KR102252429B1 - 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 composition comprising a liquid crystal polymer together with a (co)polymer containing a photopolymerizable divalent organic group, 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.

Description

A liquid crystal aligning agent composition, a method of manufacturing a liquid crystal aligning film using the same, and a liquid crystal aligning film using the same, a liquid crystal display device BACKGROUND OF THE INVENTION 1.

The present invention relates to a liquid crystal aligning agent composition capable of implementing excellent liquid crystal alignment characteristics and afterimage characteristics, a method of manufacturing a liquid crystal alignment film using the same, and a liquid crystal alignment film and a liquid crystal display device using the same.

In a liquid crystal display device, the liquid crystal alignment layer plays a role of aligning the liquid crystal in a predetermined direction. Specifically, the liquid crystal alignment layer acts as a director in the arrangement of liquid crystal molecules, so that the liquid crystal moves by an electric field to form an image, so that the liquid crystal aligns the proper direction. In order to obtain uniform brightness and high contrast ratio in a liquid crystal display device, it is essential to uniformly align the liquid crystal.

As one of the conventional methods of aligning the liquid crystal, a polymer film such as polyimide is applied to a substrate such as glass, and the surface is rubbed in a predetermined direction using fibers such as nylon or polyester. However, the rubbing method may generate fine dust or electrical discharge (ESD) when the fibers 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 light irradiation rather than friction, and arranging liquid crystals using the same has been studied.

Various materials are 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 layer. However, since polyimide has poor solvent solubility, it is difficult to apply it directly to a manufacturing process in which an alignment layer is formed by coating in a solution state.

Therefore, after coating in the form of a precursor such as polyamic acid or polyamic acid ester having excellent solubility, a heat treatment process is performed at a temperature of 200 ℃ to 230 ℃ to form a polyimide, and light irradiation is performed thereon to achieve initial anisotropy through orientation treatment. After inducing, and then performing an additional high-temperature heat treatment process, as well as imidization conversion, as well as orientation stabilization due to anisotropy are achieved at the same time.

However, in the high-temperature firing process, the polyamic acid remaining in the polyimide or the side reaction of the polyamic acid formed by the depolymerization reaction from the polyimide proceeds, thereby realizing high-quality driving characteristics in the liquid crystal display device. There was a limit to not satisfying the high level of afterimage characteristics for this.

Accordingly, there is a need to develop a liquid crystal aligning agent composition capable of realizing excellent afterimage characteristics while achieving alignment characteristics as a liquid crystal alignment layer.

The present invention relates to a liquid crystal aligning agent composition capable of implementing excellent liquid crystal alignment characteristics and afterimage characteristics.

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

In addition, the present invention is to provide a liquid crystal alignment layer manufactured by the above manufacturing method and a liquid crystal display device including the same.

In order to solve the above problems, in the present specification, including at least one 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) )polymer; And it provides a liquid crystal aligning agent composition comprising an aromatic polyester-based polymer.

[Formula 1]

[Formula 2]

[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 rest are hydrogen, and X ₁ to X ₃ are the same as or different from each other, and each independently a tetravalent organic group, Y ₁ to Y ₃ are the same as or different from each other, and each independently, a divalent organic group represented by the following formula (4),

[Formula 4]

In Formula 4, A is one of -O-, -S-, -NH-, or an alkylene group having 1 to 10 carbon atoms, and R _a and R _b are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms Is one.

In the present specification, further, a step of forming a coating film by applying the liquid crystal aligning agent composition to a substrate; Drying the coating film; Performing alignment treatment by irradiating light or rubbing the dried coating film; And there is provided a method of manufacturing a liquid crystal alignment film comprising the step of curing the alignment-treated coating film by heat treatment.

In the present specification, a liquid crystal alignment layer including an alignment cured product of the liquid crystal alignment 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 using the same, and a liquid crystal display device will be described in more detail.

Ⅰ. Liquid crystal aligning agent composition

According to an embodiment of the present invention, a (co)polymer including at least one 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 liquid crystal aligning agent composition including an aromatic polyester-based polymer may be provided.

In the case of a liquid crystal aligning agent composition comprising an aromatic polyester polymer together with a (co)polymer, as in the above embodiment, in addition to excellent liquid crystal alignment properties in a liquid crystal cell in which a liquid crystal alignment film obtained from the liquid crystal alignment agent composition is installed, It was confirmed through an experiment that an improved afterimage characteristic could be implemented, and the invention was completed.

This, while inducing the anisotropy of the liquid crystal alignment layer by using the (co)polymer, while increasing the anisotropy and alignment of the liquid crystal alignment layer through an aromatic polyester-based polymer that can have liquid crystal by maintaining a crystal state even in a molten state, The liquid crystal properties (crystallinity in the molten state) of the aromatic polyester polymer are expressed within the temperature range of 100°C to 150°C in which the low-temperature sintering of the (co)polymer proceeds, so that the resistance of the finally produced liquid crystal alignment layer is reduced. As it is lowered, excellent afterimage characteristics can be implemented.

Accordingly, it is possible to solve the problem that the existing liquid crystal alignment agent composition containing only the (co)polymer has a low imidation rate when sintering at a low temperature of 150° C. or lower and has poor image retention and alignment characteristics.

