KR101829501B1 - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Abstract

A liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display device which have a high effect of shortening the time until the afterimage caused by the DC voltage disappears, improve the ultraviolet resistance, and do not reduce the cut-off characteristics. At least one polymer selected from the group consisting of a polyimide precursor and a polyimide and a compound represented by the following formula [1] (wherein R ₁ represents a hydrogen atom or a vinyl group and n represents an integer of 0 to 2) And the liquid crystal alignment treatment agent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a liquid crystal alignment treatment agent and a liquid crystal display element using the same,

The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film, and a liquid crystal display device using the same.

At present, a so-called polyimide-based liquid crystal alignment film in which a liquid crystal alignment treatment agent containing a solution of a polyimide precursor such as polyamic acid or a soluble polyimide solution as a main component is applied to a substrate and baked is mainly used as a liquid crystal alignment film of a liquid crystal display element . The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.

From the viewpoint of reducing the afterimage phenomenon with a high definition of a liquid crystal display element, a material for which the charge accumulated by the DC voltage is fast in a liquid crystal alignment film used therefor is demanded. In the polyimide-based liquid crystal alignment film, a liquid crystal aligning agent containing a tertiary amine having a specific structure is used in addition to the polyamic acid or the imide group-containing polyamic acid as a short time until the after-image caused by the DC voltage disappears (See, for example, Patent Document 1), and a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton or the like is used as a raw material (see, for example, Patent Document 2).

A liquid crystal alignment treatment agent is required to have a material that is not shaved even if a rubbing alignment treatment is performed, from the viewpoint of reducing display unevenness, in addition to the fact that accumulated charges are quick to be relieved. In addition to these properties, a recent liquid crystal display device manufacturing process includes a process of irradiating ultraviolet rays in an ODF process, a PSA process, or the like, and a material resistant to ultraviolet rays is required.

Japanese Patent Application Laid-Open No. 9-316200 Japanese Patent Application Laid-Open No. 10-104633

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide an additive which has a high effect of shortening the time until the afterimage caused by the DC voltage disappears, enhances the ultraviolet resistance and does not reduce the cut-off property, And a liquid crystal display element using the same.

The inventors of the present invention have conducted intensive studies in order to achieve the above objects. As a result, the present inventors have found that, in addition to at least one kind of polymer selected from the group consisting of a polyimide precursor and a polyimide, The present invention has been accomplished on the basis of the finding that the above object can be achieved by the liquid crystal alignment treatment agent comprising the liquid crystal alignment treatment agent.

(1) at least one polymer selected from the group consisting of a polyimide precursor and a polyimide; and a compound represented by the following formula [1]: wherein R ₁ is a hydrogen atom or a vinyl group, and n is an integer of 0 to 2 And a liquid crystal alignment treatment agent.

[Chemical Formula 1]

(2) The liquid crystal alignment treating agent according to (1), wherein the compound represented by the formula [1] is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the at least one polymer selected from the polyimide precursor and the polyimide.

(3) The liquid crystal alignment treating agent according to (1) or (2), wherein R _{1 in the} formula [1] is a vinyl group.

(4) The liquid crystal alignment treating agent according to any one of (1) to (3), wherein the compound represented by the formula [1] is M1, M2, M3 or M4.

(2)

(5) The liquid crystal alignment treatment agent according to any one of (1) to (4), wherein the solid content is 0.5 to 10 mass%.

(6) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (5).

(7) A liquid crystal display element comprising the liquid crystal alignment film according to (6) above.

(8) A compound represented by the following formula [2]: wherein n represents an integer of 0 to 2.

(3)

According to the present invention, there is provided a liquid crystal alignment treatment agent capable of shortening the time until the afterimage caused by the DC voltage disappears, improving the ultraviolet resistance, and not reducing the cut-off characteristics.

Some of the compounds added to the liquid crystal alignment treatment agent of the present invention are novel compounds before the present application, and according to the present invention, these novel compounds are also provided.

[additive]

To the liquid crystal alignment treatment agent of the present invention, a compound represented by the following formula [1] (hereinafter also referred to as an additive of the present invention) is added.

[Chemical Formula 4]

In the formulas, R ₁ represents a hydrogen atom or a vinyl group, and n represents an integer of 0 to 2, preferably 1 or 2.

R ₁ represents a hydrogen atom or a vinyl group, but a vinyl group is preferable from the viewpoint of after-image characteristics of the obtained liquid crystal alignment film.

