WO2008114846A1 - 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, R01 represents 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

 Technical Document Liquid Crystal Alignment Agent and Liquid Crystal Display Device Technical Field

 The present invention relates to a liquid crystal display element and a liquid crystal aligning agent therefor. More specifically, the present invention relates to a liquid crystal display element excellent in liquid crystal alignment and storage stability and a liquid crystal aligning agent therefor. Background Technology ''

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

 The alignment of liquid crystal in a liquid crystal display element such as this TN type liquid crystal display element is usually realized by a liquid crystal alignment film provided with alignment ability of liquid crystal molecules by rubbing treatment. Here, as materials for the liquid crystal alignment film constituting the liquid crystal display element, resins such as polyimide, polyamide, and polyester, and an epoxy-based crosslinking agent are conventionally known. In particular, polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, and mechanical strength. In addition, the rubbing resistance can be improved by adding an epoxy crosslinking agent to the resin. Furthermore, even in a vertical alignment film that does not use a rubbing process, the addition of an epoxy crosslinking agent is effective in achieving a high voltage holding ratio.

However, the conventionally known epoxy-based crosslinking agents have a problem in that the storage stability is not sufficient, and sufficient liquid crystal alignment cannot be obtained particularly in an alignment mode adapted for rubbing treatment. Disclosure of the invention

 The present invention has been made on the basis of the circumstances as described above, and the first object of the present invention is to provide excellent adhesion to a substrate and to prevent rubbing scratches even by rubbing treatment performed under various conditions. Provided is a liquid crystal aligning agent that can form a tough film that is difficult to stick, and can form a liquid crystal alignment film with excellent alignment regulating power of liquid crystal molecules by rubbing the surface of the film. It is in.

 A second object of the present invention is to provide a liquid crystal aligning agent having excellent storage stability. The third object of the present invention is to provide a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

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

 According to the present invention, the above objects and advantages of the present invention are as follows. First, [a] at least one polymer selected from polyamic acid and its imidized polymer, and [b] the following formula (1): This is achieved by a liquid crystal aligning agent characterized in that it contains a compound containing two epoxy groups in the molecule represented.

(In the formula, R ^{Q 1} is a hydrogen atom or a monovalent organic group having 6 to 30 carbon atoms bonded to the N atom represented in the above formula by an aliphatic carbon.)

 According to the present invention, the above objects and advantages of the present invention are secondly achieved by a liquid crystal display device comprising a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the details of the present invention will be described.

<Polyamic acid> The polyamic acid constituting the liquid crystal aligning agent of the present invention can be obtained by reacting tetracarboxylic dianhydride with a diamine compound.

 [Tetracarboxylic dianhydride]

Examples of tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dixotetrahydro-3-furanyl, 1) 3-Methyl _ 3-Cyclohexene 1, 2, 2-dicarboxylic anhydride, 1, 2_dimethyl-1, 2, 3, 4-cyclobutantetracarboxylic 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 dianhydride, 3, 3 ', 4, 4'—Dicyclohexyltetracarboxylic dianhydride, 2, 3 , 5-tricarboxycyclopentylacetic acid dianhydride, 3, 5, 6-tricarboxynorpolnan mono 2-oxalic acid dianhydride, 2, 3, 4, 5-tetrahydrofurantetracarboxylic dianhydride, 1, 3, 3 a, 4, δ, 9 b—Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) 1-naphtho [1, 2-c] 1-furan 1,3-dione 1, 3, 3 a, 4, 5, 9 b—Hexahydro 1-Methyl-5 (Tetrahydro 1,2,5-Dioxo_3-Furanyl) One naphtho [1, 2-c] — Furan 1,3-Dione 1, 3, 3 a , 4, 5, 9 b—Hexahydro-1,5-ethyl-5 (tetrahydro-1,5-dioxo-3-furanyl) 1 naphtho [1, 2 — c] —furan 1,3-dione, 1, 3, 3 a, 4, 5, 9 b-Hexahydro 1-Methyl 1-5 (tetrahydro-2,5-dioxo 3-furanyl) 1-naphtho [1,2-c] 1-furan 1,3 Dione, 1, 3, 3 a, 4, 5, 9b—Hexahydro-7-ethyl-5 (tetrahydro_ 2,5-dioxo-3-furanyl) —naphtho [1,2-c] —furan 1,3 —Dione, 1, 3, 3 a, 4, 5, 9 b—Hexahydro-8_methyl-1-5 (tetrahydro-1,5-dioxone 3-frael) 1 naphtho [1, 2-c] —furan — 1, 3—Dione, 1, 3, 3 a, 4, 5, 9 b—Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) 1-naphtho [1, 2-c] —furan-1,3-dione, 1, 3, 3 a, 4, 5, 9 b-Hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) 1-naphtho [1,2-c] -furan-1,3-dione, 5-- (2, 5 —Dioxotetrahydrofural) 1 3-Methyl 1-3-cyclohexene 1,2-dicarboxylic dianhydride, bicyclo [2, 2, 2] Oct 7 7 1, 2, 5, 5, 6-tetracarboxylic Acid dianhydride, 3-oxabicyclo [3.2.1] Octane 1,2,4-dione 6-Spiro 3,-(tetrahydrofuran 1 ', δ' dione), 3, 5, 6-tricarboxy 2— Carboxynorbornane 2: 3, δ: 6-dianhydride, bicyclo [3. 3. 0] octane 1, 2, 4,

