WO2019139332A1 - Liquid crystal aligning agent composition, method for manufacturing liquid crystal aligning film using same, liquid crystal aligning film using same, and liquid crystal display device - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent composition comprising, together with a polyimide or a precursor polymer thereof, a urea-based compound containing at least two urea functional groups and having a structure in which hydroxyalkyl groups are substituted at terminal amino groups of the urea functional groups.

Description

 [Name of invention]

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

 Technical Field

Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0003580 dated January 10, 2018 and Korean Patent Application No. 10-2019-0001975 dated January 7, 2019. All content disclosed in the literature is included as part of this specification.

 The present invention relates to a liquid crystal aligning agent composition capable of realizing improved film strength at the same time as an excellent level of electrical properties applicable to a high performance liquid crystal display device, 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.

 【Technology behind the invention】

 In the liquid crystal display device, the liquid crystal aligning film is responsible for aligning the liquid crystal in a certain direction. Specifically, the liquid crystal alignment film is arranged in the arrangement of liquid crystal molecules. It acts as a dictor, allowing the liquid crystal to move in the form of an electric field (electr ic f i eld) to form the proper direction. 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.

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

 In order to solve the problem of the rubbing method, recently, an optical alignment method of inducing anisotropy (anisotropy, ani sotropy) to a polymer film by light irradiation instead of friction and arranging liquid crystals using the same has been studied.

As materials that can be used in the optical alignment method, various materials are introduced. \ ¥ 0 2019/139332 1 »（： 1 ^ 1 {2019/000278

Among them, polyimide is mainly used for good overall performance of the liquid crystal alignment layer. However, polyimide is difficult to apply directly to the manufacturing process of the solvent solubility is poorly coated in a solution state to form an alignment film.

Therefore, after coating in the form of a precursor such as polyamic acid or polyamic acid ester having excellent solubility, 200

The polyimide is formed through a heat treatment step at a temperature of from 230 X to 230 X, and light irradiation is performed thereon to perform alignment treatment.

 However, in recent years, as the required performance of the liquid crystal display device is improved and a low power display is required, the development of an alignment film that satisfies a high level of electrical properties is important for realizing high quality driving characteristics in the liquid crystal display device.

 Accordingly, there is a demand for the development of a liquid crystal alignment composition that can achieve excellent electrical characteristics that can be applied to a high performance liquid crystal display device while achieving alignment stability as a liquid crystal alignment film.

 [Content of invention]

 [Task to be solved]

 The present invention relates to a liquid crystal aligning agent composition capable of realizing improved film strength at the same time as excellent electrical properties applicable to high performance liquid crystal display devices.

 Moreover, this invention is providing the manufacturing method of the liquid crystal aligning film using the said liquid crystal aligning agent composition.

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

 [Measures of problem]

 In order to solve the above problems, in the present specification, a polymer containing a polyamic acid repeating unit; And it provides a liquid crystal alignment composition comprising a urea-based compound represented by the formula (1).

[Formula 1] 2019/139332 1 »（： 1/10 公 019/000278

In Chemical Formula 1,

 The show is a two to four functional group,

 Is an integer from 2 to 4,

At least one of ¾ and _¾ is a hydroxyalkyl group having 1 to 20 carbon atoms, and the rest is one of hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

 In the present specification, the step of applying the liquid crystal aligning agent composition to a substrate to form a coating film; Drying the coating film; Irradiating or rubbing the light on the dried coating layer to perform alignment; And it is provided a method for producing a liquid crystal alignment film comprising the step of curing the alignment-treated coating film.

 In the present specification, there is also provided a liquid crystal aligning film and a liquid crystal display device comprising the same, which are manufactured according to the method for producing a liquid crystal aligning film.

 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 will be described in detail.

I. Liquid Crystal Alignment

 According to one embodiment of the invention, a polymer comprising a polyamic acid repeat unit; And a urea-based compound represented by Formula 1 may be provided.

The present inventors, as in the liquid crystal aligning agent composition of the above embodiment, the urea-based compound added together with the polymer including the polyamic acid repeating unit includes two or more urea functional groups as shown in Formula 1, and the urea functional group ends 2019/139332 1 »（： 1 ^ 1 {2019/000278

As the amino group has a structure in which a hydroxyalkyl group is substituted, it has a high voltage retention in the liquid crystal cell in which the liquid crystal alignment film obtained from the liquid crystal aligning agent composition is installed, and has a high voltage retention rate. It was confirmed through experiments to realize the improved electrical properties such as low content and high film strength and completed the invention.

 In the case of the polyimide alignment layer, it exists in the form of a polyamic acid as a precursor on the alignment composition for synthesizing the polyimide alignment layer, and the electrical properties are weakened due to the carboxyl groups contained in the polyamic acid. In addition, in the alignment film, there was a limit that the strength of the alignment film was insufficient because there was no crosslinking between the repeating units except for the coupling between the repeating units forming the polyimide main chain.

 The present inventors apply the urea compound represented by the formula (1) as a crosslinking agent capable of forming a crosslinking structure between internal repeating units with respect to the polyamic acid corresponding to the polyimide precursor, the carboxyl group and the urea compound at the terminal of the polyamic acid Through the covalent to intermolecular bonds between the hydroxy groups of the terminal to form a cross-linked to ensure excellent mechanical strength, and confirmed the experiment through the experiment that the activity of the carboxyl groups of the polyamic acid is reduced to improve the electrical properties.

 Specifically, the carboxyl groups present in the doliamic acid have high reactivity such as hydrolysis and are likely to cause afterimage, which is not suitable for a highly reliable liquid crystal alignment film, and is a major cause of reducing electrical characteristics.

 In the liquid crystal aligning agent composition of the embodiment, as shown in Chemical Formula 1, a hydroxyalkyl group is substituted with a urea functional terminal amino group so that the hydroxyl group can be easily crosslinked with the carboxyl group in the polyamic acid. Accordingly, the cross-linked structure between the polyimide main chains is introduced into the finally synthesized liquid crystal alignment layer, thereby improving the strength of the alignment layer, and reducing the carboxyl group having high reactivity, thereby minimizing the reduction of the electrical characteristics due to the carboxyl group.

In particular, while the urea-based compound included in the liquid crystal aligning agent composition includes two or more urea functional groups as in Formula 1, two or more urea functional groups are linked through a linker group, 2019/139332 1 »（： 1 ^ 1 {2019/000278

In addition to improving the electrical properties, the elasticity and strength of the crosslinked structure increases through the linker group, thereby significantly improving the mechanical properties of the alignment layer. Hereinafter, the present invention will be described in more detail. Unless otherwise specified herein, the following terms may be defined as follows.