In the liquid crystal aligning composition of one embodiment, the (co)polymer and the aromatic polyester polymer are not simply mixed together, but when mixed at a specific weight ratio of 11:89 to 89:11, from the liquid crystal aligning composition It was confirmed that the alignment characteristics and afterimage characteristics of the obtained liquid crystal alignment film or liquid crystal alignment cell can be improved to an optimum level.

Hereinafter, the present invention will be described in more detail.

In the present specification, the following terms may be defined as follows unless there is a specific limitation.

In the present specification, (co)polymer is meant to include all polymers or copolymers, and the polymer means a homopolymer composed of a single repeating unit. That is, in the present specification, the (co)polymer may include both a homopolymer or a copolymer.

In the present specification, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In the present specification, examples of the substituent are described below, but are not limited thereto.

In the present specification, the term "substitution" means that other functional groups are bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which 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.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the aforementioned substituents. . For example, "a substituent to which two or more substituents are connected" 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 의미하고, 직접결합은 L 로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,

, or

Means a bond connected to another substituent, and a direct bond means a case in which a separate atom does not exist in the portion represented by L.

In the present specification, the alkyl group is a monovalent functional group derived from alkane and may be linear or branched, and the number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the branched chain alkyl group has 3 to 20 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, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, 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, 2,6-dimethylheptan-4-yl, and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, the haloalkyl group refers to a functional group in which a halogen group is substituted with the above-described 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 cycloalkyl group is a monovalent functional group derived from cycloalkane, may be monocyclic or polycyclic, and is not particularly limited, but has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 10 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,2,1]heptyl, and the like, but are not limited thereto. The cycloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the alkylene group is a divalent functional group derived from alkane, and the description of the above alkyl group may be applied except that these are divalent functional groups. For example, as a linear or branched type, it may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, and the like. The alkylene group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied except that these are divalent functional groups. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and one or more heteroatoms, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 4 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, p Nanthrolyl group (phenanthroline), thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, aziridyl group, azaindolyl group, isoindole group, inda Sleepy, purine, pteridine, beta-carbolyl, naphthyridine, ter-pyridyl, phenazinyl, imidazopyridyl, pyropyridyl, azepine , A pyrazolyl group and a dibenzofuranyl group, but are not limited thereto. The heteroaryl group may be substituted or unsubstituted.

In the present specification, the cycloalkylene group is a divalent functional group derived from cycloalkane, and the description of the cycloalkyl group described above may be applied except that it is a divalent functional group. The cycloalkylene group may be substituted or unsubstituted.

In the present specification, in the present specification, the heteroarylene group has 2 to 20, or 2 to 10, or 6 to 20 carbon atoms. An arylene group containing O, N, or S as a hetero atom, except that it is a divalent functional group, may be applied to the description of the heteroaryl group described above. The heteroarylene group may be substituted or unsubstituted.

In the present specification, a multivalent organic group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound has been removed, and examples thereof include a divalent organic group, a trivalent organic group, and a tetravalent organic group. . As an example, a tetravalent organic group derived from cyclobutane refers to a residue in which any 4 hydrogen atoms bonded to cyclobutane have been removed.

In the present specification, a direct bond or a single bond means that no atom or group of atoms exists at the corresponding position and is connected by a bonding line. Specifically, it refers to a case where no separate atom exists in the portion represented by _{L 1} or L _{2 in the formula.}

(1) (co)polymer

The (co)polymer may include at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. Specifically, the (co)polymer may include one polyamic acid repeating unit, one polyamic acid ester repeating unit, one polyimide repeating unit, or a copolymer in which two or more repeating units thereof are mixed.

At least one repeating unit selected from the group consisting of the polyamic acid repeating unit, the polyamic acid ester repeating unit, and the polyimide repeating unit may form the main chain of the (co)polymer.

The (co)polymer may react during photo-alignment or rubbing-alignment treatment to induce anisotropy of the finally prepared liquid crystal alignment layer, and after alignment, it may be converted into imidation through a high-temperature firing process to achieve alignment stabilization.

More specifically, the polyimide repeating unit includes the repeating unit represented by Formula 1, the polyamic acid ester repeating unit includes the repeating unit represented by Formula 2, and the polyamic acid repeating unit is represented by Formula 3 It may include a displayed repeating unit.

The Y ₁ to Y ₃ may be a functional group derived from a polyamic acid, a polyamic acid ester, or a diamine compound used in synthesizing a polyimide. In the case where Y ₁ to Y ₃ are each independently a divalent organic group represented by Formula 4, the repeating unit represented by Formula 4 is a structure in which a photoreactive group is introduced into the main chain of polyamic acid, polyamic acid ester, or polyimide. As a result, since the photoreactive group is included in the main chain and alignment occurs due to bonding between the main chains, the liquid crystal alignment performance can be kept constant even under AC driving conditions. Particularly, when polarized ultraviolet rays are irradiated to the polyimide precursor or polyimide, a [2+2] cycloaddition reaction is induced. This reaction causes the liquid crystal to be vertically or parallel to the direction of the irradiated polarized ultraviolet rays. Can be oriented. In addition, the photoreaction rate and stability may be further improved by an additional photoreaction of the C=C bond introduced into the polymer.

Specifically, in Formula 4, R _a and R _b are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen, 2-methyl, 3-methyl, 2,3-dimethyl, 2, It may be 6-dimethyl, 3,5-dimethyl.

