KR20090127865A - Liquid crystal aligning agent and liquid crystal display - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing (a) at least one polymer selected from the group consisting of polyamic acids and imidized polymers thereof, and (b) a compound represented by the formula (A) below and having two epoxy groups in a molecule. (In the formula, Rrepresents a hydrogen atom or a monovalent organic group having 6-30 carbon atoms and bonded to the N atom by an aliphatic carbon.) This liquid crystal aligning agent is excellent in storage stability and adhesion to a substrate, and enables to form a tough coating film which hardly suffers from scratches due to rubbing processes performed under various conditions. Consequently, this liquid crystal aligning agent enables to form a liquid crystal alignment film having excellent liquid crystal aligning ability by performing a rubbing process on the surface of the coating film.

Description

Liquid crystal aligning agent and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT AND LIQUID CRYSTAL DISPLAY}

This invention relates to a liquid crystal display element and the liquid crystal aligning agent used for this. More specifically, it is related with the liquid crystal display element excellent in liquid crystal alignability and storage stability, and the liquid crystal aligning agent used for this.

Conventionally, a layer of a nematic liquid crystal having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment film is formed on the surface via a transparent conductive film to form a sandwich cell, and the long axis of the liquid crystal molecules is one substrate. A TN type liquid crystal display element having a TN type liquid crystal cell which is twisted 90 degrees continuously from the side toward the other substrate is known.

Orientation of the liquid crystal in liquid crystal display elements, such as this TN type liquid crystal display element, is normally implement | achieved by the liquid crystal aligning film to which the orientation ability of liquid crystal molecules was provided by the rubbing process. Here, as a material of the liquid crystal aligning film which comprises a liquid crystal display element, resin and epoxy type crosslinking agents, such as a polyimide, a polyamide, and polyester, are known conventionally. In particular, since polyimide is excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc., it is used for many liquid crystal display elements. Moreover, improvement of rubbing tolerance is achieved by adding an epoxy type crosslinking agent to the said resin. Moreover, even in the vertical alignment film which does not use a rubbing process, addition of an epoxy type crosslinking agent is effective for achieving high voltage retention.

However, there existed a problem that storage stability is inadequate with the epoxy crosslinking agent known conventionally, and sufficient liquid-crystal orientation is not obtained especially in the orientation mode which applies a rubbing process.

<Start of invention>

The present invention has been made on the basis of the above circumstances, and the first object of the present invention is to form a strong film that is excellent in adhesion to a substrate and hardly causes rubbing damage even by a rubbing treatment performed under various conditions. It is providing the liquid crystal aligning agent which can form the liquid crystal aligning film excellent in the orientation regulation force of liquid crystal molecule by performing a rubbing process on the surface of this film.

The 2nd object of this invention is to provide the liquid crystal aligning agent excellent in storage stability.

The 3rd object of this invention is to provide the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention.

Other objects and advantages of the present invention are apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are firstly [a] containing at least one polymer selected from a polyamic acid and an imidized polymer thereof, and [b] containing two epoxy groups in a molecule represented by formula (A) It is achieved by the liquid crystal aligning agent which consists of containing the compound to make.

(Wherein R ⁰¹ is a monovalent organic group having 6 to 30 carbon atoms bonded to a hydrogen atom or an N atom represented by the above formula and aliphatic carbon)

According to this invention, the said objective and advantage of this invention are 2nd achieved by the liquid crystal display element provided with the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<Polyamic acid>

The polyamic acid which comprises the liquid crystal aligning agent of this invention is obtained by making tetracarboxylic dianhydride and a diamine compound react.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride, a butane tetracarboxylic dianhydride, a 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3- Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane- 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1.3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetra Drupural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracar Acid dianhydrides, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 3,5,6- Tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, the following formulas I and II Aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by;

[Formula I]

[Formula II]