Aliphatic and alicyclic tetracarboxylic dianhydrides such as 6,8-tetracarboxylic dianhydride, compounds represented by the following formulas (I) and (I I);

(Wherein R ¹ and R ³ represent a divalent organic group having an aromatic ring, R ² and R ⁴ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ^{4 each} represent They may be the same or different.)

Pyromellitic dianhydride, 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4' — biphenyl sulfone tetracarboxylic acid Water, 1, 4, 5, 8—naphthalene tetracarboxylic dianhydride, 2, 3, 6, 7 —naphthalene tetracarboxylic dianhydride, 3, 3 ', 4, 4, 1 biphenyl ether Tertetracarboxylic dianhydride, 3, 3 4, 4, -dimethyldiphenylsilan tetracarboxylic dianhydride, 3, 3 ', 4, 4, -tetraphenylsilane terephthalic acid dianhydride, 1, 2 , 3, 4 Monofurantetracarboxylic dianhydride, 4, 4, — Bis (3, 4-dicarboxyphenoxy) Diphenyl sulfide dianhydride, 4, 4 ′ — Bis (3, 4− Dicarboxyphenoxy) Diphenylsulfone dianhydride, 4, 4 'monobis (3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3, 3', 4, 4 '— Perfluoro Loisopropylidenediphthalic acid dianhydride, 3, 3 ', 4, 4' — biphenyltetracarboxylic dianhydride, (Phthalic acid) Phenylphosphine oxide dianhydride, p-Phenylene monobis (Triphenyl phthalic acid) dianhydride, m-Phenylene mono bis (Triphenyl phthalic acid) Dihydrate, Bis (Trif Enylphthalic acid) _4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) —4,4'-diphenylmethane dianhydride, ethylene glycol monobis (anhydrotrimellitate), propylene Glycol monobis (anhydro trimellitate), 1,4-butanedio rubis (anhydro trimellitate), 1,6-hexanediol monobis (anhydro trimellitate), 1,8-octanediol monobis (Anhydro trimellitate), 2, 2-bis (4-hydroxyphenyl) propane monobis (anhydro trimellitate), Serial formula (1) and aromatic tetracarboxylic dianhydrides such as compounds represented by - (4). These may be used alone or in combination of two or more.

Of these, butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-hydr F

Ranyl) 1 3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1, 2, 3, 4— Cyclopentane tetra-luronic acid dianhydride, 1, 2, 4, 5—cyclohexanetetracarboxylic dianhydride, 2, 3, 5-tricarboxycyclopentyl acetic acid dianhydride, 5-— (2, 5-Dioxotetrahydrofural) 1 3-Methyl _3-Cyclohexene 1 1,2-Dicarboxylic dianhydride, 1, 3, 3 a, 4, 5, 9 b-Hexahydro-5- (Tetrahydro 2 , 5-dioxo-3-furanyl) —naphtho [1,2-c] furan-1,3-dione, 1,3,3 a, 4,5,9b monohexahydro-1-methyl-5- (tetrahydro-2 , 5—Dioxo 3—Frael) 1 naphtho [1, 2— c] 1 franc 1, 3-dione, 1, 3, 3 a, 4, 5, 9b—Hexahydro-5,8-dimethyl-5_ (tetrahydro-2,5-dioxo_ 3-furanyl) 1-naphtho [1,2-c] furan-1,3-dione, bicyclo [2, 2, 2] — Oct-7-en-1,2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro_3,1 (tetrahydrofuran ', 5'-dione), 3, 5, 6-tri-force lupoxy-2-carboxynorbornane 1: 3,5: 6-dianhydride, bicyclo