 In the present specification, when a part is said to "include" a certain component, it means that other components may be included other than to exclude other components unless specifically stated otherwise.

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

 In the present specification, the term "substituted" 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 Or two or more substituents may be the same as or different from each other In this specification, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl groups; Sulfonic acid groups; Sulfonamide groups; Phosphine oxide groups; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkalsulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkoxy silyl alkyl group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of 0 and heterocyclic groups including one or more of atoms, or substituted or unsubstituted with two or more substituents from the above-described substituents. For example, "a 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 一一^· ^ means a bond connected to another substituent. 2019/139332 1 »（： 1 ^ 1 {2019/000278

In the present specification, the alkyl group

The derived monovalent functional group may be linear or branched, and the carbon number of the linear alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the branched alkyl group has 3 to 20 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, !!-propyl, isopropyl, butyl, _11- butyl, isobutyl, 1 _61. Butyl, _860- butyl, methyl-butyl, ethyl-butyl, pentyl, ^ pentyl, isopentyl, neopentyl, ratchetpentyl, nuclear chamber, ₁₁ -nuclear chamber, 1-methylpentyl, 2-methylpentyl, 4-methyl 2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, II-heptyl, 1-methylnuclear, octyl, _11- octyl, 1 ₆ -octyl, 1-methylheptyl, 2-ethylnuclear, 2 -Propylpentyl, _11- nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl, 4-methylnuclear chamber, 5-methylnuclear chamber, 2,6 -Dimethylheptane-4 -one, and the like, but are not limited to these.

 In the present specification, the halo alkyl group refers to a functional group in which one or more halogen is substituted for the above-described alkyl group, and the description of the above-described alkyl group may be applied.

 In the present specification, the hydroxyalkyl group means at least one hydroxy group (-0 substituted functional group), and the description of the aforementioned alkyl group may be applied.

 In the present specification, the aryl group is a monovalent functional group derived from arene (near), and 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, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, peryleneyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the alkenyl group is derived from alkyne (1 _{½ 1½} )

The monovalent functional group may be linear or branched, and the carbon number is not particularly limited, but is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, and 3-methylone 1-. Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-l-yl) vinyl-l-yl, 2,2-bis (diphenyl-l-yl) vinyl-l-yl, stilbenyl group, styrenyl group, and the like.

In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n_propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n_ pentyloxy, neopentyloxy, isopentyl Oxy, n-nuxyloxy, 3, 3-dimethylbutyloxy, 2-ethylbutyloxy, _n- octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p_methylbenzyloxy, and the like, but are not limited thereto. It doesn't work.

 In the present specification, the halo alkoxy group means a functional group in which at least one halogen is substituted for the alkoxy group described above, and the description of the alkoxy group described above may be applied.

 In the present specification, the alkylten group is derived from alkane (amane)

As the divalent functional groups, the description of the aforementioned alkyl groups can be applied except that they are divalent functional groups. For example, it may be a methyl or group, ethylene group, propylten group, isobutylten group, sec-butylten group, tert-butylene group, pentylene group, nuclear silane group or the like as a straight chain or branched.

 In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aforementioned aryl group may be applied except that these are divalent functional groups. For example, it may be a phenylene group, a biphenyltene group, a terphenyltene group, and the like.

 In the present specification, the alkylenebisarylene group is a divalent functional group in which two arylten groups are bonded to the end of the alkylene group, and the description of the alkylene group and the arylene group described above may be applied. For example, a methylene bisphenylene group can be mentioned.

In the present specification, a multivalent organic group is a residue in a form in which a plurality of hydrogen atoms bonded to an arbitrary compound are removed, and examples thereof include a divalent organic group, a trivalent organic group, and a tetravalent organic group. . In one example, the tetravalent organic group derived from cyclobutane is any bond to cyclobutane. 2019/139332 1 »（： 1 ^ 1 {2019/000278

Represents a moiety in the form of four hydrogen atoms removed.

 In the present specification, a direct bond or a single bond means that no atom or atom group exists at a corresponding position, and thus, is connected by a bond line. Specifically, it means a case where no separate atom exists in the moiety represented by, in the formula.

(1) a polymer

 The polymer may comprise a polyamic acid repeat unit. In addition, if necessary, the polymer may further include one or more repeating units selected from the group consisting of polyamic acid ester repeating units and polyimide repeating units.

 That is, the polymer is a homopolymer containing only a polyamic acid repeating unit, or a polyamic acid repeating unit as necessary, and if necessary, one polyamic acid ester repeating unit, one polyimide repeating unit, or two of them. The repeating units of the phases may include mixed copolymers.

 The polyamic acid repeating unit, polyamic acid ester repeating unit, or polyimide repeating unit may form a main chain of the polymer.

 Specifically, the polyamic acid repeating unit may include a repeating unit represented by Formula 3 below.

 [Formula 3]

In Chemical Formula 3, ¾ may be a tetravalent organic group. The ¾ may be a functional group derived from a polyamic acid, a tetracarboxylic acid anhydride compound used in synthesis. The silver may be a functional group derived from a diamine compound used in polyamic acid synthesis.

In addition, the polyamic acid ester repeating unit is represented by the following formula (4) 2019/139332 1 »（： 1 ^ 1 {2019/000278

It may include a repeating unit, the polyimide repeating unit may include a repeating unit represented by the following formula (5).

 [Formula 4]

In Chemical Formulas 4 to 5, ¾ to ¾ may be a tetravalent organic group. The ₂ to ¾ may be a functional group derived from a polyamic acid ester, or a tetracarboxylic acid anhydride compound used in the synthesis of polyimide. The ¾ to 九 may be a functional group derived from a polyamic acid ester, or a diamine compound used in polyimide synthesis.

 More specifically, in Chemical Formulas 3 to 5, the to ¾ are the same or different from each other, each independently may be one of a tetravalent organic group represented by the following formula (10).

[Formula 10]

\ 0 2019/139332 1 »（： 1/10 公 019/000278

In the above, R _l5 and R _! e is independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group, and is an integer of 1 to 10.

 More preferably, Xi to ¾ are each independently an organic group of formula 10-1 derived from pyromellitic acid anhydride (pyromel 1 i t i c di anhydride, PMDA); ， 4,4 '_biphenyltetracarboxylic acid dianhydride (3,3', 4,4'-

An organic group of formula 10-2 derived from Bi phenyl Tetracarboxyl i c Acid Di anhydride (BPDA); An organic group represented by the following Chemical Formula 10-3 derived from 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (1,2,4,5-Cyclohexanetetracarboxyl i c Di anhydride, HPMDA); Or 1,3-dimethyl-cyclobutane_5 1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA), an organic group of formula 10'4; An organic group of the formula (10-5) derived from cyclobutane-1, 1,2,3,4-tetracarboxylic dianhydride; Or an organic group represented by the following Chemical Formula 10-6 derived from tetrahydro- [3,3'_bifuran] _2,2 ', 5,5'_tetraone.

