal aligning agent polymer (R-4) of Comparative Synthesis Example 4 was dissolved in a mixed solvent of NMP 8.65 g, GBL 19.95 g, and 2—butoxyethanol 11.4 g to obtain a 5 wt% solution. Got it. Then, the obtained solution was filtered under pressure with a filter having a pore size of 0.1 (Λ ΛΠ) made of poly (tetrafluoreneethylene) to prepare a liquid crystal aligning agent R'-4.

<Experimental Example: Measurement of physical properties of liquid crystal aligning agents obtained in Examples and Comparative Examples> A liquid crystal aligning cell was prepared using the liquid crystal aligning agents obtained in the above Examples and Comparative Examples, and the respective physical properties were obtained from the liquid crystal aligning cells by the following method. It measured, and the result is shown in Table 1.

Specifically, the ITO electrode having 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 is spin-coated on each of the upper and lower substrates for the voltage holding ratio (VHR) patterned. The liquid crystal aligning agent obtained by the said Example and the comparative example was apply | coated. Subsequently, the substrate to which the liquid crystal aligning agent was applied was placed on a hot plate of about 80 ^° C., dried for 2 minutes to evaporate the solvent.

Thereafter, after firing (curing) the dried upper and lower plates at about 230 ^° C. in Aubon for 2000 seconds, in order to orient the coating film thus obtained, while rotating the rubbing roller attached with a cloth of rubbing cloth to the metal roller, The surface was rubbed in one direction.

Thereafter, the orientation-treated upper and lower plates were baked (cured) for 15 minutes in an oven at about 230 ^° C. to obtain a coating film having a film thickness of 0.1 m. Then, a sealing agent impregnated with a 4.5 mi ball spacer was applied to the edges of the upper plate except for the liquid crystal injection hole. The alignment films formed on the upper and lower plates face each other and are aligned so that the alignment directions are parallel to each other. Then, the upper and lower plates are bonded to each other, and an empty cell is prepared by UV and thermal curing the sealing agent. Then, a 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.

1 · voltage holding ratio (VHR)

With respect to the liquid crystal cell aligned, using the equipment of 6254C T0Y0 corporat ion to the measuring equipment, to measure the voltage retention rate at 1Hz, 60 ^° C temperature.

2. AC afterimage The polarizing plates were attached to the upper and lower plates of the liquid crystal cell so as to be perpendicular to each other. The liquid crystal cell to which the said polarizing plate was attached was attached on the back light of 000 cd / m <^2> , and the brightness | luminance of a black state was measured using the PR-880 equipment which is a brightness brightness measuring instrument. Then, the liquid crystal cell was driven for 24 hours at 5V at room temperature. Then, the brightness of the black state was measured in the same manner as described above with the voltage of the liquid crystal cell turned off. The difference between the initial luminance L0 measured before driving 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 variation rate. The calculated luminance fluctuation rate is closer to 0%, which means that the orientation stability is excellent. The afterimage level was evaluated based on the following criteria through the measurement results of the luminance change rate.

Excellent: Less than 10% luminance change

Normal: Luminance variation rate is 10% to 20%

[Table 1]

Experimental Example Measurement Results of Examples and Comparative Examples

Example 24 P-24 Preparation Example 1, MDA DMCBDA 70 Excellent

(10: 86)

Example 25 P-25 Production Example 1 MDA DMCBDA, PMDA 68 Excellent

(10: 86) (45: 45)

Comparative Example 1 R-1 p-PDA PMDA 55 Normal Comparative Example 2 R-2 0DA PMDA 63 Normal Comparative Example 3 R-3 MDA PMDA 64 Normal Comparative Example 4 R-4 Formula A PMDA 55 Normal As shown in Table 1 above As the liquid crystal aligning agent of Example included polymers prepared from reactants including diamines having an asymmetric structure as in Preparation Examples 1 to 3, the voltage retention (VHR) was improved to 82% to 90%, and AC afterimage was equivalent. It was confirmed that the level can be maintained above.

Example 22 In the case of the liquid crystal aligning agent of Examples 22 to 25, the voltage retention ratio (VHR) was found to be 60% to 70%, but the luminance variation was measured to be less than 10%, and it was confirmed that AC afterimage was greatly improved.

On the other hand, the liquid crystal aligning agent of the comparative example does not contain diamines having the same asymmetric structure as those of Preparation Examples 1 to 3 in the preparation of the polymer, and exhibits a significantly lower voltage retention (VHR) of 54% to 64% than the Examples As the rate of change increased from 10% to 20%, it was confirmed that the AC afterimage characteristic was poor.