In addition, the A may be -O-, -S-, -NH-, or an alkylene group having 1 to 10 carbon atoms, preferably -O-, -NH-, -(CH ₂ )-, or -( CH ₂ ) ₂ -may be.

Meanwhile, in Formulas 1 to 3, X ₁ to X ₃ may be a functional group derived from a polyamic acid, a polyamic acid ester, or a tetracarboxylic acid dianhydride compound used in synthesizing a polyimide.

More specifically, X ₁ to X ₃ may each independently be one of a tetravalent organic group represented by Formula 6 below.

[Formula 6]

In Formula 6, R ₆ to R ₁₁ 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 ₁₂ R ₁₃ -, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO(CH ₂ ) _t OCO-, -CONH-, phenylene or a combination thereof It is any one selected from the group consisting of, wherein R ₁₂ and R ₁₃ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group, and t is an integer of 1 to 10.

More preferably, X ₁ to X ₃ may each independently be one functional group selected from the group consisting of the following Formulas 6-1 to 6-4:

[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

In Formulas 6-3 and 6-4,

R ₁₂ to R ₁₅ are each independently a direct bond, -O-, -S-, -C(O)-, -S(O)-, -C(O)O-, -O(C)O- , Alkylene having 1 to 10 carbon atoms, and at least one divalent functional group selected from the group consisting of -C(R')(R")-, and when R ₁₂ to R ₁₅ contain two or more functional groups, They are connected to each other,

Each of R'and R" is independently an alkyl group having 1 to 10 carbon atoms, which is unsubstituted or substituted with hydrogen or halogen.

In addition, X may be selected from the group consisting of the following formula:

,

,

,

,

,

,

,

,

, 및

,

,

,

,

,

,

,

,

, And

(2) Aromatic polyester polymer

In addition to the (co)polymer, the liquid crystal aligning agent composition of the embodiment may include an aromatic polyester polymer. The anisotropy of the liquid crystal alignment layer can be improved through an aromatic polyester-based polymer capable of maintaining a crystal state even in a molten state and having liquid crystal properties, while remarkably improving the afterimage characteristics of the liquid crystal alignment layer.

The aromatic polyester-based polymer may include an aromatic polyester or a derivative polymer thereof, and the aromatic polyester refers to a case in which all functional groups in the repeating unit constituting the polyester are aromatic.

The term “a derivative polymer of the aromatic polyester” refers to a case in which the aromatic polyester further includes an aliphatic functional group or an alicyclic functional group together with an aromatic functional group in the repeating unit constituting the polyester.

The aromatic polyester polymer may include at least one or more of a residue derived from an aromatic diol, or a residue derived from an aromatic dicarboxylic acid or a derivative thereof, or a residue derived from an aromatic dicarboxylic acid containing a hydroxy group or a derivative thereof, and Accordingly, the aromatic polyester-based polymer may form a liquid crystal in a solution or molten state based on the rigidity of the main chain. That is, the aromatic polyester polymer is a liquid crystal polymer (LCP).

Specifically, the aromatic polyester polymer may include a repeating unit represented by the following formula (5). The physical/chemical properties of the aromatic polyester polymer as a liquid crystal polymer appear to be due to the specific structure of the following formula (5).

[Formula 5]

In Formula 5, R ₃ and R ₄ are the same as or different from each other, _{and at least one of R 3} and R ₄ is one of an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and the remainder is 6 carbon atoms. It is one of an arylene group of to 20, a heteroarylene group of 2 to 20 carbon atoms, an alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of 3 to 20 carbon atoms.

That is, in Formula 5, R ₃ is one of an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and R ₄ is an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, It may be one of an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms.

In addition, in Formula 5, R ₄ is one of an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and R ₃ is an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, It may be one of an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms.

In Formula 5, R ₃ is a functional group derived from a monomer containing a hydroxy group forming an ester bond, and R ₄ is a functional group derived from a monomer containing a carboxy group or an acyl group forming an ester bond.

That is, the formula 5 is a repeating unit included in the main chain of the polyester, and in the formula 5, when R ₃ and R ₄ are different from each other, two kinds of monomers (hydroxy group) used to synthesize the polyester main chain At least one of the monomers containing or a monomer containing a carboxy group or an acyl group) may necessarily include an aromatic arylene group or a heteroarylene group.

In addition, in Formula 5, when R ₃ and R ₄ are the same as each other, one type of monomer including both a hydroxy group and a carboxyl group or an acyl group in the molecule may necessarily include an aromatic arylene group or a heteroarylene group.

More specifically, the aromatic polyester polymer may include a repeating unit represented by Formula 5-1 below.

[Chemical Formula 5-1]

In Formula 5-1, Ar is an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 6 to 20 carbon atoms, and R ₅ is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms.

Preferably, in Formula 5-1, R ₅ may be an alkylene group having 8 to 14 carbon atoms, and Ar may be an arylene group having 10 to 15 carbon atoms (specifically, a biphenylene group).

In Formula 5-1, Ar is a functional group derived from a diol monomer containing a hydroxy group forming an ester bond, and R ₅ is a functional group derived from a dicarboxylic acid or dicarboxylic acid containing an acyl group or a carboxyl group forming an ester bond. to be.