Preferable specific examples of the additive of the present invention include M1 to M12 described below. Among them, M1, M2, M3, or M4 is preferable,

[Chemical Formula 5]

The content of the additive of the present invention in the liquid crystal alignment treatment agent is preferably from 0.1 to 10 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the at least one polymer selected from the group consisting of the polyimide precursor and polyimide More preferably 1 to 5 parts by mass.

[Method of synthesizing additives]

The method for synthesizing the additive of the present invention can be synthesized by combining the techniques of organic synthetic chemistry and is not particularly limited. For example, it can be synthesized by the following method.

The additive represented by the general formula [1] of the present invention can be obtained by reacting the compound (i) with an organometallic reagent such as vinyl magnesium bromide or by reacting the compound ( I) with a reducing agent such as sodium borohydride.

[Chemical Formula 6]

The aldehyde compound represented by the formula (i) in the synthetic schemes (A) and (B) may be a commercially available compound or may be synthesized by cross-coupling reaction of the corresponding aniline compound and the halogenated aryl using a palladium catalyst.

Preferred specific methods for the synthesis scheme (A) and the synthesis scheme (B) are as described in the respective synthesis examples described later.

[Polyimide precursor and polyimide]

In the present invention, the polyimide precursor means a polyamic acid (also referred to as polyamide acid) and a polyamic acid ester. Polyamic acid is obtained by the reaction of a diamine component with a tetracarboxylic dianhydride. The polyamic acid ester is obtained by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base, or by reacting a tetracarboxylic acid diester and a diamine in the presence of a suitable condensing agent and a base. The polyimide of the present invention is obtained by subjecting the polyamic acid to dehydration ring closure, or by heating and closing the polyamic acid ester. Such a polyamic acid, a polyamic acid ester, and a polyimide are both useful as a polymer for obtaining a liquid crystal alignment film.

The diamine component used in the production of the polyimide precursor is not particularly limited, and examples thereof include alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, heterocyclic diamines, aliphatic diamines and the like, same.

Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3 ' -Dimethyldicyclohexylamine, isophoronediamine, and the like.

Examples of the aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, , 4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, Dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostyrene Benzene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4 ' Diaminodiphenylsulfone, 4,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis Benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [ Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- Bis (4-aminophenyl) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, 4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- , 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, (4-aminophenyl) ethane, 1,3-bis (4- Bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis Bis (4-aminophenyl) decane, 1,1-bis (4-aminophenyl) decane, Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, (4-aminophenoxy) decane, di (4-aminophenyl) propane-1,3-dioate, , Di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di -Dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) decane- Bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] Heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.

Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, Amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, Aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- .

Examples of the heterocyclic diamine include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, Diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole Sol and the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.

Also, when a diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a dihydroxy substituent formed therefrom (hereinafter, also referred to as another diamine) do. Specific examples of other diamines include diamines represented by the following formulas [DA1] to [DA26].

(7)

(Wherein [DA1] ~ formula [DA5] of, R ₆ is an alkyl group or a fluorine-containing alkyl group having a carbon number of 1 to 22)

[Chemical Formula 8]

(Wherein [DA6] ~ formula [DA9] of, S ₅ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, represents a -CO-, or -NH- , And R ₆ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[Chemical Formula 9]

(Wherein [DA10] and formula [DA11] of, S ₆ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 -, or represents a -CH ₂ OCO-, R ₇ is C 1 -C An alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

[Chemical formula 10]

(Of the formulas [DA12] to [DA14], S ₇ Is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH 2 -, or -CH ₂ - represents a, R ₈ is An alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

(11)

(Wherein [DA15] and formula [DA16] of, S ₈ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH _{2 -, -CH 2 -, -O-} , or -NH- to indicate, R ₉ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group to be)

[Chemical Formula 12]

(Wherein [DA17] ~ [DA20] one, R ₁₀ is a sheath having a carbon number of an alkyl group of 3-12, 1,4-cyclohexylene-trans reason the respective trans-isomer)

[Chemical Formula 13]

[Chemical Formula 14]

The diamines shown below may also be used in combination.

[Chemical Formula 15]

In the formula [DA31], m is an integer of 0 to 3, and in the formula [DA34], n is an integer of 1 to 5). [DA-29] to [DA-34] can reduce the accumulated charge reduction of the liquid crystal display element by introducing [DA-27] or [DA- And therefore, it is preferable.

Further, diaminosiloxane represented by the following formula [DA35] and the like are also exemplified.