[3. 3. 0] Octane 1, 2, 4, 6, 8—tetracarboxylic dianhydride, pyromeritic dianhydride, 3, 3 ′, 4, 4 ′ monobenzophenone tetracarboxylic dianhydride Water, 3, 3 ', 4, 4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, represented by the above formula (I) Among the compounds, the compound represented by the following formulas (5) to (7) and the compound represented by the following formula (8) among the compounds represented by the above formula (II) have good liquid crystal orientation. It is preferable from the viewpoint that it can be expressed, and more preferable is 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dixotetrahydro 3-furanyl) —Methyl—3-cyclohexene— 1,2-dicarboxylic anhydride, 1,3-dimethyl-1, 2, 3, 4-cyclobutanetetracar Boronic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 2, 3, 5-tricarboxycyclopentyl acetic acid dianhydride, 1, 3, 3 a, 4, 5, 9b —Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan 1,3-dione, 1,3,3 a, 4, 5, 9 b- Xahydro-8-methyl-5- (tetrahydro-2,5-dixo-3-furanyl) 1-naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2 , 4-dione, 6-spiro-1, 3, (tetrahydrofuran-2 ', 5'-dione), 3, 5, 6-tricarboxyl 2-carboxynorpolnan-2: 3, 5: 6-dianhydride And bicyclo [3.3.0] octane-1,2,4,6,8-tetracarboxylic dianhydride, pyromellitic dianhydride, and a compound represented by the following formula (5). Of these, particularly preferred are 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) 1 3-methyl-3-cyclohe Xene-1,2-dicarboxylic anhydride, 2,3,5-tri-stroxyloxycyclopentyl acetyl dianhydride, 1, 3, 3 a, 4, δ, 9 b-hexahydro-5- (tetrahydro- 2,5-Dioxo_ 3-furanyl) One naphtho [1,2, c] furan 1,3-Dione, 1,3,3a, 4,5,9b-Hexahydro 8-Methyl-5- ( Tetrahydro-2,5-dioxo-3-furanyl) 1-naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride.

[Diamine compounds]

Examples of diamine compounds used in the synthesis of the polyamic acid include P-phenylenediamine, m-phenylenediamine, 4, 4'-diaminodiphenyl methane, 4, 4'-diaminodiphenylethane, 4, 4 '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'- Diaminodiphenyl, 1,5-diaminonaphtholene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-11 (1,4'-aminominophenyl) -1,3,3-trimethylindane 6-Amino 1- (4, 1-aminophenol) 1 1, 3, 3-Trimethylindane, 3, 4'-Diaminodiphenyl ether Le, 3, 3 '— Gaminobenzofenone, 3, 4' Diaminobenzofenone, 4, 4, Diaminobenzofenone, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 2, 2-bis [4-1- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [41- (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) Hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenol) fluorene, 4,4'-methylenbis (2-chloroaniline), 2, 2 ', 5, 5' Tet Lachloro-4,4'-diaminobiphenyl, 2, 2, —Diclonal 4,4'-Diamino-1,5,5'—Dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 '— (P-phenylene isopropylidene) bisaniline, 4, 4,-(m-phenylene isopropylidene) bisaniline, 2, 2, 1 bis [4 1 (4 1 amino-2-trifluoromethylphenoxy) C) Phenyl] Hexafluoropropane, 4, 4'-diamino-1, 2, 2 '— Bis (trifluoromethyl) biphenyl, 4, 4' — Bis [((4-amino-2- trifluoromethyl) phenoxy ] Fluorophenyl, 2,7-diaminofluorene, 3,6-diaminocarbazol, N-methyl-3,6-diaminocarbazol, N-ethylyl-3,6-diaminocarbazol Le, N—Hue Nilu 3, 6-Diaminocarbazole, N, N '— Bis (4-Aminophenyl) Aromatic diamines such as monobenzidine; 1, 1-metaxylylenediamine, 1, 3-propanediamine, tetramethylenediamine, pentamethylene Diamine, Hexamethylenediamine, Heptamethylethylenediamine, Octamethylenediamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophorone diamine, Te Bok La hydro dicyclopentanol evening Kisahidoro one 4-Genis range § Min to,, 7 Ichimeyu Noin mite range methylenedioxy § Min, tricyclo [6.2.2 1.0 ^{2 '7]} - © down decimeter range methyldichlorosilane § Min, 4, 4, monomethylenebis (cyclohexylamino Aliphatic and cycloaliphatic diamines such as