In addition to the repeating unit represented by Chemical Formula 5, the aromatic polyester-based polymer may further include other repeating units according to intended physical properties. Examples of the other repeating units include polyester repeating units derived from aliphatic alcohol components and aliphatic dicarboxylic acid components, polyester repeating units derived from aliphatic alcohol components and alicyclic dicarboxylic acid components, alicyclic alcohol components and aliphatic dicarboxylic acid components. Polyester repeating unit derived from, polyester repeating unit derived from alicyclic alcohol component and alicyclic dicarboxylic acid component, polyester repeating unit derived from aliphatic dicarboxylic acid component containing hydroxy group, alicyclic dicarboxylic acid containing hydroxy group And polyester repeating units derived from components.

That is, the aromatic polyester polymer is at least among a diol component including an aromatic diol, a dicarboxylic acid component including an aromatic dicarboxylic acid or an aromatic diacyl compound, or an aromatic dicarboxylic acid containing a hydroxy group, or an aromatic diacyl compound containing a hydroxy group. It can be prepared through an esterification reaction with one or more monomers.

In the esterification reaction, in addition to the above-described monomers, if necessary, aliphatic diols, diol components including alicyclic diols, aliphatic dicarboxylic acids, aliphatic diacyl compounds, alicyclic dicarboxylic acids, and dicarboxylic acid components including alicyclic diacyl compounds. , Or an aliphatic dicarboxylic acid containing a hydroxy group, an aliphatic dicarboxylic acid containing a hydroxy group, an alicyclic dicarboxylic acid containing a hydroxy group, and an alicyclic dicarboxylic acid containing a hydroxy group. You can proceed.

Specific conditions for the esterification reaction are not particularly limited, and various conventionally known synthetic methods can be applied without limitation.

The weight average molecular weight of the aromatic polyester polymer may be 10000 g/mol to 100000 g/mol. In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analysis device, a detector such as a Refractive Index Detector, and a column for analysis may be used. Conditions, solvents, and flow rates can be applied. As a specific example of the measurement conditions, using a Polymer Laboratories PLgel MIX-B 300mm length column using a Waters PL-GPC220 instrument, the evaluation temperature is 160 ℃, 1,2,4-trichlorobenzene used as a solvent The flow rate was 1 mL/min, the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL, and the value of Mw can be calculated using a calibration curve formed using a polystyrene standard. 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.

The aromatic polyester polymer may have liquid crystallinity at 100°C to 150°C. The liquid crystalline refers to a property of the aromatic polyester polymer having crystallinity in a molten state. The temperature range of 100° C. to 150° C. in which the aromatic polyester polymer can have liquid crystal properties is a temperature range in which the (co)polymer added together is calcined, and the aromatic polyester polymer is calcined together with the aromatic polyester polymer. The liquid crystal properties of the polymer may be expressed, so that the resistance of the finally produced liquid crystal alignment layer may be lowered. Accordingly, the afterimage characteristic of the liquid crystal alignment layer can be remarkably improved.

(3) liquid crystal aligning agent composition

The (co)polymer and the aromatic polyester polymer may be mixed in a weight ratio of 11:89 to 89:11, or 15:85 to 85:15, or 20:80 to 80:20. As described above, since the (co)polymer contains a certain amount of imide repeating units that have already been imidized, the anisotropy is generated by irradiating light immediately without a high-temperature heat treatment process after forming the coating film, and then heat treatment is performed to create an alignment layer. There is a feature that can be completed, and the aromatic polyester-based polymer has a feature of improving the afterimage properties.

When the (co)polymer and the aromatic polyester polymer having the above characteristics are mixed in the above weight ratio range, the aromatic polyester polymer has excellent photoreaction properties and liquid crystal orientation characteristics of the (co)polymer. Since the afterimage characteristics can be mutually complemented, a liquid crystal alignment layer having more excellent alignment properties and afterimage characteristics at the same time can be manufactured.

If the (co)polymer is added in an excessively small amount at a mixing ratio of less than 11:89 compared to the aromatic polyester polymer, the orientation is due to the lack of (co)polymer content that can induce the orientation of the aromatic polyester polymer. It can be difficult to improve enough.

In addition, the liquid crystal aligning agent composition may be dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrroli Don, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, j butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy- N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl 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 lifted. These may be used alone or may be used 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 composition is applied, the uniformity of the film thickness or surface smoothness is improved, the adhesion between the liquid crystal aligning film and the substrate is improved, or the dielectric constant or conductivity of the liquid crystal aligning film is changed. Alternatively, an additive capable of increasing the density of the liquid crystal alignment layer may be additionally included. Examples of such additives include various solvents, surfactants, silane compounds, dielectrics or crosslinkable compounds.

Ⅱ. Method for producing a liquid crystal alignment film

In addition, the present invention comprises the steps of forming a coating film by applying the liquid crystal aligning agent composition of the embodiment to a substrate (step 1); Drying the coating film (step 2); Performing alignment treatment by irradiating light or rubbing treatment on the dried coating film (step 3); And it provides a method of manufacturing a liquid crystal alignment film comprising the step (step 4) of curing the alignment-treated coating film by heat treatment.

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 the contents described above in the embodiment.

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

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

The drying step of the coating film may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, or the like, and may be performed at 50° C. to 130° C., or 50° C. to 110° C., or 60° C. to 100° C., or 70° C. to 90° C. It can be carried out at a temperature in °C.

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

In the present specification, the "coating film immediately after the drying step" refers to irradiation with light immediately after the drying step without proceeding with the step of heat treatment at a temperature equal to or higher than the drying step, and other steps other than the heat treatment may be added.