[Chemical Formula 16]

(In the formula [DA35], m is an integer of 1 to 10)

The above-mentioned other diamine compounds may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

The tetracarboxylic acid dianhydride to be reacted with the diamine component to obtain the polyamic acid of the present invention is not particularly limited. Specific examples thereof are given below.

Examples of the tetracarboxylic acid dianhydride having an alicyclic or aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-Dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7- Butylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, tricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid-3 , 4: 7,8-2 anhydride, hexacyclo [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-2 Anhydride, and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

Further, when aromatic tetracarboxylic acid dianhydride is used in addition to the tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure, the liquid crystal alignability can be improved and the accumulated charge of the liquid crystal cell can be reduced Therefore, it is preferable. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid Biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4- Benzophenone tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid 2-anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and the like.

The tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

[Synthesis of polyamic acid]

The polyamic acid of the present invention can be obtained by reaction of a tetracarboxylic acid dianhydride and a diamine component by a known synthetic method. Generally, the tetracarboxylic acid dianhydride and the diamine component are reacted in an organic solvent. The reaction of the tetracarboxylic acid dianhydride with the diamine is advantageous in that it proceeds comparatively easily in an organic solvent and does not generate any by-products.

The organic solvent used for the reaction of the tetracarboxylic acid dianhydride and the diamine is not particularly limited as long as it dissolves the produced polyamic acid. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, An organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isobutanol, isobutanol, isobutanol, , Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3- Methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylacetamide, propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, Dimethyl propanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination. The polyamic acid may be a solvent that does not dissolve the polyamic acid, or may be mixed with the solvent in the range where the produced polyamic acid is not precipitated.

In addition, the water content in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyamic acid. Therefore, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

When the tetracarboxylic acid dianhydride and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred to disperse or dissolve the tetracarboxylic acid dianhydride as it is or in an organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine component, and the like, Either method may be used. When the tetracarboxylic acid dianhydride or the diamine component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, and the low molecular weight compounds which are sequentially reacted individually are mixed and reacted, May be used.

The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to carry out uniform stirring. Therefore, The total concentration of the acid dianhydride and the diamine component in the reaction solution is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyamic acid, the ratio of the total number of moles of the tetracarboxylic acid dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid.

[Synthesis of polyamic acid ester]

As a method for synthesizing a polyamic acid ester, a reaction of a tetracarboxylic acid diester dichloride with a diamine or a reaction of a tetracarboxylic acid diester and a diamine in the presence of a suitable condensing agent and a base gives a polyamic acid Ester can be obtained. Or by preliminarily polymerizing a polyamic acid and then esterifying the carboxylic acid in the amic acid by using a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and the diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours Followed by reaction.

Although pyridine, triethylamine or 4-dimethylaminopyridine can be used as the base, pyridine is preferred for mild reaction. The amount of the base to be added is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

When a polycondensation reaction is carried out in the presence of a condensing agent, it is preferable to use a condensation agent such as triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, Imidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, N, N ', N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzoxazolyl ) Phosphinic acid diphenyl, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholinium chloride n-hydrate and the like.

Further, in the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount with respect to (C1).

The solvent used in the above reaction may be a solvent used when the polyamic acid shown above is polymerized. From the solubility of the monomer and the polymer, N-methyl-2-pyrrolidone or? -Butyrolactone is preferable These may be used alone or in combination of two or more. The concentration in the synthesis is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that the precipitation of the polymer is hardly caused and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the introduction of outside air in a nitrogen atmosphere.

In the present invention, the tetracarboxylic acid diester to be reacted with the diamine component in order to obtain the polyamic acid ester is not particularly limited, but an aliphatic tetracarboxylic acid diester or an aromatic tetracarboxylic acid dialkylester is preferable, Are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclo Diethyl hexyltetracarboxylate Stearyl, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, Tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.12,7.03,6.19,14.010,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran- , 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, and the like.

Specific examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-bis Phenyl tetracarboxylic acid dialkyl ester, 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6 -Naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like.

[Synthesis of polyimide]

The polyimide of the present invention is a polyimide obtained by dehydrocondylating the polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film. In the polyimide of the present invention, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Examples of a method for imidizing a polyimide precursor such as polyamic acid include heat imidization in which a solution of a polyamic acid is heated as it is, and catalyst imidation in which a catalyst is added to a solution of a polyamic acid.