0 [Formula 10-1]

2019/139332 1 »（： 1 ^ 1 {2019/000278

[Formula 10-2]

 In Chemical Formulas 3 to 5, to may be the same as or different from each other, and may each independently be a divalent organic group represented by Formula 6 below.

[Formula 6]

 In Formula 6, at least one of ¾ to ¾ is nitrogen, the remainder is carbon, I) is 4®'- or -0-, and the parent 'is hydrogen or an alkyl group having 1 to 6 carbon atoms.

On the other hand, in the organic group represented by the formula (6), at least one of ¾ to 0 ₄ is nitrogen, the rest is carbon, ¾ to ₈ is carbon, I)- 2019/139332 1 »（： 1 ^ 1 {2019/000278

Can be '-'. More preferably, in Chemical Formula 6, ¾ to ¾ of ¾ is nitrogen, and the remainder is carbon, and from 0 ₅ to

Carbon and I) is -1'_.

[Formula 7]

 More specifically, Chemical Formula 7 satisfying the above may include functional groups represented by the following Chemical Formulas 7-1 to 7-3.

 [Formula 7-1]

In addition, in the organic group represented by Formula 6, ¾ to

At least one is nitrogen, the remainder is carbon, at least one of ¾ to 0 ₈ is nitrogen, the remainder is carbon, and

May be- More preferably, in formula 6, ¾ to about 0 ₄₄ The nitrogen of the remainder carbon atoms, and from 0 ₅ to ¾ John ₅ The nitrogen in, and the others are carbon, is - · - in to the general formula (8) Can be lifted.

[Formula 則 2019/139332 1 »（： 1 ^ 1 {2019/000278

 More specifically, Chemical Formula 8 satisfying the above may include functional groups represented by the following Chemical Formulas 8-1 to 8-2.

 [Formula 8-1]

Meanwhile, in the organic group represented by Chemical Formula 6, at least one of ¾ to 0 ₄ is nitrogen, the remainder is carbon, 0 ₅ to ¾ is carbon, and I) may be -0-. More preferably, in Chemical Formula 6, ¾ of ¾ to ¾ is nitrogen, the remainder is carbon, ¾ to ¾ is carbon, and I) is -0-.

[Formula 9]

 More specifically, Chemical Formula 9 satisfying the above may include functional groups represented by the following Chemical Formulas 9-1 to 9-3.

[Formula 9-1]

[Formula 9-2] \ ¥ 0 2019/139332 1 »（： 1/10 公 019/000278

 That is, the divalent organic group represented by Formula 6 may include a divalent organic group represented by Formula 7, a divalent organic group represented by Formula 8, and a divalent organic group represented by Formula 9, As the functional group represented by Chemical Formula 6 is included, the liquid crystal display device to which the polymer for liquid crystal aligning agent of the embodiment is applied may implement high voltage retention and liquid crystal alignment.

 In addition, in Formula 4, at least one of ¾ and ¾ is 1 to

10 alkyl, the remainder may be hydrogen.

 More specifically, the polyamic acid repeating unit represented by Chemical Formula 3 may include a combination of tetracarboxylic dianhydride and diamine. The combination of the tetracarboxylic dianhydride and the diamine corresponds to the reaction product of the tetracarboxylic dianhydride and the diamine, wherein in Formula 3, XI is a polyamic acid, a functional group derived from a tetracarboxylic acid anhydride compound used in the synthesis The kappa may be a functional group derived from a diamine compound used in polyamic acid synthesis.

 That is, the tetracarboxylic dianhydride may be represented by the following Chemical Formula 3-1, and the content of ¾ in the following Chemical Formula 3-1 may include the details described above in Chemical Formula 3.

[Formula 3-1] 2019/139332 1 »（： 1 ^ 1 {2019/000278

 In addition, the sangadiamine may be represented by the following formula 3-2, the content of ¾ to ¾, I) in the following formula 3-2 may include the details described above in the formula (6).

 [Formula 3-2]

 On the other hand, the polymer may further include a repeating unit represented by the following formula (11) or formula (12). That is, the polymer may include one type of repeating unit represented by Formula 11, or one type of repeating unit represented by Formula 12, or both the repeating unit represented by Formula 11 and the repeating unit represented by Formula 12. have.

 [Formula 11]

[Formula 12] 2019/139332 1 »（： 1 ^ 1 {2019/000278

In Formula 11 or Formula 12, X ″ is X _I of Formula 3, “is of Formula 3, and 1 / is derived from a hydroxyalkyl group having 1 to 20 carbon atoms of at least one of Formula 1 and ¾. Alkylten groups, or alkylene groups derived from hydroxyalkyl groups having 1 to 20 carbon atoms of at least one of ¾ and ¾ of formula (2), or from hydroxyalkyl groups having 1 to 20 carbon atoms of at least one of ¾ and ¾ of formula (2) The alkylene group is derived from Formula 11 or Formula 12, wherein the polyamic acid repeating unit represented by Formula 3 is a urea compound represented by Formula 1;

₁₀ As a repeating unit having a crosslinked structure, excellent mechanical strength can be realized as a crosslinked structure is introduced between the polymer for a liquid crystal aligning agent and the final main chain of the liquid crystal alignment layer through the repeating unit represented by Formula 11 or Formula 12.

More specifically, the repeating unit of Formula 11 or Formula 12 may be formed while the carboxyl group of the polyamic acid repeating unit represented by Formula ₁₅ is reacting with the terminal hydroxyl group of the urea compound represented by Formula 1.

The repeating unit represented by Formula 11 or Formula 12 may be crosslinked through a central polyvalent functional group represented by Formula 13 below. That is

 It can be coupled to the center of the multifunctional group displayed.

[Formula 13] 2019/139332 1 »（： 1/10 公 019/000278

 Show "In Formula 13" is of the formula (1) or formula (2), and: is an integer of 2 to 4.

 Repetition unit represented by the formula (11) or formula (12), the cross-linking through the central polyvalent functional group represented by the formula (13), repeating represented by the formula (11) or formula (12) at the end of the central polyvalent functional group represented by the formula (13) By unit bonding, it means that the repeating unit represented by the formula (11) or (12) is bonded through the central polyvalent functional group represented by the formula (13).

 More specifically, for example, two repeating units of Formula 11 may be bonded to the central polyvalent functional group of Formula 13 to form a crosslinked compound represented by the following Formula 14.

[Formula 14]

2019/139332 1 »（： 1 ^ 1 {2019/000278

As shown in Chemical Formula 14, crosslinking through a crosslinking functional group may be formed instead of direct linkage between repeating units forming the main chain of the polyamic acid.