More specifically, in the case of manufacturing a liquid crystal aligning film using a liquid crystal aligning agent containing a polyamic acid or a polyamic acid ester, the step of irradiating light after essentially performing a high-temperature heat treatment for imidization of the polyamic acid is performed. However, in the case of manufacturing a liquid crystal alignment layer using the liquid crystal aligning agent composition of the above-described embodiment, the heat treatment step is not included, and the alignment layer is immediately irradiated with light to perform alignment treatment, and then heat-treat and cure the alignment-treated coating layer. Can be manufactured.

In the step of performing the alignment treatment, the light irradiation may be irradiation of polarized ultraviolet rays having a wavelength of 150 nm to 450 nm. At this time, the intensity of exposure varies depending on the type of the liquid crystal aligning polymer, and the energy is 10 mJ/cm2 to 10 J/cm2, or 30 mJ/cm2 to 2 J/cm2, or 0.5 J/cm2 to 1.5 J/cm2. The energy of can be investigated.

As the ultraviolet light, a polarizing device using a substrate coated with a dielectric anisotropic material on the surface of a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, a polarizing plate on which aluminum or metal wire is finely deposited, or quartz glass. Orientation treatment is performed by irradiating a selected polarized ultraviolet ray from among polarized ultraviolet rays by passing through or reflecting a Brewster polarizing device by reflection. At this time, the polarized ultraviolet rays 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 liquid crystal molecules is imparted to the coating film.

In addition, in the step of performing the orientation treatment, a method of using a rubbing cloth may be used for the rubbing treatment. More specifically, in the rubbing treatment, the surface of the coating film after the heat treatment step may be rubbed in one direction while rotating the rubbing roller in which the cloth of rubbing cloth is attached to the metal roller.

Step 4 is a step of curing the orientation-treated coating film by heat treatment. In this case, the heat treatment may be performed by a heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 100°C to 150°C, or 110°C to 150°C, or 120°C to 140°C.

In the step of heat-treating and curing the alignment-treated coating film, firing of the (co)polymer proceeds, and the liquid crystal properties of the aromatic polyester-based polymer are expressed together with the firing of the (co)polymer, so that the final produced liquid crystal aligning film The resistance of can be lowered. Accordingly, the afterimage characteristic of the liquid crystal alignment layer can be remarkably improved.

On the other hand, when the heat treatment temperature in the step of heat-treating and curing the alignment-treated coating film is less than 100°C or more than 150°C, the liquid crystal property of the aromatic polyester polymer is not induced, so that the afterimage of the final produced liquid crystal alignment film It is difficult to fully implement the characteristics.

Ⅲ. Liquid crystal alignment film

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

As described above, a (co)polymer including at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit; And when the liquid crystal aligning agent composition including the aromatic polyester polymer is used, a liquid crystal aligning film having improved electrical properties, such as having a high voltage preservation rate in a liquid crystal cell, can be prepared.

Although the thickness of the liquid crystal alignment layer is not largely limited, for example, it can be freely adjusted within the range of 0.01 µm to 1000 µm. When the thickness of the liquid crystal alignment layer increases or decreases by a specific value, physical properties measured in the liquid crystal alignment layer may also change by a predetermined value.

In addition, the liquid crystal alignment layer may have a Retardation value of 5 nm or more, or 8 nm or more, 5 mn to 15 nm, or 8 nm to 15 nm, or 8 nm to 11 nm, or 8.1 nm to 10.4 nm. The Retardation can be measured by irradiating polarized light with a wavelength of 550 nm to the liquid crystal alignment layer using Axomertics' AxoStep.

In general, the Retardation of a birefringent material at a predetermined wavelength λ can be defined as the product of the birefringence Δη and the layer thickness d at the wavelength. In this case, the birefringence Δη can be obtained through the following equation.

[Equation]

△η = η _e- η ₀

In the above equation, refraction in a direction having a constant speed regardless of the polarization direction of light is defined as η ₀ , and a refractive index in a direction having a different speed depending on the polarization direction is defined _{as η e.}

The liquid crystal alignment layer having a relatively high Retardation value of 5 nm or more, or 8 nm or more, 5 mn to 15 nm, or 8 nm to 15 nm, or 8 nm to 11 nm, or 8.1 nm to 10.4 nm, It seems that this is because the liquid crystal alignment film was prepared using a liquid crystal alignment composition in which a (co)polymer and an aromatic polyester polymer were mixed.

The liquid crystal alignment layer having such a high retardation value not only exhibits excellent alignment characteristics, but also can implement excellent afterimage characteristics.

IV. Liquid crystal display element

In addition, the present invention provides a liquid crystal display device including the liquid crystal alignment layer described above.

The liquid crystal alignment layer may be introduced into a liquid crystal cell by a known method, and the liquid crystal cell may likewise be introduced into a liquid crystal display device by a known method. The liquid crystal alignment layer is prepared from the liquid crystal alignment agent composition of the embodiment, and thus excellent stability can be realized along with excellent general properties. Accordingly, a liquid crystal display device capable of exhibiting high reliability is provided.

Meanwhile, the initial luminance before driving of the liquid crystal display device is 0.3 cd/cm ² or less, or 0.1 cd/cm ² to 0.3 cd/cm ² , or 0.15 cd/cm ² to 0.3 cd/cm ² , or 0.153 cd/cm ^It may be 2 to 0.268 cd/cm ^2.