When the polyamic acid is thermally imidized in the solution, the temperature is preferably 100 ° C to 400 ° C, and more preferably 120 ° C to 250 ° C. It is preferable to carry out the removal while removing water generated by the imidization reaction out of the system.

The catalyst imidation of polyamic acid can be carried out by adding a basic catalyst and acid anhydride to a solution of polyamic acid and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

[Polymer recovery]

In the case of recovering the resulting polyamic acid, polyamic acid ester, and polyimide from the reaction solution of polyamic acid, polyamic acid ester, and polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or by heating. In addition, by repeating the operation of re-dissolving the precipitated and recovered polymer in an organic solvent and repeating the precipitation and recovering 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the polyimide precursor and polyimide such as the polyamic acid contained in the liquid crystal alignment treatment agent of the present invention is preferably in the range of from 1 to 10, The weight average molecular weight measured by Permeation Chromatography is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

≪ Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film and is a solution in which at least one polymer selected from the group consisting of the polyimide precursor and polyimide and the additive of the present invention are dissolved in an organic solvent. The solid content concentration in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the setting of the thickness of the liquid crystal alignment film to be formed, but it is preferably 0.5 to 10 mass%, more preferably 1 to 8 mass%. When the solid concentration is less than 0.5% by mass, it is difficult to form a uniform and defect-free coating film. When the solid concentration is more than 10% by mass, the storage stability of the solution may be deteriorated. The term "solid component" as used herein refers to a component from which a solvent is removed from a liquid crystal aligning agent and means at least one kind of polymer selected from the above-mentioned polyimide precursor and polyimide, the additive of the present invention, and various additives described below. Specifically, in order to measure the content of the solid content, a small amount of the liquid crystal alignment treatment agent is placed in an aluminum container whose weight has been measured in advance and the weight is measured. The resultant is heated in an oven at 200 ° C for 1 hour to evaporate the solvent, The weight of the aluminum container is measured. Are calculated from their values.

The method for producing the liquid crystal alignment treatment agent of the present invention is not particularly limited. Typically, it is prepared by mixing a polyimide solution or a solution of polyimide with a polyimide precursor solution such as a polyamic acid. In the case of a polyimide precursor such as polyamic acid, a reaction solution of a polyamic acid obtained by polycondensation may be used as it is, and once the polyamic acid is obtained, it may be redissolved in an organic solvent and used as a polyamic acid solution. The polyamic acid solution may be diluted to a desired concentration.

On the other hand, in the case of polyimide, the reaction solution of soluble polyimide obtained by imidization may be used as it is, and once the polyimide powder is obtained, it may be redissolved in an organic solvent and used as a polyimide solution. The polyimide solution may be diluted to a desired concentration.

The organic solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving at least one kind of polymer selected from the group consisting of the polyimide precursor and polyimide (hereinafter also referred to as resin component). Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy- Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, Hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination.

The liquid crystal alignment treatment agent of the present invention may contain components other than those described above. Examples thereof include a solvent and an additive for improving film thickness uniformity and surface smoothness when the liquid crystal alignment treatment agent is applied, and an additive for improving the adhesion between the liquid crystal alignment film and the substrate.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness or the surface smoothness include the following. Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol , A solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

These poor solvents may be used alone or in combination. When such a solvent is used, it is preferably 5 to 80 mass%, and more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal alignment treatment agent.

Examples of the additives that improve the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

(For example, EF301, EF303, and EF352 (manufactured by Tohchem Products)), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Fluoride FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.

Specific examples of the additive for improving the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3 -Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

[Liquid Crystal Alignment Layer]

The liquid crystal alignment treatment agent of the present invention can be used as a coating film by preferably filtering it before application to a substrate and then applying it to the substrate and drying and baking the liquid crystal alignment treatment agent to carry out an orientation treatment such as rubbing treatment or light irradiation Thereby being used as the liquid crystal alignment film of the present invention.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used and a substrate on which an ITO electrode or the like for liquid crystal driving is formed is used Is preferable from the viewpoint of simplification of the process. In the reflection type liquid crystal display device, an opaque substrate such as a silicon wafer can be used only for a substrate on one side. In this case, a material for reflecting light such as aluminum can also be used as the electrode in this case.

As a method of applying the liquid crystal alignment treatment agent, a spin coating method, a printing method, an ink jet method, or the like can be mentioned. In view of productivity, however, the flexographic printing method is widely used industrially. In the liquid crystal aligning agent of the present invention Is preferably used.