 [Formula 14] is one of hydrogen, a hydroxyalkyl group of 1 to 20 carbon atoms, an alkyl group of 1 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms. In the formula (14), when “” is a hydroxyalkyl group having 1 to 20 carbon atoms, the remaining hydroxy group may be crosslinked with another polyamic acid repeating unit.

In addition, in Formula 14, X ″ is X of Formula 3, V ″ is of Formula 3, and “ne” is at least one carbon number of Formula 1 and ¾ 2019/139332 1 »（： 1 ^ 1 {2019/000278

An alkyltene group derived from a hydroxyalkyl group of 1 to 20, or at least one carbon atom of ¾ and ¾ of formula 2, or an alkylene group derived from a hydroxyalkyl group of 1 to 20, or at least one carbon number of ¾ and ¾ of formula 2 It is an alkylene group derived from the hydroxyalkyl group of 1-20, and 'is of the said Formula (1) or (2).

(2) urea compounds

 The liquid crystal aligning agent composition of the embodiment may include a urea-based compound in addition to the polymer described above, and the urea-based compound may have a specific chemical structure represented by Chemical Formula 1. The physical / chemical properties of the urea-based compound appear to be due to the specific structure of Chemical Formula 1 described above.

 Specifically, in the case of the structure containing two or more urea functional groups, such as the formula (1), wherein at least one hydroxyalkyl group is substituted in the urea functional terminal amino group, the hydroxy group present at the terminal is polymerized in the liquid crystal aligning agent composition It is easy to form covalent to intermolecular bonds with the carboxyl group at the end of the polyamic acid contained therein.

 Through this, it is possible to realize high reliability and improved electrical properties by lowering the reactivity such as hydrolysis by carboxyl groups present in the polyamic acid in the polymer, and the urea-based compound performs the crosslinking role between the main chains in the polymer and is most polymerized alignment film. The film strength can be improved through the formation of a crosslinked body.

 The urea-based compound may be used as a urea-based crosslinking agent, and the urea-based compound may include a urea compound itself or a derivative compound thereof as a compound containing a urea functional group.

Specifically _{, in} Chemical Formula 1 _, yaw is a divalent to tetravalent functional group, _II is

It can be an integer from 2 to 4. The / I is a functional group located in the center of the urea-based compound, and the terminal functional groups included in the show may bind as many as II functional groups represented by the curly brackets' ′ □ ″ in the general formula (1).

That is, in Formula 1, when II is 2, urine is a divalent functional group. Also, II 2019/139332 1 »（： 1/10 公 019/000278

If 3, urine is a trivalent functional group. Also, if II is 4, the show is a tetravalent functional group. Preferably, in Chemical Formula 1, II is 2, and may be any one of an arylten group having 6 to 30 carbon atoms, an alkylten group having 1 to 20 carbon atoms, or an alkylenebisarylene group having 7 to 40 carbon atoms.

 In addition, in Chemical Formula 1, at least one of ¾ and ¾ is 1 to

It may be a hydroxyalkyl group of 20, the remainder may be one of hydrogen, an alkyl group having 1 to 2 carbon atoms, or an aryl group having 6 to 20 carbon atoms. That is, in Chemical Formula 1, ¾ may be a hydroxyalkyl group having 1 to 2 carbon atoms, ¾ may be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In addition, in Chemical Formula 1, both ¾ and ¾ may be hydroxyalkyl groups having 1 to 20 carbon atoms.

Preferably _, the urea compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 2.

 [Formula 2]

In Formula 2, yo 'is one of an arylene group having 6 to 30 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylenebisarylene group having 7 to 4 carbon atoms, at least one of ¾ and ¾ is 1 to 20 is a hydroxyalkyl group, the remainder is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

At least one is a hydroxyalkyl group having 1 to 2 carbon atoms, and the other is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

That is, in Chemical Formula 2, ¾ may be a hydroxyalkyl group having 1 to 20 carbon atoms, ¾ hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In addition, in Chemical Formula 2, both ¾ and ¾ may be hydroxyalkyl groups having 1 to 20 carbon atoms. 2019/139332 1 »（： 1 ^ 1 {2019/000278

In addition, in Chemical Formula 2, ¾ may be a hydroxyalkyl group having 1 to 20 carbon atoms, ¾ may be one of hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In addition, in Chemical Formula 2, both ¾ and ¾ may be hydroxyalkyl groups having 1 to 20 carbon atoms.

 More specifically, in Chemical Formula 2, the arylten group having 6 to 30 carbon atoms may be an arylene group having 6 to 10 carbon atoms, specifically, a phenylene group. In addition, in Formula 2, the alkylene group having 1 to 20 carbon atoms may be an alkylene group having 1 to 10 carbon atoms, specifically, a nuclear silane group having 6 carbon atoms. In addition, in the show 'in Formula 2, the alkylenebisarylene group having 7 to 40 carbon atoms may be an alkylenebisarylten group having 7 to 20 carbon atoms, specifically, a methylenebisphenyl group.

 Specific examples of the urea-based compound represented by Chemical Formula 2 may include a compound represented by Chemical Formula 2-1, a compound represented by Chemical Formula 2-2, a compound represented by Chemical Formula 2-3, and Chemical Formula 2-4. 1 type of compounds chosen from the group which consists of a compound represented, the compound represented by following formula (2-5), and the compound represented by following formula (2-6) can be mentioned.

 [Formula 2-1]

[Formula 2-3] 2019/139332 1 »（： 1/10 公 019/000278

The urea compound represented by Chemical Formula 1 may be contained in an amount of 0.1 wt% to 20 wt%, or 1 wt% to 5 wt% based on the total weight of the liquid crystal aligning agent composition. When the content of the urea-based compound is excessively large, as the degree of crosslinking of the polymer for the liquid crystal aligning agent is excessively increased, the flexibility of the polymer may decrease, and the coating on the substrate may be caused by an increase in the viscosity of the composition or a gelation reaction in the composition. Sex can be reduced.

On the other hand, if the content of the urea-based compound is too small, it may be difficult to sufficiently implement the electrical characteristics improvement effect of the addition of the urea-based compound in the liquid crystal alignment composition. 2019/139332 1 »（： 1 ^ 1 {2019/000278

11. Manufacturing method of liquid crystal aligning film

 In addition, the present invention comprises the steps of applying a liquid crystal aligning agent composition of the embodiment to a substrate to form a coating film (step 1); Drying the coating film (step 2); irradiating or rubbing the light on the dried coating film (step 3); and curing and curing the alignment-coated film by heat treatment (step 4). To provide a method for producing a liquid crystal alignment film.