The initial luminance L0 measured before driving of the liquid crystal display device is the luminance in a black state by attaching a polarizing plate to the upper and lower panels of the liquid crystal display so that they are perpendicular to each other, and attaching it on a backlight of 7,000 cd/m2.

A liquid crystal alignment cell having such a low initial luminance value before driving can implement excellent alignment characteristics.

According to the present invention, a liquid crystal aligning agent composition capable of implementing excellent liquid crystal alignment characteristics and afterimage characteristics, 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 can be provided.

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

<Synthesis Example>

Synthesis Example 1: Preparation of polyamic acid polymer P-1

Water and oxygen in the flask were removed by flowing nitrogen into a 500 ml 3-neck round flask, and (E)-4-aminophenyl 3-(4-aminophenyl)acrylate (10.639 g, 0.042 mol) was added to N-methylpyrroly. After dissolving in 205.473 g of pig (NMP), the mixture was stirred for 1 hour. The temperature of the reactor was maintained at 0 ~ 10 ℃ using ice.

Then, 9.217 g (0.047 mol) of cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (CBDA), pyridine (8.180 g, 0.103 mol) and 51.368 g of NMP were added dropwise, polymerization was performed for 24 hours, and polyamic acid. A polymer (P-1) was obtained.

The obtained polyamic acid polymer (P-1) was precipitated in a mixed solution of distilled water and methanol to obtain 25.5 g of a solid. This was diluted in a NMP:BE=8:2 solvent, and then passed through a 0.1 μm filter to obtain a polyamic acid solution from which impurities were removed.

Synthesis Example 2: Preparation of liquid crystal polymer Q-1

4,4'-biphenol (4,4'-biphenol) and diacyl chloride represented by the following formula (A) were added and mixed in the reaction vessel, and the reaction proceeds while heating, represented by the following formula (B). A liquid crystal polymer Q-1 (weight average molecular weight: 10,000 to 100,000 g/mol) having a repeating unit structure was prepared.

[Formula A]

[Formula B]

In Formulas A and B, m is an integer of 10 to 16.

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

Example 1

(1) Preparation of liquid crystal aligning agent composition

Dissolve 0.4 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 and 1.6 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol, and 5% by weight I got a solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 µm to prepare a liquid crystal aligning agent composition A-1.

(2) Preparation of liquid crystal alignment film

A substrate on which a comb-shaped IPS (in-plane switching) mode type ITO electrode pattern with a thickness of 60 nm, an electrode width of 3 μm, and an inter-electrode spacing of 6 μm is formed on a square glass substrate having a size of 2.5 cm x 2.7 cm ( The liquid crystal aligning agent composition A-1 obtained in (1) of Example 1 was applied to each of the lower plate) and the glass substrate (upper plate) without an electrode pattern using a spin coating method.

Subsequently, the substrate to which the liquid crystal aligning agent was applied was placed on a hot plate at about 80° C. and dried for 100 seconds to evaporate the solvent. In order to orientate the coating film thus obtained, ultraviolet rays of 254 nm were irradiated at an exposure amount of 1.0 J/cm 2 using an exposure machine (UIS-S2021J7-YD01, Ushio LPUV) with a linear polarizer attached to each of the upper and lower plates.

Thereafter, the alignment-treated upper/lower plates were baked (cured) in an oven at about 130° C. for 30 minutes to obtain a liquid crystal alignment film having a thickness of 0.1 μm.

(3) Preparation of liquid crystal alignment cell

Thereafter, a sealing agent impregnated with a 3 μm-sized ball spacer was applied to the edge of the upper plate excluding the liquid crystal injection hole. Then, the liquid crystal alignment films obtained in (2) of Example 1 formed on the upper and lower plates face each other and align them so that the alignment directions are parallel to each other, and then the upper and lower plates are bonded and the sealing agent is cured to prepare an empty cell. In addition, liquid crystal was injected into the empty cell to prepare an IPS mode liquid crystal cell.

Example 2

(1) Preparation of liquid crystal aligning agent composition

1.0 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 and 1.0 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 were dissolved in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol, and 5% by weight I got a solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 μm to prepare a liquid crystal aligning agent composition A-2.

(2) Preparation of a liquid crystal aligning film and a liquid crystal aligning cell

Liquid crystal in the same manner as in Example 1, except that the liquid crystal aligning agent composition A-2 obtained in Example 2 (1) was used instead of the liquid crystal aligning agent composition A-1 obtained in Example 1 (1). An alignment film and a liquid crystal alignment cell were prepared.

Example 3

(1) Preparation of liquid crystal aligning agent composition

1.6 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 and 0.4 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 were dissolved in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol, and 5% by weight I got a solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 µm to prepare a liquid crystal aligning agent composition A-3.

(2) Preparation of a liquid crystal aligning film and a liquid crystal aligning cell

Liquid crystal in the same manner as in Example 1, except that the liquid crystal aligning agent composition A-3 obtained in Example 3 (1) was used instead of the liquid crystal aligning agent composition A-1 obtained in Example 1 (1). An alignment film and a liquid crystal alignment cell were prepared.

Comparative Example 1

(1) Preparation of liquid crystal aligning agent composition

2.0 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 was dissolved in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol to obtain a 5% by weight solution. Then, the obtained solution was pressure-filtered with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 μm to prepare a liquid crystal aligning agent composition B-1.