The step of drying after application of the liquid crystal alignment treatment agent is not necessarily required. However, when the time from the application to the firing is not constant for each substrate or when the firing is not carried out immediately after the application, it is preferable to include a drying step. The drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coated film is not deformed by conveyance of the substrate or the like. For example, a method of drying on a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes may be mentioned.

The substrate to which the liquid crystal alignment treatment agent is applied can be baked at any temperature of 100 to 350 캜, preferably 150 to 300 캜, and more preferably 180 to 250 캜. The polyamic acid contained in the liquid crystal aligning agent changes in conversion from amic acid to imide by firing, but the polyamic acid does not necessarily have to be imidized to 100%. However, it is preferable to perform firing at a temperature of 10 ° C or more higher than the heat treatment temperature such as seal hardening necessary for the liquid crystal cell manufacturing process.

When the thickness of the coated film after firing is excessively large, the power consumption of the liquid crystal display element is deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may be deteriorated. Therefore, the thickness is preferably 10 to 200 nm, more preferably 50 to 100 Nm.

Conventional rubbing apparatuses can be used for the rubbing treatment of the coating film surface formed on the substrate as described above. Examples of the material of the rubbing cloth at this time include cotton, rayon, nylon and the like.

The liquid crystal display element of the present invention is obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, and then manufacturing a liquid crystal cell by a known method to obtain a liquid crystal display element.

For example, a pair of substrates on which a liquid crystal alignment film is formed may be formed with a spacer having a rubbing direction of 0 to 270 degrees with a spacer of preferably 1 to 30 mu m, more preferably 2 to 10 mu m therebetween, And the periphery is fixed with a sealant, and liquid crystal is injected and sealed. The method of sealing the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which liquid crystal is injected after reducing the pressure in the produced liquid crystal cell, and a dropping method in which a liquid crystal is dropped and then sealed.

The liquid crystal display device obtained by using the liquid crystal alignment treatment agent of the present invention is excellent in afterimage characteristics and liquid crystal alignability and has poor display defects accompanied by flaws in the liquid crystal alignment film and peeling of the film caused during rubbing treatment, And the reliability of the liquid crystal display device can be improved.

Example

EXAMPLES The present invention will be described in further detail with reference to the following examples, but the invention is not construed as being limited thereto.

&Quot; Synthesis of additives "

Synthesis examples of additives in the present invention are shown. Each measurement method and analysis apparatus used are as follows.

<Measurement of NMR>

The compound was dissolved in deuterated chloroform and measured by ¹ H NMR (manufactured by Verian) at 400 MHz.

(Synthesis Example 1) Synthesis of additive (M1)

To a 500 ml (liter) four-necked flask, 11.5 g of bis (4-formylphenyl) phenylamine and 230 g of tetrahydrofuran were added and cooled in an ice bath. 60.1 ml of a tetrahydrofuran solution of magnesium chloride at a concentration of 1.46 mol / l was added dropwise at 0 占 폚 and the mixture was stirred at room temperature for 18 hours. Thereafter, a 15 wt% aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, the solvent was distilled off using a rotary evaporator to obtain 13.2 g of a viscous reddish brown liquid.

The result of measurement of this reddish brown liquid by NMR is shown below. From this result, it was confirmed that the obtained reddish brown liquid had the following formula (M1).

[Chemical Formula 17]

(Synthesis Example 2) Synthesis of additive (M2)

In a 500 ml four-necked flask, 11.7 g of 4- (N, N-diphenylamino) benzaldehyde and 240 g of tetrahydrofuran were added and cooled in an ice bath. 32.3 ml of a tetrahydrofuran solution of magnesium chloride at a concentration of 1.46 mol / l was added dropwise at 0 占 폚, and the mixture was stirred at room temperature for 48 hours. Thereafter, a 15 wt% aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and after filtration, the solvent was distilled off using a rotary evaporator to obtain 12.6 g of a viscous reddish brown liquid.

The result of measurement of this reddish brown liquid by NMR is shown below. From this result, it was confirmed that the obtained reddish brown liquid was represented by the following formula (M2).

[Chemical Formula 18]

(Synthesis Example 3) Synthesis of additive (M3)

In a 500 ml four-necked flask, 11.5 g of bis (4-formylphenyl) phenylamine and 220 g of methanol were added and cooled in an ice bath. At a temperature of 0 占 폚, 3.1 g of sodium borohydride was added, and the mixture was stirred at room temperature for 24 hours. After cooling in an ice bath, a 10 wt% aqueous solution of ammonium chloride was added and extracted with ethyl acetate. Water was added to the organic layer to separate the layers, and then anhydrous magnesium sulfate was added to the organic layer. After the magnesium sulfate was filtered off, the solvent was distilled off using a rotary evaporator to obtain 11.6 g of a white solid.