(In formula, R <^1> and R <^3> represents the divalent organic group which has an aromatic ring, R <^2> and R <^4> represents a hydrogen atom or an alkyl group, and ^two or more R <^2> and R <^4> may be same or different, respectively.)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride , m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride , Ethylene glycol -bis (anhydrotrimelitate), propylene glycol -bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotrimelitate), 1,6-hexanediol-bis (an Hydrotrimellitate), 1,8-octanediol-bis (anhydrotrimelitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimelitate), Aromatic tetracarboxylic dianhydrides, such as a compound represented by these, are mentioned. These are used individually by 1 type or in combination of 2 or more types.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic acid anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofural) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-fura Nil) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7- En-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, bicyclo [3.3.0] octane-2,4,6,8- Tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride Water, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the compound represented by the following formulas 5 to 7 of the compound represented by the formula (I) and the compound represented by the formula (8) among the compound represented by the formula (II) It is preferable from a viewpoint that a compound can express favorable liquid crystal aligning property, As a more preferable thing, 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxyl Acid anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'- Dione), 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-anhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxyl Acid dianhydride, pyromellitic dianhydride, and the compound represented by following formula (5) are mentioned. Especially preferable among these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-di Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- And 2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione and pyromellitic dianhydride.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Diamine Compound]

As a diamine compound used for the synthesis | combination of the said polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4, for example , 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4 , 4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1 , 3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether, 3,3'-diaminobenzo Phenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diamino ratio Phenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoro Methylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoro Rhomethyl) phenoxy] -octafluorobiphenyl, 2,7-diaminofluorene, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6 -Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis- (4-aminophenyl) -benz Aromatic diamine and the like;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, Powders such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (III) to (VI) Diamines having two primary amino groups and nitrogen atoms other than the primary amino group in the ruler;

[Formula III]

(Wherein R ⁵ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X represents a divalent organic group)

[Formula IV]

(Wherein R ⁶ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X represents a divalent organic group, and a plurality of X can be the same or different)

Mono substituted phenylenediamine represented by the following formula (V); Diaminoorganosiloxane represented by the following formula (VI);

[Formula V]

(Wherein R ⁷ represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, R ⁸ represents a steroid skeleton, a trifluoromethyl group and Monovalent organic group having a group selected from a fluoro group or an alkyl group having 6 to 30 carbon atoms)

[Formula VI]

(In formula, R <^9> represents a C1-C12 hydrocarbon group, two or more R <^9> may be same or different, p is an integer of 1-3, q is an integer of 1-20.)

The compound etc. which are represented by each of following General formulas 9-13 are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

(Wherein y is an integer from 2 to 12 and z is an integer from 1 to 5)

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4, 4'-diaminodiphenylether, 2,2-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis ( 4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ' -(p-phenylenediisopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine) , 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,7-diaminofluorene, 3,6-diaminocarbazole, N -Methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis- (4-aminophenyl ) -Benzidine, the formula 9 to 13 Compounds represented by each, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, of the compounds represented by Formula III Among the compounds represented by Formula 14, the compound represented by Formula IV, among the compounds represented by Formula 15 below, the compound represented by Formula V among the compounds represented by Formulas 16 to 23, and the compounds represented by Formula VI The compound represented by following formula (24) is preferable.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Synthesis reaction of polyamic acid]

The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under temperature conditions of -20 to 150 ° C, more preferably 0 to 100 ° C. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be illustrated. Moreover, it is preferable that the usage-amount (a) of an organic solvent is an amount which will be 0.1-30 weight% with respect to the total amount (a + b) of the total reaction solution (b) of tetracarboxylic dianhydride and a diamine compound.

[Poor Solvent]

Moreover, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc. which are poor solvents of polyamic acid can be used together with the said organic solvent in the range which does not precipitate the produced polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, di Ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Recall monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o -Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. are mentioned.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. In addition, a polyamic acid can be obtained by pouring this reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.

<Imidated Polymer>

The imidation polymer used for the liquid crystal aligning agent of this invention can be synthesize | combined by dehydrating and ring-closing the said polyamic acid. The imidation polymer here includes the partial imide polymer which partially imidated the said polyamic acid, and the polymer which imidated 100%, and these are collectively described as "imidization polymer." The dehydration ring closure of the polyamic acid may be carried out by (i) a method of heating the polyamic acid, or (ii) by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. Is done.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

On the other hand, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, as an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. In addition, the reaction temperature of the dehydration ring closing reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of a polyamic acid with respect to the reaction solution obtained in this way.