(2) Preparation of a liquid crystal aligning film and a liquid crystal aligning cell

In the same manner as in Example 1, except that the liquid crystal aligning agent composition B-1 obtained in Comparative Example 1 (1) was used instead of the liquid crystal aligning agent composition A-1 obtained in Example 1 (1). An alignment film and a liquid crystal alignment cell were prepared.

Comparative Example 2

(1) Preparation of liquid crystal aligning agent composition

2.0 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 was dissolved in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol to obtain a 5% by weight solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 µm to prepare a liquid crystal aligning agent composition B-2.

(2) Preparation of a liquid crystal aligning film and a liquid crystal aligning cell

In the same manner as in Example 1, except that the liquid crystal aligning agent composition B-2 obtained in Comparative Example 1 (1) was used instead of the liquid crystal aligning agent composition A-1 obtained in Example 1 (1). An alignment film and a liquid crystal alignment cell were prepared.

Reference Example 1

(1) Preparation of liquid crystal aligning agent composition

Dissolve 0.2 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 and 1.8 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol, and 5% by weight I got a solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 µm to prepare a liquid crystal aligning agent C-1.

(2) Preparation of a liquid crystal aligning film and a liquid crystal aligning cell

Liquid crystal in the same manner as in Example 1, except that the liquid crystal aligning agent composition C-1 obtained in (1) of Reference Example 1 was used instead of the liquid crystal aligning agent composition A-1 obtained in (1) of Example 1. An alignment film and a liquid crystal alignment cell were prepared.

Reference Example 2

(1) Preparation of liquid crystal aligning agent composition

1.0 g of the polyamic acid polymer (P-1) obtained in Synthesis Example 1 and 1.0 g of the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 were dissolved in a mixed solvent of 30 g of NMP and 8 g of n-butoxyethanol, and 5% by weight I got a solution. Then, the obtained solution was filtered under pressure with a filter made of poly(tetrafluoreneethylene) having a pore size of 0.2 µm to prepare a liquid crystal aligning agent C-2.

(2) Preparation of liquid crystal alignment film

A substrate on which a comb-shaped IPS (in-plane switching) mode type ITO electrode pattern with a thickness of 60 nm, an electrode width of 3 μm, and an inter-electrode spacing of 6 μm is formed on a square glass substrate having a size of 2.5 cm x 2.7 cm ( The liquid crystal aligning agent composition C-2 obtained in (1) of Reference Example 2 was applied to each of the lower plate) and the glass substrate (upper plate) without an electrode pattern using a spin coating method.

Subsequently, the substrate to which the liquid crystal aligning agent was applied was placed on a hot plate at about 80° C. and dried for 100 seconds to evaporate the solvent. In order to orientate the coating film thus obtained, ultraviolet rays of 254 nm were irradiated at an exposure amount of 1.0 J/cm 2 using an exposure machine (UIS-S2021J7-YD01, Ushio LPUV) with a linear polarizer attached to each of the upper and lower plates.

Thereafter, the alignment-treated upper/lower plates were calcined (cured) in an oven at about 180° C. for 30 minutes to obtain a liquid crystal alignment film having a thickness of 0.1 μm.

(3) Preparation of liquid crystal alignment cell

Thereafter, a sealing agent impregnated with a 3 μm-sized ball spacer was applied to the edge of the upper plate excluding the liquid crystal injection hole. Then, the liquid crystal alignment films obtained in (2) of Reference Example 2 formed on the upper and lower plates face each other and align them so that the alignment directions are parallel to each other, and then the upper and lower plates are bonded and the sealing agent is cured to prepare an empty cell. In addition, liquid crystal was injected into the empty cell to prepare an IPS mode liquid crystal cell.

<Experimental Example: Measurement of physical properties of a liquid crystal aligning agent composition, a liquid crystal alignment film, and a liquid crystal aligning cell>

The physical properties of the liquid crystal aligning agent composition obtained in Examples and Comparative Examples (or Reference Examples), or the liquid crystal aligning film, and the liquid crystal aligning cells prepared using the same, were measured by the following method, and the results are shown in Table 1.

1. Evaluation of liquid crystal orientation characteristics

Polarizing plates were attached to the upper and lower plates of the liquid crystal cell prepared as described above so as to be perpendicular to each other. At this time, the polarization axis of the polarizing plate attached to the lower plate was parallel to the alignment axis of the liquid crystal cell. In addition, a liquid crystal cell with a polarizing plate was attached to a backlight having a brightness of 7,000 cd/m 2, and the luminance in a black state was measured using a luminance brightness measuring device, a PR-880 device, and liquid crystal alignment characteristics were evaluated based on the following criteria.

Good: 0.3 cd/cm ² or less

Poor: Exceeding 0.3 cd/cm ²

2. Retardation(R)

Retardation (R) of the liquid crystal alignment film obtained in the above Examples and Comparative Examples was measured. Specifically, each Retardation was measured by irradiating polarized light with a wavelength of 550 nm using AxoStep of Axomertics, and the average value of the measured values was obtained by repeating the measurement five times, and the retardation characteristics were evaluated based on the following criteria.