 Step 1 is a step of coating the liquid crystal aligning agent composition described above on a substrate to form a coating film. The content of the liquid crystal aligning agent composition includes all of the above contents in the embodiment.

 The method of applying the liquid crystal alignment composition to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, ink jet, and the like may be used.

The liquid crystal aligning agent composition may be dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include -dimethylformamide, -dimethylacetamide, methyl-2-pyrrolidone, methylcaprolactam, 2-pyrrolidone, ethylpyrrolidone, vinylpyrrolidone, dimethyl sulfoxide, tetra Methylurea, pyridine, dimethylsulfone, nuxamethylsulfoxide, V-butyrolactone, 3-methoxy- -dimethylpropanamide, 3-ethoxy- 1 dimethylpropanamide, 3-butoxy-dimethylpropanamide, 1,3-Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, cyclonuxanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydro Roxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether ace Site, there may be mentioned ethylene glycol monomethyl 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. They can be used alone or in combination. 2019/139332 1 »（： 1 ^ 1 {2019/000278

In addition, the liquid crystal aligning agent composition may further include other components in addition to the organic solvent. As a non-limiting example, when the liquid crystal aligning agent composition is applied, 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 capable of increasing the compactness of the liquid crystal alignment layer. Such additives may be exemplified by various solvents, surfactants, silane-based compounds, dielectric 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 composition to a board | substrate.

The drying step of the coating film is hot plate, hot air circulation furnace, infrared furnace, etc.

 Step 3 is a step of orientation treatment by irradiating light or rubbing the dried coating film.

The light irradiation in the alignment process may be to irradiate polarized ultraviolet rays of 150 11111 to 450 L wavelength. At this time, the intensity of exposure depends on the type of liquid crystal aligning jeyong polymer, one can examine the 10/10 to its / ™ of energy, preferably from 30 _1/11 to 2, "its energy.

 As the ultraviolet rays, a polarizer 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 fine aluminum or metal wires are deposited, or quartz glass The polarizing ultraviolet rays selected from the polarized ultraviolet rays are irradiated by passing through or reflecting the Brewster polarizer by reflection or the like to perform alignment treatment. 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 is performed after the heat treatment step while rotating the rubbing roller with the cloth of rubbing cloth on the metal roller 2019/139332 1 »（： 1 ^ 1 {2019/000278

The surface of the coating film can be rubbed in one direction.

Step 4 is a step of curing the alignment-treated coating film by heat treatment. At this time, the heat treatment may be carried out by heating means such as a hot plate, hot air circulation furnace, infrared furnace, etc., 180 X: to 300 ° (), or 200

At temperatures up to 300 V. m. Liquid crystal alignment film

 Moreover, this invention provides the liquid crystal aligning film manufactured according to the manufacturing method of the liquid crystal aligning film mentioned above. Specifically, the liquid crystal alignment layer may include an alignment cured product of the liquid crystal alignment agent composition of the embodiment. The alignment cured product means a material obtained through an alignment process and a curing process of the liquid crystal aligning agent composition of the embodiment.

As described above, polymers including polyamic acid repeat units; And using a liquid crystal aligning agent composition comprising a urea compound represented by the formula (1), having a high voltage retention in the liquid crystal cell,

It is possible to produce a liquid crystal aligning film having improved electrical properties such as a low speed and a low content of IX: remaining in the alignment film.

 Although the thickness of the liquid crystal aligning film is not particularly limited, for example, it can be freely adjusted within the range of 0.01! M to 1000 ^. When the thickness of the liquid crystal alignment layer increases or decreases by a specific value, the physical property measured in the liquid crystal alignment layer may also change by a certain value.

IV. Liquid crystal display

 Moreover, this invention provides the liquid crystal display element containing the liquid crystal aligning film mentioned above.

The liquid crystal alignment film 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 element by a known method. The liquid crystal alignment layer may be prepared from the liquid crystal alignment agent composition of the embodiment to implement excellent stability with excellent overall physical properties. Accordingly, it is possible to provide a liquid crystal display device capable of exhibiting high reliability. 2019/139332 1 »（： 1 ^ 1 {2019/000278

【Effects of the Invention】

 According to the present invention, there is provided a liquid crystal aligning agent composition capable of realizing improved film strength at the same time as excellent electrical properties applicable to a high performance liquid crystal display device, 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

 [Specific contents for carrying 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 to the following examples.

<Production Example: Production of Diamine>

Preparation Example 1

2-chloro-5-nitropyridine (2- 此 101 0-5_ to! "Compound 1) for 18.3 (1001 ^ 1101), paraphenylene of 12.5 sugars (98.6_01)

Compound 2) was dissolved in 20 dimethylsulfoxides (1 ₁₁₁₆₁ : 1 ₁₇ 1 _{311 0} (1 ₆ , 완전히), then triethylamine for 23.4 (200 _{111] 110} 1)! · 61 ± 71311 ^ 116, table show ) Was added and stirred at room temperature for 12 hours. Upon completion of the reaction, the reaction was placed in a vessel containing 50 water and stirred for 1 hour. The solid obtained by filtration was washed with 200 cc of water and 200 ethanol to give 16 ^ 61. 3 3 ₀ 1) was synthesized. (Yield: 60%)

The compound 3 of ethyl acetate and比display 1® "1:. 200 ₁₁₁ was dissolved in a mixed solution of 1 to 1, the input of the 0.8 ₈ air palladium / carbon (which was stirred for 12 hours in a hydrogen environment after the end of the reaction The filtrate filtered on the celite pad was concentrated to prepare diamine (Compound 4) of Preparation Example 1 of 11-saccharide. (Yield: 89%)

4-nitrophenol of the nitropyridine (2-此-5- 1 _{010 1 1 time!)} _ _71, compound 5), (98.6_ ₀ 1) per 12.5 - chloro - - 5 17.1 _§ 2 of ₍₀ 100_ 1) (4- 1: ₁ , ₀₁ ) 1 ₁₆₁₁₀ 1, compound 6) was used as the dimethyl sulfoxide (1) ^ _61; 1 ₁ 1 ₃₁₁ 1 ^ (1, _6, and then completely dissolved in ⑴, _§ 27.2 (200 _1, when () 1) of potassium carbonate and 0切: ₀₃₎ was added at room temperature

Stir for 16 hours. Upon completion of the reaction, the reaction was placed in a vessel containing 500 ₁ water and stirred for 1 hour. The solid obtained by filtration was washed with 200 kPa of water and 200 kPa of ethanol to synthesize Compound 7 for 16 (61.3_ ₀ 1). (Yield: 57%)