The result of measurement of this white solid by NMR is shown below. From this result, it was confirmed that the obtained white solid was the following formula (M3).

[Chemical Formula 19]

(Synthesis Example 4) Synthesis of additive (M4)

In a 500 ml four-necked flask, 13.0 g of bis (4-formylphenyl) phenylamine and 260 g of methanol were added and cooled in an ice bath. At a temperature of 0 占 폚, 2.0 g of sodium borohydride was added, and the mixture was stirred at room temperature for 9 hours. After cooling in an ice bath, a 10 wt% aqueous solution of ammonium chloride was added and extracted with ethyl acetate. Water was added to the organic layer to separate the layers, and then anhydrous magnesium sulfate was added to the organic layer. After the magnesium sulfate was filtered off, the solvent was distilled off using a rotary evaporator to obtain 13.0 g of a white solid.

The result of measurement of this white solid by NMR is shown below. From this result, it was confirmed that the obtained white solid was the following formula (M4).

[Chemical Formula 20]

&Quot; Synthesis of polyamic acid, polyimide &quot;

An example of synthesis of the resin and the resin solution in the present invention is shown. Each measurement method and analysis apparatus used are as follows.

Explanation of the abbreviation used

&Lt; Tetracarboxylic acid dianhydride &gt;

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

TDA: 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

PMDA: pyromellitic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride

<Diamine>

DDM: 4,4'-diaminodiphenylmethane

PDA: p-phenylenediamine

APC18: 1,3-Diamino-4-octadecyloxybenzene

DADPA: 4,4'-diaminodiphenylamine

<Organic solvent>

NMP: N-methyl-2-pyrrolidone

γ-BL: Butyrolactone

BCS: butyl cellosolve

&Lt; Measurement of molecular weight &

The molecular weight of the polyimide was measured by a GPC (room temperature gel permeation chromatography) apparatus and the number average molecular weight and the weight average molecular weight were calculated as polyethylene glycol and polyethylene oxide conversion values.

GPC apparatus: manufactured by Shodex Co., Ltd. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: 30 mmol / l of lithium bromide-hydrate (LiBr 占 O 2O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF ) &Lt; / RTI &gt; 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150000, 100000, 30000) manufactured by Tosoh Corporation; and polyethylene glycol (molecular weight: about 12,000, 4000, 1000) manufactured by Polymer Laboratories.

&Lt; Measurement of imidization rate &

The imidization rate of the polyimide was determined by dissolving the polyimide in d6-DMSO (dimethylsulfoxide-d6) and measuring it using ¹ H NMR (manufactured by Verian) at 400 MHz, and measuring the amide The ratio of the acid groups was calculated from the ratio of the integrated value of the proton peaks.

&Quot; Production Example of Polymer Solution &quot;

(Production Example 1)

In a 500 ml four-necked flask, 11.7 g of PDA, 4.5 g of APC18 and 206 g of NMP were added to dissolve and 35.3 g of TDA was added. And the mixture was reacted at room temperature for 11 hours under a nitrogen atmosphere to prepare a polymer solution (P-1).

To 180 g of the obtained polymer solution (P-1), 270 g of NMP was added and diluted. 56.2 g of acetic anhydride and 43.5 g of pyridine were added and reacted at 40 DEG C for 3 hours to imidize. The reaction solution was cooled to room temperature, and then poured into 2000 ml of methanol, and the precipitated solid was recovered. This solid was washed several times with methanol, and then dried under reduced pressure at 100 占 폚 to obtain a white powder. This polyimide had a number average molecular weight of 6,500 and a weight average molecular weight of 14,400. The imidization rate was 80%.

24 g of the obtained powder and 216 g of? -BL were added to a one liter type flask and stirred at 50 占 폚 for 14 hours to obtain a polymer solution (P-2). 120 g of BCS and 40 g of? -BL were further added to the resulting polymer solution (P-2) and stirred at room temperature for 18 hours to obtain a polymer solution (P-3).

(Production Example 2)

In a 500 ml four-necked flask, 39.6 g of DDM, 222 g of NMP and 222 g of? -BL were added and dissolved, and 19.6 g of CBDA and 19.2 g of PMDA were added. The reaction was conducted at room temperature for 5 hours in a nitrogen atmosphere to prepare a polymer solution (P-4). This polymer had a number average molecular weight of 10,900 and a weight average molecular weight of 27,300.