<Polymer of Terminal Modified Type>

The polyamic acid and the imidized polymer may be terminally modified with molecular weight controlled. By using this terminal modified polymer, the coating property of a liquid crystal aligning agent, etc. can be improved, without impairing the effect of this invention. Such terminal-modified form can be synthesize | combined by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. to a reaction system when synthesize | combining a polyamic acid. Here, as acid anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. Can be. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine , n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n -An eicosylamine etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

Logarithmic viscosity of the polymer

As for the polyamic acid and imidation polymer obtained as mentioned above, the value of the logarithmic viscosity ((eta) _ln ) becomes like this. Preferably it is 0.05-10 dl / g, More preferably, it is 0.05-5 dl / g.

The value of the logarithmic viscosity (η _ln ) in the present invention uses N-methyl-2-pyrrolidone as a solvent, and the viscosity is measured at 30 ° C with respect to a solution having a concentration of 0.5 g / 100 ml, It is obtained by the equation i.

<Epoxy group-containing compound>

The epoxy compound used in the present invention is represented by the following formula (A).

<Formula A>

(Wherein R ⁰¹ is a monovalent organic group having 6 to 30 carbon atoms bonded to a hydrogen atom or an N atom represented by the above formula and aliphatic carbon)

The monovalent organic group of R ⁰¹ preferably contains an alicyclic hydrocarbon group having a cyclohexane ring, a norbornene ring, an adamantane ring, or the like or an aromatic hydrocarbon group such as a benzene ring or a naphthalene ring.

As an epoxy compound represented by the said Formula (A), the compound represented by each of following formula (A) -1, (A) -2, and (A) -3 is mentioned, for example.

[Formula (A) -1]

[Formula (A) -2]

[Formula (A) -3]

In formulas (A) -1, (A) -2 and (A) -3, R ⁰² represents a hydrogen atom or a monovalent organic group such as an alkyl group or a phenyl group, and in the case of plural plural groups, may be different from each other. It may be formed. In addition, R ⁰² may be bonded to the ring-forming carbon of the cyclohexane ring or the benzene ring represented by (A) -1, (A) -2 and (A) -3 to form a ring structure. R <^03> is monovalent organic group, such as a hydrogen atom, an alkyl group, or a phenyl group, and when there are several, they may differ. In addition, R ⁰² and R ⁰³ may be crosslinked in the same molecule.

As a specific example of such an epoxy compound, N, N- diglycidyl cyclohexylamine, N, N- diglycidyl-2-methylcyclohexylamine, N, N- diglycidyl-4-methyl, for example Cyclohexylamine, N, N-diglycidyl-2,3-dimethylcyclohexylamine, N, N-diglycidyl-3,3,5-trimethylcyclohexylamine, N, N-diglycidyl 4-tert-butylcyclohexylamine, N, N-diglycidyl-2-aminonorbornane, N, N-diglycidyl-1-ethynylcyclohexylamine, N, N-diglyci Dil-1-adamantaneamine, 1,2,3,4-tetrahydro-1-naphthylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidyl-1- Adamantanemethylamine, N, N-diglycidyl-1-cyclohexylethylamine, N, N-diglycidyl-1-adamantan-1-yl-ethylamine, N, N-digly Cydylbenzylamine, N, N-diglycidyl-2-methylbenzylamine, N, N-diglycidyl-3-methylbenzylamine, N, N-diglycidyl-4-methylbenzylamine, N, N-diglycidyl-2,5-dimethylbenzylamine, N, N-digly Dyl-2-methoxybenzylamine, N, N-diglycidyl-3-methoxybenzylamine, N, N-diglycidyl-4-methoxybenzylamine, N, N-diglycidyl1 -Aminoindan, N, N- diglycidylbenzhydrylamine, N, N- diglycidyl-1-phenyleneethylamine, N, N- diglycidyl-1-phenyl-1-propanamine , N, N-diglycidyl-1- (4-methoxyphenyl) ethylamine, N, N-diglycidyl-1- (1-naphthyl) ethylamine, N, N-diglycidyl -1- (p-tolyl) ethylamine, N, N- diglycidyl-1-phenyl-2- (p-tolyl) ethylamine, N, N- diglycidyl-triphenylmethylamine, etc. are mentioned. Can be. Preferred among these are N, N-diglycidylaminomethylcyclohexane, N, N-diglycidyl benzylamine and the like.