The compound 7 was dissolved in a 200 mL solution of 1: 1 mixed ethyl acetate, seedlings and THF, and 0.8 g of palladium (Pd) / carbon (C) was added thereto, followed by stirring for 12 hours in a hydrogen environment. After completion of the reaction, the filtrate was filtered and concentrated on a celite pad to prepare diamine (Compound 8) of Preparation Example 2 of llg. (Yield: 89%) Preparation Example 3

15.¾ (95_ ₀ 1) 2-chloro-4-nitropyridine (2- （± 1 ₀₁₀ _4- ₁ 1: ₁ ( ₇₁ 1 _16, compound 9), 5-nitro of (99_ ₀ 1) per 13.8 Pyridine-2-amine (5- 1: ₁ ) _{1 ·} -2- 犯, compound 10) dissolved in 20 dimethylformamide (1 ₁₁₁₆₁ : 1 ₁₇ 1 £ _0011311 ^ (1 _6, 0)) _{Triethylamine} for 23.4 (200 _1111110 1)

1 seed show) was added and stirred for 16 hours at 90 I. When the reaction is over, the reactant Into a vessel containing 500 _[此 of water and stirred for 1 hour. The solid obtained by filtration was washed with 200 _kV ultrapure water to synthesize 15 _{§ (42.5-01)} . (Yield 45%)

The above compound 11 in tetrahydrofuran作抑) In a was dissolved in 200 ₁ 0.8 ₈ palladium / carbon (0 and stirred for 12 hours under hydrogen environment. After the reaction was concentrated to a filtrate filtered through a celite Pat 9.0 The diamine (Compound 12) of Preparation Example 3 of _§ was prepared (yield: 60%).

<Example: Preparation of liquid crystal aligning composition and liquid crystal aligning film>

 As shown in Table 1, after dissolving 14.637 g (0.073ramol) of diamine of Preparation Example 1 in NMP 225.213 sugar, 3,3, ， 4,4′-Biphenyl tetracarboxylic acid di anhydride 20.Og (0.068 mmol ) Was stirred at 25 ° C. for 16 hours to synthesize a polyamic acid polymer. Thereafter, l, l '-(4,4'-methylenebi s (4, l-phenylene)) bi s (3,3-bi s (2-hydroxyethyl) urea) represented by the following Chemical Formula a [MDI-U 3 wt% of the total composition was added and stirred for 20 hours to prepare a liquid crystal aligning agent composition.

 [Formula a]

 (2) Preparation of Liquid Crystal Alignment Film

The liquid crystal aligning agent composition obtained in Example 1 (1) was spin coated on a rectangular glass substrate having a thickness of 60 ■, an area of 1 L x 1 L and a pattern of 2.5 011 X 2.7 L. Applied. Then liquid crystal 2019/139332 1 »（： 1 ^ 1 {2019/000278

The substrate to which the alignment agent composition was applied was placed on an 80 hot plate and dried for 2 minutes. Subsequently, an ultraviolet ray of 2541 ^ 1 was irradiated with an exposure dose of 0.25 "by using a linear polarizer-attached exposure device, followed by alignment treatment, and then baked (cured) for 15 minutes in an oven at 230 ° (:) to produce a liquid crystal alignment film having a thickness of 0.1 _/ pe. Implementation ^ 12

As shown in Table 1, 1, 1b represented by the formula ( ₃ )

Instead, 1, G- (hexane-l, 6-diyl) bis (3,3-bis (2- 1 _¾ year _{1 '} ¥ _{61 7} 1) represented by the following Chemical Formula 1 ₃ [¾ ₈ 1) 1-1 [] A liquid crystal aligning agent composition and a liquid crystal aligning film were prepared in the same manner as in Example 1, except that was added.

 [Chemical formula cost]

Example 3

As shown in Table 1, 1,1 '-represented by the formula ( ₃ )

(4,4 ''-11161; 11 1 18 (4, 1-1) 1161171

Instead of adding 1, l '-(l, 4-phenylene) bis (3,3-bis (2-hydroxyethyl) ^ ₆₃₎ [1¾ ₆ 1) 1-11] In the same manner as in Example 1, a liquid crystal aligning agent composition and a liquid crystal aligning film were prepared.

[Formula ₍ ：)] \ ¥ 0 2019/139332! »（T1710 公 019/000278

Examples 4-6

 As shown in Table 2, in the same manner as in Examples 1 to 3, except that 14.708 g (0.073_ol) of diamine of Preparation Example 2 was added instead of 14.637 g (0.073 mmol) of Diamine of Preparation Example 1. The liquid crystal aligning agent composition and the liquid crystal aligning film were produced. Implementation ^ 17

 As shown in Table 3, the diamine prepared in Preparation Example 3

1.408 g (7_ol) was completely dissolved in 15.37 sugar of anhydrous N-methylpyrrolidone (NMP). And cyclobutane_ under ice bath.

1.304 g (6.65 mmol) of 1,2,3,4-tetracarboxylic dianhydride (Cyc 1 obut ane-1, 2,3,4-t et r acarboxy 1 ic di anhydride, CBDA) are added to the solution The mixture was stirred at room temperature for 16 hours to synthesize a polyamic acid polymer.

 Thereafter, as in Example 1, 1,1 '-(4,4'_me t hy 1 eneb is (4, 1-pheny 1 ene)) represented by the formula a, bi s (3,3-bi s (2-hydroxyoxyt hy 1) urea) [MDI-U] 3 wt% of the total composition was added and stirred for 20 hours to prepare a liquid crystal aligning agent composition.

 In addition, a liquid crystal aligning film was produced in the same manner as in Example 1. Implementation ^] 8

 As shown in Table 3, 1, 1 '_ represented by the formula a

(4,4 '-me t hy 1 eneb is (4, 1-pheny 1 ene)) bi s (3,3_bi s (2-hydr oxyethy 1) urea) 2019/139332 1 ^» （： 1 ^ 1 {2019/000278

1, 1 '-(1½ 3116-1,6- (1 1) 3 (3,3- 3 (2-

In the same manner, a liquid crystal alignment composition and a liquid crystal alignment film were prepared. Implementation ^ 19

 As shown in Table 3 below, 1,1'- represented by Chemical Formula 3

(4,4 '-[1; 1 year 13 (4, 1-1)] 1611 1 «)) 5 £ (3, 3 children 1 (2¾ 3 0 61; 11 1) Gank) instead of the above formula ₍ Same as Example 7, except that 1, l '-(l, 4-phenylene) bis (3,3-bis (2-hydroxyethyl) urea) [1¾61) 1-11] The liquid crystal aligning agent composition and the liquid crystal aligning film were manufactured by the method. Example 10

 As shown in Table 1, 1, 1'_ represented by the formula &

Example 11

As shown in Table 1, 1,1'_ (4,4'-1116 '11 1 13 (4, 1-1) 11611716116)) 1) (3,3- 3 (2) represented by Chemical Formula ₃ -] ¾ ^ 0 61: 11 1) a) 1,1 '-(1 _{16 3116-1} , 6- ₍ 1 1) 1 ₃ : 1 _{3 (} 3- (2- _nesan0761) 1 ₁₇ 1) A liquid crystal aligning composition and a liquid crystal aligning film were produced in the same manner as in Example 1 except that bar ₆₈₎ was added.