Good: 5nm or more

Bad: less than 5nm

Experimental Example Measurement Results of Examples and Comparative Examples division P-1: Q-1 weight ratio Orientation film firing temperature (℃) Liquid crystal orientation characteristics Retardation Example 1 20: 80 130 Good (0.239 cd/cm ² ) Good (8.1nm) Example 2 50: 50 130 Good (0.153 cd/cm ² ) Good (9.5nm) Example 3 80: 20 130 Good (0.268 cd/cm ² ) Good (10.4nm) Comparative Example 1 100: 0 130 Good (0.56 cd/cm ² ) Bad (3.7nm) Comparative Example 2 0: 100 130 Bad (not measurable) Bad (0nm) Reference Example 1 10: 90 130 Bad (0.45cd/cm ² ) Bad (4.2nm) Reference Example 2 50: 50 180 Bad (0.68cd/cm ² ) Bad (2.9nm)

As shown in Table 1, Examples 1 to using a liquid crystal aligning agent composition comprising the liquid crystal polymer (Q-1) obtained in Synthesis Example 2 together with the polyamic acid polymer (P-1) obtained in Synthesis Example 1 The liquid crystal alignment layer of 3 has a high Retardation value of 8.1 nm to 10.4 nm and can implement excellent AC afterimage characteristics, and the obtained liquid crystal alignment cell has a low initial luminance value of ^{0.153 cd/cm 2} to 0.268 cd/cm ^2. It was confirmed that it had good liquid crystal alignment characteristics.

On the other hand, the liquid crystal alignment film of Comparative Example 1 using only one polyamic acid polymer (P-1) obtained in Synthesis Example 1 and Comparative Example 2 using only one liquid crystal polymer (Q-1) obtained in Synthesis Example 2 was 0 nm. To 3.7 nm showed a lower Retardation value compared to the Example, and the liquid crystal alignment cell of Comparative Example 1 had ^{a high initial luminance value of 0.56 cd/cm 2} , so that the liquid crystal alignment property was poor, and the liquid crystal alignment cell of Comparative Example 2 was It was confirmed that the orientation itself was impossible.

In addition, as in Reference Example 1, when the polyamic acid polymer (P-1) obtained in Synthesis Example 1 is contained too little, the Retardation value of the liquid crystal alignment layer is 4.2 nm, which is lower than that of the Example, resulting in poor AC afterimage properties, The initial luminance value of the liquid crystal alignment cell obtained therefrom was 0.45 cd/cm ^{2, which} was higher than that of the example, confirming that it had poor liquid crystal alignment characteristics.

And, in the case of firing at 180° C. as in Reference Example 2, the Retardation value of the liquid crystal alignment layer was 2.9 nm, which was lower than that of the example, so that the AC afterimage property was poor, and the initial luminance value of the liquid crystal alignment cell obtained therefrom was 0.68. It was confirmed that it had a poor liquid crystal alignment characteristic as it was higher than the example in cd/cm ^2.

Claims (14)

(Co)polymer including at least one 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); And
Including an aromatic polyester-based polymer comprising a repeating unit represented by the following formula 5-1,
The aromatic polyester polymer is a liquid crystal aligning agent composition that is a liquid crystal polymer having liquid crystal properties at 100° C. to 150° C.:
[Formula 1]

[Formula 2]

[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, and the rest are hydrogen,
X ₁ to X ₃ are the same as or different from each other, and each independently a tetravalent organic group,
Y ₁ to Y ₃ are the same as or different from each other, and each independently, a divalent organic group represented by the following formula (4),
[Formula 4]

In Chemical Formula 4,
A is one of -O-, -S-, -NH-, or an alkylene group having 1 to 10 carbon atoms,
R _a and R _b are each independently hydrogen or one of an alkyl group having 1 to 10 carbon atoms,
[Chemical Formula 5-1]

In Formula 5-1,
Ar is a biphenylene group,
R ₅ is an alkylene group having 1 to 20 carbon atoms.
The method of claim 1,
The (co)polymer: the weight ratio of the aromatic polyester polymer is 11:89 to 89:11, the liquid crystal aligning agent composition.
The method of claim 1,
The weight average molecular weight of the aromatic polyester-based polymer is 10000 g / mol to 100000 g / mol, the liquid crystal aligning agent composition.
delete delete delete delete The method of claim 1,
The X ₁ to X ₃ are each independently, one of the tetravalent organic groups represented by the following formula (6), a liquid crystal aligning agent composition:
[Formula 6]

In Chemical Formula 6,
R ₆ to R ₁₁ 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 ₁₂ R ₁₃ -, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO(CH ₂ ) _t OCO-, -CONH-, selected from the group consisting of phenylene or a combination thereof Which one is
In the above, R ₁₂ and R ₁₃ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group, and t is an integer of 1 to 10.
Forming a coating film by applying the liquid crystal aligning agent composition of claim 1 to a substrate;
Drying the coating film;
Performing alignment treatment by irradiating light or rubbing the dried coating film; And
A method of manufacturing a liquid crystal alignment layer comprising the step of heat-treating and curing the alignment-treated coating layer.
The method of claim 9,
Drying the coating film proceeds to a temperature of 50 ℃ to 130 ℃, a method of manufacturing a liquid crystal alignment film.
The method of claim 9,
The step of heat-treating and curing the alignment-treated coating film is performed at a temperature of 100°C to 150°C.
A liquid crystal aligning film containing an alignment cured product of the liquid crystal aligning agent composition of claim 1.
The method of claim 12,
A liquid crystal alignment film having a Retardation value of 5 nm or more.
A liquid crystal display device comprising the liquid crystal alignment layer of claim 12.