<Liquid crystal aligning agent>

[B] The liquid crystal aligning agent of this invention contains the [a] component containing the at least 1 sort (s) of polymer chosen from a polyamic acid and its imidation polymer, and the at least 1 sort (s) chosen from the epoxy compound represented by the said Formula (A). A component is comprised by melt | dissolving and containing in an organic solvent.

Here, as the content ratio of the components [a] and [b], the ratio of the component [b] to 100 parts by weight of the component [a] is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 30 parts by weight. More preferably, it is 1-20 weight part.

The organic solvent for dissolving the [a] component and the [b] component is not particularly limited as long as it can dissolve them, and examples thereof include the same solvents as those exemplified as those used for synthesis of polyamic acid or dehydration ring closure. .

In addition, the functional silane containing compound may be contained in the liquid crystal aligning agent of this invention for the purpose of further improving adhesiveness to a board | substrate. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxy silyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

Although solid content concentration (the total concentration of [a] component, [b] component, and additive) in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 0.1-20 weight%. When solid content concentration is less than 0.1 weight%, the film thickness of a coating film (film) becomes too small and a favorable liquid crystal aligning film cannot be obtained, and when solid content concentration exceeds 20 weight%, the film thickness of a coating film becomes too large and a favorable liquid crystal It is hard to obtain an alignment film, the viscosity of a liquid crystal aligning agent may increase, and application | coating characteristic may fall.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example by the following method.

(1) Applying the liquid crystal aligning agent which forms the liquid crystal aligning film of this invention to one surface of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, the printing method, and the inkjet method, for example. Then, a coating film is formed by heating a coating surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used. The photoetching method and the method of using a mask beforehand are used for the patterning of these transparent conductive films. At the time of application | coating of a liquid crystal aligning agent, in order to make the adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film further favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. The heating temperature after liquid crystal aligning agent application becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film used as an oriented film by removing an organic solvent after application | coating, it can also be made into a more imidized coating film by advancing dehydration ring closure by further heating. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) The rubbing treatment which rubs the film surface formed with the liquid crystal aligning agent in the fixed direction with the roll which wound the cloth containing fibers, such as nylon, a rayon, a cotton, for example in a fixed direction is performed. Thereby, the orientation ability of liquid crystal molecules is provided to a film, and it becomes a liquid crystal aligning film. In addition to the method by rubbing treatment, the surface of the resin film is irradiated with polarized ultraviolet rays, ion beams, electron beams, etc. to impart orientation capability, or by a method of obtaining a film by a uniaxial stretching method, a Langmuir brozet method, or the like. You may form a liquid crystal aligning film. In addition, it is preferable to wash the formed liquid crystal alignment film with isopropyl alcohol or the like in order to remove the fine powder (foreign matter) generated during the rubbing treatment and to make the surface clean. Moreover, the process of changing a pretilt angle by partially irradiating an ultraviolet-ray, an ion beam, an electron beam, etc. to the surface of the formed liquid crystal aligning film (for example, Unexamined-Japanese-Patent No. 6-222366, Unexamined-Japanese-Patent No. 6-) 281937, Japanese Patent Laid-Open No. 7-168187, Japanese Patent Laid-Open No. 8-234207), and a resist film is partially formed on the surface of the formed liquid crystal aligning film, and is different from the rubbing treatment performed previously. After performing the rubbing treatment in the direction, the viewing angle of the liquid crystal display device manufactured by performing the treatment (refer to JP-A-5-107544, for example) of removing the resist film to change the alignment capability of the liquid crystal alignment film. Properties can also be improved.

(3) As described above, two substrates on which the liquid crystal alignment film was formed were prepared, and the two substrates were spaced apart (cell spacing) so that the alignment processing direction, that is, the rubbing direction, in each liquid crystal alignment film was perpendicular or antiparallel to each other. It arrange | positions and opposes, two peripheral parts of a board | substrate are bonded together using a sealing agent, the liquid crystal is injected-filled in the cell gap partitioned by the substrate surface and the sealing agent, and an injection hole is sealed and a liquid crystal cell is comprised. In addition, the polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell, by bonding the polarizing direction so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate. A display element is obtained.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

Examples of the liquid crystals include nematic liquid crystals, for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, and flutes. A midine liquid crystal, a dioxane liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are sold, for example, as cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). It is also possible to add and use the same chiral agent.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called H film | membrane which absorbed iodine, and extended | stretched polyvinyl alcohol between the cellulose acetate protective films, or the polarizing plate which consists of H film itself is mentioned.