[Formula 2019/139332 1 »（： 1/10 公 019/000278

 Example 12

 As shown in Table 1, 1,1 '-represented by the formula (3)

_{(4,4 '16 1 ¥ 6 3} (4, 16 1 6)) 5 (3,3- 3 (2-11 (0761; 1171) 11 3) to replace one of the formula 11, 1' Liquid crystal aligning composition in the same manner as in Example 1, except that-(116X3116-1, 6- (1 1) 1 3 (3- (2-urinane "0761; 1171) 106k) was added; and A liquid crystal aligning film was produced.

<Comparative Example: Production of Liquid Crystal Alignment Composition and Liquid Crystal Alignment Film>

 Comparison ^ 11

 As shown in Table 1, 1,1 '-represented by the formula (3)

（4,4'-Mi 6 1 6 3 （4, 1- 6 16）） Except 3 (3,3- 3 (2-Nesan 1 «761; 1¾1) bar 6) not added Prepared a liquid crystal aligning composition and a liquid crystal aligning film in the same manner as in Example 1. Comparison ^ 12

As shown in Table 1 below, 1,1'_ (4,4'-mi 6 1 ¥ (4, 1-6 ^ 16 6)) 3 (3,3- 3 (2) represented by Chemical Formula 3 -N 7 0 61:11> ， 1） 1 63) Instead of 1,1 '-(1,4-1) 11611716] 16 represented by the following formula (1) 1 3 (3- (3- (1; 1) A liquid crystal aligning composition and a liquid crystal aligning film were prepared in the same manner as in Example 1, except that 1 ± 07 ^ 1) 1) 1 (71) 1063) were used. 2019/139332 1 »(： 1 ^ 1 {2019/000278

[Formula 1]

Comparative Example 3

As shown in Table 1, 1, 1'_ represented by the formula &

Instead of using the liquid crystal aligning agent composition in the same manner as in Example 1 except for using 1, 1, 3,3-1 to _{3 (} 1 ₁ 1 ₁ «> 0 _{1161;] 17} 1 represented by the following Chemical Formula _: A liquid crystal aligning film was produced.

 Formula

Comparative Example 4

As shown in Table 2, 1,1'_ (1 (4, 1-1 1-6) in 4,4'16) represented by Chemical Formula ₃ , 3 (3,3- 3 (2-117 (11) A liquid crystal aligning composition and a liquid crystal aligning film were prepared in the same manner as in Example 4 except that («761; 1¾1) bark) was not added.

As shown in Table 2 below, 1,1'- represented by Chemical Formula ₃

1, 1 '-(1,4_ ₁₃ 1 ₁₆₁₁₇ 1 ₆₁₁₆₎ 1 _{3 (} 3- (3-

A liquid crystal aligning composition and a liquid crystal aligning film were prepared in the same manner as in Example 4 except for the use. 2019/139332 1 »（： 1 ^ 1 {2019/000278

Comparison ^ 16

As shown in Table 2, 1, 1'_ represented by the formula ( ₃ )

(4,4'16 16 3 (4, 1-66)) 3 (3, 3 - (2-Seine 0 61; 1171 ⑴) instead of 1, 1, 3, 3 of the formula _6. O ₈ A liquid crystal aligning agent composition and a liquid crystal aligning film were prepared in the same manner as in Example 4 except that 1 ₃ ( _1¾ line _{1 ′ 0} X ^ ₆₁ : 1 ₁₇ 1 size was used. Comparative Example 7

As shown in Table 3, 1,1'- (4,4'16 ^ 1-6 6 (4, 1-6 166)) 3 (3,3- 3 (2 [«represented by Formula ₃ ) 61;] ¾, 1) 11 8) A liquid crystal aligning composition and a liquid crystal aligning film were prepared in the same manner as in Example 7 except that no addition was made. Compare F 18

As shown in Table 3 below, 1,1'_ represented by Chemical Formula ₃

(4,4'-near) 1 1 15 （4,1-61171 root）） 3 （3,3-13 （2_1 ^ 0 6] 1 1） Instead of an equivalent chemical formula (1,1 'represented by 1) - a (1,4_ ₁₎ 1 ₁₆₁₁ 1 _{6116) 13} (3- (3- (1 1 Ke greater) and a liquid crystal aligning agent composition and a liquid crystal alignment film in the same manner as example 7 except for using to prepare . Comparative Example 9

As shown in Table 3, 1,1 '_ represented by the formula (3)

Instead of using the liquid crystal aligning agent composition and the liquid crystal in the same manner as in Example 7, except that 1,1,3,3A61 3 30¾ line 1 ^' («,] 171) 10 ^' 63 represented by Chemical Formula 6 was used instead. An alignment film was prepared.

<Experimental Example: Measurement of physical properties of liquid crystal aligning agent composition and liquid crystal aligning film obtained in Examples and Comparative Examples>

Liquid crystal aligning agent composition obtained by the said Example and comparative example, or liquid crystal Physical properties of the alignment layer and the liquid crystal alignment cell manufactured using the same were measured by the following methods, and the results are shown in Table 1.

 The manufacturing method of a specific liquid crystal aligning cell is as follows. After aligning the liquid crystal alignment layers formed on two glass substrates each used as the upper plate / lower plate, facing each other and having the alignment directions parallel to each other, the upper and lower plates were bonded and cured with a sealing agent to prepare an empty cell. Then, a liquid crystal was injected into the empty cell and the inlet was sealed with a sealing agent to prepare a liquid crystal alignment cell.

1.Voltage holding ratio (vol tage holding rat io, VHR)

 About the said liquid crystal aligning cell, voltage retention was measured at 1 Hz and 60 temperature using the 6254C equipment of T0Y0 corporat ion as a measuring equipment.

2. RDC evaluation (residual DC voltage, residual DC)

 For the liquid crystal aligning cell, after applying DC stress at + 60 ° C of 0.5-1Y for 1 minute at 60 ° C. and leaving no voltage applied for 2 minutes, the remaining amount of DC is regarded as the residual DC. Measured.

3. Membrane strength

About the alignment film obtained by the said Example and the comparative example, film intensity | strength was measured and the result is shown in following Table 1. Specifically, the film strength of the alignment layer

Using a pencil hardness tester

The weights were lifted and measured using pencils of various hardness.