 2,3-Diaminopyridine, 2,6-Diaminopyridine, 3,4-Diaminopyridine, 2,4-Diaminopyrimidine, 5,6_Diamino 2,3-Dicyanovirazine, 5,6-Diamino-2,4-Dihydroxypyrimidine 2,4-diamino-1,6-dimethylamino-1,3,5-triazine, 1,4 monobis (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-Phenol, 1, 3, 5-Triazine, 2, 4-Diamino 6-Methyl s- 卜Liazine, 2,4-Diamino-1,3,5-Triazine, 4,6-Diamino-2-vinyl-s-Triazine, 2,4-Diamino-5-phenylthiazole, 2,6-Diaminopurine, 5,6-Diaminopurine 1, 3—Jime Ruracil, 3,5-Diamino-1,2,4-triazol, 6,9-Diamino-1-Two-ethoxylactyl lactate, 3,8-Diamino-6-phenylphenanthridine, 1,4-Diamino Two primary amino groups such as biperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and compounds represented by the following formulas (III) to (VI), Diamines having nitrogen atoms other than primary amino groups;

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

(In the formula, 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 The existing X may be the same or different.)

 Monosubstituted phenylenediamine represented by the following formula (V); diaminoorganosiloxane represented by the following formula (V I);

(V)

, '

(Wherein R ⁷ represents a divalent organic group selected from 1 O—, —COO—, _OCO_, 1 NHCO—, —CONH —, and 1 CO—, and R ⁸ represents a steroid skeleton, trifluoro A monovalent organic group having a group selected from a methyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms.

(In the formula, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, p is an integer of 1 to 3, and q is 1) It is an integer of ~ 20.)

Examples thereof include compounds represented by the following formulas (9) to (13). These diamine compounds can be used alone or in combination of two or more.

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)

Of these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4 , 4'—Diaminodiphenyl ether, 2,2-Dimethyl-4,4′-diaminobiphenyl, 2,2-bis [4 (4- (aminophenoxy) phenyl] propane, 9,9-bis (4-aminominophenyl) Fluore 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane, 2,2_bis (4-aminophenyl) hexafluoropropane, 4, 4,1, (p-phenylene diisopropylidene ) Bisaniline, 4, 4, 1 (m-phenylene diisopropylidene) Bisaniline, 1, 4-cyclohexanediamin, 4, 4, -methylenebis (cyclohexylamine), 1, 4 monobis (4-aminophenoxy) Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,7-diaminofluorene, 3,6-diaminocarbazol, N-methyl-3,6-diaminocarbazole, N-ethyl 3, 6-Diaminocarbazole, N-phenyl 3,6-Diaminocarbazol, N, N '-Bis (4-aminophenyl) monobenzidine, represented by the above formulas (9) to (13) Of the compounds represented by the above formulas, 2, 6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, and the compounds represented by the above formula (III) 14), among the compounds represented by the above formula (IV), the compound represented by the following formula (15), among the compounds represented by the above formula (V): Of the compound represented by each of (23) and the compound represented by the above formula (VI), a compound represented by the following formula (24) is preferred.

CH ₃ CH ₃

H ₂ N-(CH ₂ ) ₃ — Si-O- Si- (CH ₂ ) ₃ 1 NH ₂ (2 4)

CH ₃ CH ₃

[Synthetic reaction of polyamic acid]

 The proportion of tetracarboxylic dianhydride and diamine compound used in the polyamic acid synthesis reaction is such that the amount of acid anhydride group of tetracarboxylic dianhydride is 1 equivalent to the amino group contained in the diamine compound. The ratio force S to be 0.2 to 2 equivalents S is preferable, and the ratio to be 0.3 to 1.2 equivalents is more preferable.