As described above, the liquid crystal aligning agent of the present invention is excellent in storage stability, and thus can form a strong film which is hard to cause rubbing damage even by rubbing treatment performed under various conditions, and has excellent alignment control force of liquid crystal molecules. An alignment film can be formed. Therefore, the liquid crystal display element without orientation defect can be obtained.

The liquid crystal display element of the present invention can be effectively used in various devices, and for example, it is preferably used as a display device such as a table calculator, a wrist watch, a table clock, a mobile phone, a coefficient display panel, a word processor, a personal computer, a liquid crystal television, or the like. Can be.

[Liquid crystal orientation]

The presence or absence of the abnormal domain at the time of turning on / off (applying / releasing) the voltage to the liquid crystal display element manufactured in the Example and the comparative example was observed with the polarization microscope, and it judged that the case where there was no abnormal domain was "good". The result of evaluating liquid crystal alignability about each aligning agent was integrated in Table 1 below.

[Voltage retention rate]

After applying a voltage of 5 V to the liquid crystal display element at an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica. The case where the voltage retention was 90% or more was good, and the other cases were judged as defective. The results of evaluating the voltage retention for each of the alignment agents are summarized in Table 1.

[Storage Stability of Liquid Crystal Alignment Agent]

When the liquid crystal aligning agent is left at room temperature for one week, the viscosity of the liquid crystal aligning agent before and after standing is measured using an E-type viscometer, and the rate of change of the viscosity calculated based on the following formula (ii) is within ± 20%. Good and other cases were judged to be defective.

The results of evaluating the storage stability for each alignment agent are summarized in Table 1.

Synthesis Example 1

In a 200 ml three-necked flask equipped with a dim rod cooling tube, 12.52 ml (0.16 mol) of epichlorohydrin, 18 ml of ethanol, and 1.8 ml of pure water were mixed and heated to 50 ° C while stirring. 4.53 g (0.04 mol) of aminomethylcyclohexane was dripped at this solution in the state which adjusted reaction temperature between 48-53 degreeC, paying attention to the temperature rising of the reaction solution. Thereafter, the mixture was heated and stirred for 3 hours within the same temperature range, and then 8 g of a 50% NaOH aqueous solution was added dropwise over 45 minutes at a reaction temperature of 30 ° C, followed by heating and stirring at the same temperature for 3 hours. The precipitated salt was removed by filtration, and the filtrate was transferred to a flask equipped with filtrate to remove ethanol by an evaporator. 30 ml of toluene was added to the residue, and the solution was separated and washed four times with 15 ml of pure water and once with 15 ml of saturated aqueous sodium chloride solution. After drying the organic layer with magnesium sulfate anhydride, magnesium sulfate was filtered and the organic layer was concentrated by an evaporator.

The obtained viscous liquid was purified by column chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain 3.2 g of N, N-diglycidylaminomethylcyclohexane.

Synthesis Example 2

In a 200 ml three-necked flask equipped with a dim rod cooling tube, 12.52 ml (0.16 mol) of epichlorohydrin, 18 ml of ethanol, and 1.8 ml of pure water were mixed and heated to 50 ° C while stirring. 4.29 g (0.04 mol) of benzylamine was dripped at this solution in the state which adjusted the reaction temperature between 48-53 degreeC, paying attention to the temperature rising of the reaction solution. Thereafter, the mixture was heated and stirred for 3 hours within the same temperature range, and then 8 g of a 50% NaOH aqueous solution was added dropwise over 45 minutes at a reaction temperature of 30 ° C, followed by heating and stirring at the same temperature for 3 hours. The precipitated salt was removed by filtration, and the filtrate was transferred to a flask equipped with filtrate to remove ethanol by an evaporator. 30 ml of toluene was added to the residue, and the solution was separated and washed four times with 15 ml of pure water and once with 15 ml of saturated aqueous sodium chloride solution. After drying the organic layer with magnesium sulfate anhydride, magnesium sulfate was filtered and the organic layer was concentrated by an evaporator.