[Table 1]

Experimental Example Measurement Results of Example 1-3 and Comparative Example 1-3

2019/139332 1 »(： 1 ^ 1 {2019/000278

 Table 2

 Experimental Example Measurement Results of Example 4-6 and Comparative Example 4-6

 Table 3

 Experimental Example Measurement Results of Example 7-9 and Comparative Example 7-9

[Table 4]

Experimental Example Measurement Results of Examples 10-12

2019/139332 1 »(： 1 ^ 1 {2019/000278

 As shown in Tables 1 to 4, in the case of the liquid crystal aligning agent composition of Examples 1 to 12 in which a compound containing two or more urea groups was added while containing a hydroxy group at the terminal as a urea additive, a liquid crystal aligning film obtained therefrom In the applied liquid crystal cell, the voltage retention is higher than that of Comparative Examples 1 to 9,

5 Residual IX: The voltage exhibits low excellent electrical characteristics and at the same time, it can be seen that it has a significantly improved high film strength.

This, in the compound containing two or more urea groups, having a hydroxy group at the terminal, while the terminal hydroxy group reacts with the carboxy group of the polyamic acid polymer, forms a crosslink and at the same time suppresses the reduction of the electrical property ₀ by the carboxy group. In addition, it is believed that two or more urea groups form a crosslinked structure connected through a linker, so that the final crosslinked body secures a constant elasticity.

 Specifically, the alignment film obtained from the liquid crystal aligning agent compositions of Comparative Examples 1, 4 and 7 which did not contain the urea additive had a reduced voltage retention compared to Example 5 in which the same diamine was used, and the residual IX: voltage was higher, The figure also showed a decrease.

In addition, the liquid crystal alignment film obtained from the liquid crystal aligning agent composition of Comparative Examples 2, 5 and 8, in which the urea compound containing an alkoxysilyl group at the terminal was added as a urea additive, the voltage retention was reduced by ₀ compared to the embodiment using the same diamine. Residual IX: It was confirmed that the voltage was high and the film strength was decreased.

 In addition, the liquid crystal alignment film obtained from the liquid crystal alignment agent composition of Comparative Examples 3, 6, and 9, in which a compound containing only one urea group was added as the urea additive, the voltage retention was reduced compared to the embodiment using the same diamine, and residual IX : The voltage was increased and the film strength was decreased.

5

Claims

 2019/139332 1 »（： 1 ^ 1 {2019/000278

[Claim]

 [Claim 11

 Polymers including polyamic acid repeat units; And

 A liquid crystal aligning agent composition comprising a urea compound represented by Formula 1 below:

 [Formula 1]

In Chemical Formula 1,

 The show is a two to four functional group,

 II is an integer from 2 to 4

 At least one of ¾ and ¾ is a hydroxyalkyl group having 1 to 20 carbon atoms, and the rest is one of hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. [Claim 2]

 The method of claim 1,

 In Formula 1, is a divalent functional group, II is an integer of 2, the liquid crystal aligning agent composition. [Claim 3]

 The method of claim 1,

 The urea-based compound represented by Formula 1 includes a compound represented by Formula 2 below, a liquid crystal aligning agent composition:

[Formula 到 2019/139332 1 »（： 1 ^ 1 {2019/000278

0 in Formula 2, 6

： ⁰

 Is one of arylene groups having 6 to 30 carbon atoms, alkylene groups having 1 to 2 carbon atoms, or alkylenebisarylene groups having 7 to 40 carbon atoms,

At least one of ¾ and seedling ₄ is a hydroxyalkyl group having 6 to 20 carbon atoms, the remainder is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

 At least one of ¾ and ¾ is a hydroxyalkyl group having 1 to 20 carbon atoms,

The remainder is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

 021

 [Claim 4]

 The method of claim 3,

 The urea compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 2-1, a compound represented by Chemical Formula 2-2, a compound represented by Chemical Formula 2-3, a compound represented by Chemical Formula 2-4, A liquid crystal aligning composition comprising one compound selected from the group consisting of a compound represented by the following Chemical Formula 2-5 and a compound represented by the following Chemical Formula 2-6:

 [Formula 2-1]

[Formula 2-2] 2019/139332 1 »(： 1/10 公 019/000278

[Claim 5] 2019/139332 1 »（： 1 ^ 1 {2019/000278

The method of claim 1,

 The content of the urea-based compound represented by Formula 1 is 0.1% to 20% by weight based on the total weight of the liquid crystal aligning agent composition, the liquid crystal aligning agent composition.

[Claim 6]

 The method of claim 1,

 The polyamic acid repeating unit includes a repeating unit represented by Formula 3 below, the liquid crystal alignment composition:

 [Formula 3]

In Chemical Formula 3,

_¾ is a tetravalent organic group,

 Is a divalent organic group represented by the following formula (6),

 In Chemical Formula 6, at least one of ¾ to ¾ is nitrogen, the remainder is carbon, 1) is ^ or -0-, and is hydrogen or an alkyl group having 1 to 6 carbon atoms.

[Claim 7]

 The method of claim 6,

The divalent organic group represented by Formula 6 is a divalent organic group represented by Formula 7, a divalent organic group represented by Formula 8, and 2019/139332 1 »（： 1 ^ 1 {2019/000278

A liquid crystal aligning composition comprising a divalent organic group represented by Formula 9:

 [Formula 7]

[Claim 8]

 The method of claim 6,

 ¾ is one of the tetravalent organic groups represented by the following Chemical Formula 10, the liquid crystal alignment composition:

 [Formula 10]

In Formula 10, ¾ to ¾ ₄ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, is a single bond, -0-, -⑶-, -000-,-,- 2019/139332 1 »（： 1 ^ 1 {2019/000278

-， Three-0? ₁₅ ¾ _6- , _ （（¾） 「， -0 （抑₂入 0-，-¥ 0 （抑₂ ） ·-, — ¥ ■-, phenylene or any combination thereof , Wherein ¾ ₅ and ₆ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group, and is an integer of 1 to 10.

[Claim 9]

Applying the liquid crystal aligning agent composition of claim ₁ to a substrate to form a coating film;

 Drying the coating;

 Irradiating or rubbing the light on the dried coating layer to perform alignment treatment; And

 The heat treatment of the alignment-treated coating film comprising the step of curing. [Claim 10]

10. The method of claim _9,

The manufacturing method of liquid crystal aligning film which advances. [Claim 11]

 The method of claim 9,

The manufacturing method of a liquid crystal aligning film made to advance at the temperature of 300. [Claim 12]

 The liquid crystal aligning film containing the orientation hardened | cured material of the liquid crystal aligning agent composition of Claim 1. [Claim 13]

 A liquid crystal display device comprising the liquid crystal alignment film of claim 12.