Claims

[Claim]

[Claim 1]

A polymer for a 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:

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,.

At least one of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms, and the rest are hydrogen;

X ¹ to X ³ are each independently a tetravalent organic group,

Y ¹ to Y ³ are each independently a divalent organic group represented by the following formula (4),

[Formula 4]

In Chemical Formula ⁴ ,

A is a group 16 element,

R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

a is an integer of 0 to 3,

At least one of Zi to Z ₄ is nitrogen and the other is carbon.

[Claim 2]

The method of claim 1,

In Chemical Formula 4, one of 1γ to γ ₄ is nitrogen, and the other is carbon.

[Claim 3]

The method of claim 1,

In Formula 4, Ζ: or one of Ζ ₃ is nitrogen and the others are carbon atoms, and Ζ ₄ is a carbon, a liquid crystal alignment jeyong polymer.

[Claim 4]

In U,

In Formula 4, A is oxygen, a is 0, a polymer for a liquid crystal aligning agent.

[Claim 5]

According to claim 1,

Formula 4 is selected from the group consisting of the following formula 4-1, formula 4-2 and formula 4-3 돤 one or more repeating step _| comprising a polymer for a liquid crystal aligning agent:

[Formula 4-1]

[Claim 6]

In U,

Wherein X ¹ to X ³ each independently include the following formula organic group, a polymer for a liquid crystal aligning agent:

[Formula 5]

R ₉ to R ₁₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

L ₂ is a direct bond, -0-, -CO-, -S-, -SO-, -S0 _2- , -CRisRie-, -CONH-, -C00-,-(CH ₂ ) _b- , -0 ( CH ₂ ) _b 0-, -C00- (CH ₂ ) _b -0C0-, phenylene or any combination thereof;

R ₁₅ and Ri ₆ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, and b is an integer of 1 to 10.

[Claim 7]

According to claim 1,

A polymer for a liquid crystal aligning agent, further comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (11), a repeating unit represented by the following formula (12) and a repeating unit represented by the following formula (13):

[Formula 11]

[Formula 12]

13]

In Chemical Formulas 11 to 13,

At least one of R ³ and R ⁴ is an alkyl group having 1 to 10 carbon atoms The rest is hydrogen,

X ⁴ to X ⁶ are each independently a tetravalent organic group,

Y ⁴ to Y ⁶ are each independently a divalent organic group represented by Formula 14 or 15,

[Formula 14]

In Chemical Formula 14,

R ⁵ and R ⁶ are each independently hydrogen, halogen, cyano, d- ₁₀ alkyl, C: alkenyl, Cwo alkoxy, d-) fluoroalkyl, or do fluoroalkoxy,

P and q are each independently integers of 0 to 4

L ¹ is a single bond, -0-, -CO-, -S-, -S0 _2- , -C (CH ₃ ) _2- ᅳ -C (CF ₃ ) _2- , -CONH-, ᅳ C00-,- (CH ₂ ) _Z- , -0 (CH ₂ ) _z 0-, -0 (C¾) _Z ᅳ, -NH-, -NH (CH ₂ ) _Z -NH-, -H (CH ₂ ) _z 0-, -0CH ₂ -C (CH ₃ ) ₂ -CH ₂ 0-, -COO- (C¾) _z -OC, or -0CCKCH ₂ ) _z -C00-,

z is an integer from 1 to 10,

k and m are each independently an integer of 0 to 3, or 1 to 3 and n is an integer of 0 to 3.

Claim 8 The polymer for liquid crystal aligning agent of Formula 15 or Formula 16:

[Formula 15]

[Formula 16]

In Chemical Formula 16,

D is a direct bond, 0, S0 ₂ or C (R ₇ ) (R ₈ ), wherein R ₇ and R ₈ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

[Claim 9]

In U,

The polymer for liquid crystal aligning agents whose weight average molecular weights of the said polymer for liquid crystal aligning agents are 1000 g / mol-200, 000 g / mol.

[Claim 10]

The liquid crystal aligning agent containing the polymer for liquid crystal aligning agents of Claim 1. [Claim 11]

The liquid crystal aligning film containing the liquid crystal aligning agent of Claim 10.

[Claim 12]

A liquid crystal display device comprising the liquid crystal alignment film of claim 11.