The obtained viscous liquid was purified by column chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain 5.6 g of N, N-diglycidyl benzylamine.

Synthesis Example 3

224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra 157.14 g (0.5 mol) of hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 94.62 g of p-phenylenediamine as a diamine compound ( 0.875 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 6.43 g (0.01 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, 8.09 g of n-octadecylamine as monoamine 0.03 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 370 g of a polyamic acid having a logarithmic viscosity of 0.82 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added to dehydrate and ring-close at 110 ° C. for 4 hours, and the precipitate, washing, Decompression was carried out to obtain 18.5 g of a polyimide having a logarithmic viscosity of 0.77 dl / g (this was referred to as "polyimide (A-1)").

Synthesis Example 4

224.17 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra 157.14 g (0.5 mol) of hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 93.27 g of p-phenylenediamine as a diamine compound ( 0.8625 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 13.15 g (0.03 mol) of 4'-cyclohexyl-3,5-diaminobenzoate, and 1.40 g (0.015 mol) of aniline as monoamine It was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining 370 g of a polyamic acid having a logarithmic viscosity of 0.82 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added to dehydrate and ring-close at 110 ° C. for 4 hours, and the precipitate, washing, Decompression was carried out to obtain 18.5 g of a polyimide having a logarithmic viscosity of 0.77 dl / g (this was referred to as "polyimide (A-2)").

Synthesis Example 5

1,2,3,4-cyclobutanetetracarboxylic dianhydride 196.12 g (1.0 mol) as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'-diaminobiphenyl 212 as a diamine compound g (1.0 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 360 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g (this is referred to as "polyamic acid (B-1)").

Synthesis Example 6

109.06 g (0.5 mol) of pyromellitic dianhydrides as tetracarboxylic dianhydride and 98.06 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 4,4'- as a diamine compound 198.3 g (1.0 mol) of diaminodiphenylmethane was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 365 g of polyamic acid having a logarithmic viscosity of 0.90 dl / g (this is referred to as "polyamic acid (B-2)").

Example 1

The polyimide (A-1) obtained in Synthesis Example 3 and the polyamic acid (B-1) obtained in Synthesis Example 5 are γ-butyrolactone / N-methyl- such that polyimide: polyamic acid = 20: 80 (weight ratio). Dissolved in a 2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 70/20/10), and 10 parts by weight of N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 was added to the polymer It was set as the solution of 4 weight% of solid content concentration. After stirring sufficiently, this solution was filtered using the filter of 0.2 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was manufactured. The liquid crystal aligning agent was applied onto the transparent conductive film containing an ITO film provided on one side of a glass substrate having a thickness of 1 mm by using an inkjet printer (rotational speed: 2,000 rpm, application time: 1 minute), and at 200 ° C for 1 hour. By drying for a while, a film having a dry film thickness of 0.08 mu m was formed. By the rubbing machine which has the roll which wound the cloth made from rayon to this film, the rubbing process was performed by the roll speed of 400 rpm, the moving speed of 3 cm / sec of a stage, and 0.4 mm of hair_bricks | mouth indentation length. The liquid crystal aligning film coated substrate was immersed in isopropyl alcohol for 1 minute, and then dried for 5 minutes on a hot plate at 100 ° C. Subsequently, after apply | coating the 5.5-micrometer diameter aluminum oxide sphere containing epoxy resin adhesive agent to each outer edge part which has a liquid crystal aligning film of the said liquid crystal aligning film application board | substrate of a pair of transparent electrode / transparent electrode board | substrate, it overlaps so that a liquid crystal aligning film surface may face. And the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6221 made by Merck Co., Ltd.) between a liquid crystal injection hole and a board | substrate, the liquid crystal injection hole is sealed with an acryl-type photocuring adhesive agent, a polarizing plate is bonded to both surfaces of the outer side of a board | substrate, and a liquid crystal display element is Prepared. The voltage retention and liquid crystal orientation of the obtained liquid crystal display element were evaluated. Moreover, storage stability was evaluated about the produced liquid crystal aligning agent. The results are shown in Table 1. It was confirmed that the liquid crystal aligning agent obtained by this invention has favorable voltage retention and liquid crystal alignability.