450 g of? -BL and 150 g of BCS were added to 400 g of the resulting polymer solution (P-4) and stirred at room temperature for 2 hours to obtain a polymer solution (P-5).

(Production Example 3)

50 g of the polymer solution (P-3) obtained in Resin Production Example 1 and 400 g of the polymer solution (P-5) obtained in Resin Production Example 2 were stirred at room temperature for 20 hours to obtain a polymer solution (P-6).

(Production Example 4) BODA / DADPA

39.9 g of DADPA and 356 g of NMP were added to and dissolved in a 500 ml four-necked flask, and 49.0 g of BODA was added. The reaction was carried out at 50 캜 for 24 hours in a nitrogen atmosphere to prepare a polymer solution (P-7). This polymer had a number average molecular weight of 13,100 and a weight average molecular weight of 31,300.

500 g of NMP and 200 g of BCS were added to 300 g of the obtained polymer solution (P-7), and the mixture was stirred at room temperature for 2 hours to obtain a polymer solution (P-8).

(Production Example 5) TCA / PDA

In a 500 ml four-necked flask, 21.6 g of PDA and 369 g of NMP were added and dissolved, and 43.5 g of TCA was added. The reaction was conducted at 50 캜 for 24 hours in a nitrogen atmosphere to prepare a polymer solution (P-9). This polymer had a number average molecular weight of 12,700 and a weight average molecular weight of 24,300.

400 g of NMP and 200 g of BCS were added to 400 g of the resulting polymer solution (P-9), and the mixture was stirred at room temperature for 2 hours to obtain a polymer solution (P-10).

[Liquid crystal alignment treatment agent]

(Examples 1, 3, 5, 7, 9, 10, 11, 12)

20.0 g of each polymer solution (P-3, P-6, P-8 or P-10) shown in the following Table 1 and 20.0 g of each of the polymer solutions (M1, M2, M3 or M4) (C 1, C 3, C 5, C 7, C 9, C 10, C 11 and C 12) were obtained by stirring the mixture for 1 hour.

(Examples 2 and 4)

20.0 g of the above polymer solution P-6 shown in the following Table 1 and 0.036 g of the compound (M1 or M3) were added to a 100 ml eggplant-shaped flask and stirred for 1 hour to obtain liquid crystal alignment treatment agents (C2 and C4) .

(Example 6)

20.0 g of the above polymer solution P-3 and 0.12 g of the compound M2 shown in the following Table 1 were added to a 100 ml eggplant-shaped flask and stirred for 1 hour to obtain a liquid crystal alignment treatment agent (C6).

(Example 8)

20.0 g of the polymer solution P-3 and 0.012 g of the compound M2 shown in the following Table 1 were added to a 100 ml eggplant-shaped flask and stirred for 1 hour to obtain a liquid crystal alignment treating agent (C8).

(Comparative Example 1)

20.0 g of polymer solution P-3 and 0.06 g of triphenylamine (hereinafter referred to as TPA) were added to a 100 ml eggplant-shaped flask and stirred for 1 hour to obtain a liquid crystal alignment treatment agent C13.

&Lt; Production of liquid crystal cell &

(Example 13)

The liquid crystal alignment treatment agent C1 shown in Table 1 was spin-coated on a glass substrate having a transparent electrode formed thereon and dried on a hot plate at 80 DEG C for 70 seconds and then fired on a hot plate at 235 DEG C for 10 minutes to give a film having a thickness of 100 nm To form a coating film. The coated film surface was rubbed with a rubbing device having a roll diameter of 120 mm using a Ray-on spring under the conditions of a roll revolution rate of 1000 rpm, a roll advancing speed of 50 mm / sec, and a press-in amount of 0.3 mm to obtain a substrate having a liquid crystal alignment film formed thereon.

Two sheets of the substrates on which the liquid crystal alignment films were formed were prepared, spacers having a size of 6 mu m were dispersed on one liquid crystal alignment film surface, a sealant was printed thereon, and another substrate was rubbed Direction, and then the sealant was cured to prepare an empty cell. Liquid crystal MLC-2003 (C080) (manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method and the injection port was sealed to obtain a twisted nematic liquid crystal cell.

A method of measuring the properties of each liquid crystal cell thus manufactured and a method of irradiating UV are described below.