Example 2

(Gamma) -butyrolactone / N-methyl- so that the polyimide (A-1) obtained by the synthesis example 3 and the polyamic acid (B-2) obtained by the synthesis example 6 become polyimide: polyamic acid = 20: 80 (weight ratio). Dissolved in a 2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 70/20/10), and 10 parts by weight of N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 was added to the polymer It was set as the solution of 4 weight% of solid content concentration. After stirring sufficiently, this solution was filtered using the filter of 0.2 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was manufactured. Using the liquid crystal aligning agent manufactured in this way, the film was formed on the surface of a board | substrate similarly to Example 1, and the liquid crystal display element was manufactured using the board | substrate with which this liquid crystal aligning film was formed. Then, voltage retention and liquid crystal orientation were evaluated. Moreover, storage stability was evaluated about the produced liquid crystal aligning agent. The results are shown in Table 1.

Example 3

The polyimide (A-2) obtained in Synthesis Example 4 and the polyamic acid (B-1) obtained in Synthesis Example 5 are γ-butyrolactone / N-methyl- such that polyimide: polyamic acid = 20: 80 (weight ratio). Dissolved in a 2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 70/20/10), and 10 parts by weight of N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 was added to the polymer It was set as the solution of 4 weight% of solid content concentration. After stirring sufficiently, this solution was filtered using the filter of 0.2 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was manufactured. Using the liquid crystal aligning agent manufactured in this way, the film was formed on the surface of a board | substrate similarly to Example 1, and the liquid crystal display element was manufactured using the board | substrate with which this liquid crystal aligning film was formed. Then, voltage retention and liquid crystal orientation were evaluated. Moreover, storage stability was evaluated about the produced liquid crystal aligning agent. The results are shown in Table 1.

Examples 4-6

According to the prescription shown in Table 1 below, polyimide (A-1) to (A-2), polyamic acid (B-1) to (B-2) obtained in Synthesis Examples 3 to 6, and Synthesis Example 2 were obtained 10 parts by weight of N, N-diglycidylbenzylamine was dissolved in a γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 70/20/10) relative to the polymer. The liquid crystal aligning agent of this invention was manufactured by obtaining the solution of 4.0% of solid content concentration, and filtering this solution with the filter of 0.2 micrometer of pore diameters. Thus, using each of the liquid crystal aligning agents manufactured in this way, the film was formed on the surface of a board | substrate similarly to Example 1, and the liquid crystal display element was manufactured using the board | substrate with which the said liquid crystal aligning film was formed. Then, voltage retention and liquid crystal orientation were evaluated. Moreover, storage stability was evaluated about the produced liquid crystal aligning agent. The results are shown in Table 1.

Claims (6)

[A] A liquid crystal aligning agent comprising one or more polymers selected from polyamic acid and imidized polymer thereof, and [b] a compound containing two epoxy groups in a molecule represented by the following general formula (A). <Formula A>

(Wherein R ⁰¹ is a monovalent organic group having 6 to 30 carbon atoms bonded to a hydrogen atom or an N atom represented by the above formula and aliphatic carbon) The liquid crystal aligning agent of Claim 1 in which the monovalent organic group of R <^01> of General formula A contains an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The liquid crystal aligning agent of Claim 1 or 2 in which the said component [b] is represented by each of following General formula (A) -1, (A) -2 and (A) -3. [Formula (A) -1]

[Formula (A) -2]

[Formula (A) -3]

(Wherein R ⁰² is hydrogen or a monovalent organic group, and in the case of pluralities, they may be different from each other and may form a ring structure, and R ⁰² is (A) -1, (A) -2 and (A). ) may be in combination with a cyclohexane ring or a benzene ring forming the carbon ring represented by -3 to form a cyclic structure, R ⁰³ may be each different when there is a hydrogen or a monovalent organic group, plural, and R ⁰² R ⁰³ may be crosslinked within the same molecule) The liquid crystal aligning agent of any one of Claims 1-3 which contains 0.01-40 weight part of said components [b] with respect to 100 weight part of said components [a]. The liquid crystal aligning agent of any one of Claims 1-4 whose tetracarboxylic dianhydride of the raw material monomer of the said polymer [a] is 2,3,5- tricarboxycyclopentyl acetic dianhydride. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-5 is provided, The liquid crystal display element characterized by the above-mentioned.