&Lt; Measurement of accumulated charge (RDC) &gt;

A DC voltage was applied to a twisted nematic liquid crystal cell manufactured by the method described in &lt; Production of a liquid crystal cell &gt; at a temperature of 23 DEG C at intervals of 0 V to 0.1 V at 1.0 V and the flicker amplitude level at each voltage was measured To prepare a calibration curve. After grounding for 5 minutes, an AC voltage of 3.0 V and a DC voltage of 5.0 V were applied for 1 hour, and then the flicker amplitude level immediately after the DC voltage was changed to 0 V was measured and compared with the previously prepared calibration curve to estimate RDC This RDC estimation method is called Flicker Reference Method).

Here, the RDC improvement time was defined as the time until the RDC value decreased by 50% from the RDC value immediately after applying the DC voltage 5.0 V for 1 hour. As a result of evaluating the cell manufactured in Example 13, the RDC improvement time was 0.35 sec.

<UV irradiation>

Light irradiation was performed for 167 sec using a desktop UV curing apparatus HCT3B28HEX-1, manufactured by Sens Light Source Co., Ltd., in a twisted nematic liquid crystal cell manufactured by the method described in &lt; Production of Liquid Crystal Cell &gt; At that time, when the illuminance was measured using an illuminometer (UV Light MEASUREMODEL UV-M02 manufactured by CRC Corporation) and using a UV-35 sensor, the illuminance was 60.0 mW / cm 2.

&Lt; Measurement of voltage holding ratio (VHR) &gt;

The voltage holding ratio of the twisted nematic liquid crystal cell treated by the &lt; UV irradiation &gt; method was measured by applying a voltage of 4 V for 60 seconds under a temperature of 90 DEG C, measuring a voltage after 16.67 msec, Was calculated as the voltage holding ratio. VHR-1 voltage maintenance ratio measuring apparatus manufactured by Toyo Technica Co., Ltd. was used for measurement of the voltage holding ratio.

As a result of evaluating the cell manufactured in Example 1, the voltage holding ratio was 47%.

(Examples 14 to 16 and Comparative Example 2)

Twisted nematic liquid crystal cells were prepared in the same manner as in Example 13, using the liquid crystal alignment treatment agents shown in Table 2 and the polymer solution comprising P-6, respectively. For each of these liquid crystal cells, the RDC improvement time and the VHR after the UV treatment were evaluated. The results are shown in Table 2.

(Examples 17 to 24 and Comparative Examples 3 and 4)

Twisted nematic liquid crystal cells were prepared in the same manner as in Examples 13 to 16, respectively. The RDC improvement time and the rubbing resistance of each liquid crystal cell thus prepared were evaluated. The results are shown in Table 3.

The rubbing resistance evaluation was evaluated as follows.

&Lt; Evaluation of rub resistance &

As a test for rubbing resistance, rubbing was performed under the condition that the indentation amount was changed to 0.5 mm, and the surface of the film was observed with a confocal laser microscope. The evaluation was carried out as follows.

○: No scrapes are observed.

X: Shavings are observed.

Industrial availability

The liquid crystal alignment treatment agent of the present invention has a TN device, an STN device, a TFT liquid crystal display device, and the like, since the liquid crystal alignment treatment agent of the present invention can shorten the time until the afterimage generated by the DC voltage disappears, improve ultraviolet resistance, Device, and further, for forming a liquid crystal alignment film in a vertically aligned liquid crystal display device or the like.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-118371 filed on May 26, 2011 are incorporated herein by reference and the disclosure of the specification of the present invention.

Claims (8)

At least one polymer selected from the group consisting of a polyimide precursor and a polyimide and a compound represented by the following formula [1] (wherein R ₁ represents a hydrogen atom or a vinyl group and n represents an integer of 0 to 2) Wherein the liquid crystal alignment treatment agent is a liquid crystal alignment agent.
[Chemical Formula 1]

The method according to claim 1,
Wherein the compound represented by the formula [1] is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of at least one polymer selected from the group consisting of a polyimide precursor and a polyimide. The method according to claim 1,
Equation [1] R ₁ a treatment liquid crystal of vinyl group. The method according to claim 1,
Wherein the compound represented by the formula [1] is M1, M2, M3, or M4 described below.
(2)

The method according to claim 1,
A liquid crystal alignment treatment agent containing a solid content of 0.5 to 10 mass%. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 5. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6. A compound represented by the following formula [2] (wherein n represents an integer of 0 to 2).
(3)