The synthesis reaction of the polyamic acid is performed in an organic solvent under a temperature condition of preferably 1 20 to 15 50 t: more preferably 0 to 100. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Sulfoxide, aptilolactone, tetrame Examples include aprotic polar solvents such as tyluurea and hexamethylphosphoric triamide; and phenolic solvents such as m-cresol, xylenol, phenol, and nonogenated phenol. In addition, the amount of organic solvent used (a) is 0.1 to 30% by weight based on the total amount of tetraforce rubonic acid dianhydride and diamine compound (b) and the total amount of reaction solution (a + b). Such an amount is preferred.

 [Poor solvent]

 In addition, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc., which are poor solvents for polyamic acid, can be used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butyl diol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, Butyl Lactate, Acetone, Methyl Ethyl Ketone, Methyl Isoptyl Ketone, Cyclohexanone, Methyl Acetate, Ethyl Acetate, Ptyl Acetate, Methyl Methyl Cypropionate, Ethyl Ethoxy Propionate, Jetyl Succinate, Jetyl Malon, Jetyl Ether , Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol i-propyl ether, ethylene N-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol jetyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, jetylene 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 And xylene.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. Then, this reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and this precipitate is dried under reduced pressure. A polyamic acid can be obtained by drying. Further, 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.

<Imidized polymer>

 The imidized polymer used in the liquid crystal aligning agent of the present invention can be synthesized by dehydrating and ring-closing the polyamic acid. The imidized polymer referred to here includes a partially imidized polymer obtained by partially imidizing the polyamic acid and a polymer obtained by immobilizing 100%. “Combined”. Dehydration and ring closure of polyamic acid is required by (i) heating the polyamic acid or (i 1) dissolving polyamic acid in an organic solvent and adding a dehydrating agent and dehydration ring closure catalyst to this solution. According to the method of heating according to this.

 The reaction temperature in the above method (i) of heating the polyamic acid is preferably 50 to 200, more preferably 60 to 170. If the reaction temperature is less than 50, the dehydration ring-closing reaction does not proceed sufficiently, and if the reaction temperature exceeds 20 Ot :, the molecular weight of the resulting imidized polymer may decrease.

On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably from 0.01 to 20 mol per 1 mol of the polyamic acid repeating unit. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably from 0.01 to 10 mol per mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180, more preferably 10 to 15:50. Further, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained. <End-modified polymer>

 The polyamic acid and the imidized polymer may be of a terminal modified type with a controlled molecular weight. By using this terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when the polyamic acid is synthesized. Here, as the acid monoanhydride, for example, maleic anhydride, anhydrous fuuric acid, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride And n-hexadecyl succinic anhydride. Examples of the monoamine compound include 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-pendecylamine, n-hexadecylamine, n-heptdecylamine, n-decylamine, n-eicosylamine, etc. it can. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

<Logarithmic viscosity of polymer>

 The polyamic acid and imidized polymer obtained as described above preferably have a value of logarithmic viscosity (τ? Ϊ́ η) of preferably 0.05 to 10 d 1 /, more preferably 0.05 to 5 d 1.

The value of the logarithmic viscosity (τ? _{1 η} ) in the present invention was measured at 30 for a solution having a concentration of 0.5 g Zl 0 ml using N-methyl-2-pyrrolidone as a solvent. It is obtained by the following formula (i). 1 n (solution flow time / solvent flow time)

 i n = (1)

 (Polymer weight concentration)

<Epoxy group-containing compound>

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

(In the formula, R ^{Q 1} is a hydrogen atom or a monovalent organic group having 6 to 30 carbon atoms bonded to the N atom represented by the above formula and an aliphatic carbon.)

Examples of the monovalent organic group of R ^{Q 1} include an alicyclic hydrocarbon group having a cyclohexane ring, a norbornene ring, an adamantane ring, an aromatic hydrocarbon such as a benzene ring and a naphthenic ring. It preferably contains a group.

Examples of the epoxy compound represented by the above formula (A) include compounds represented by the following formulas (A) — 1, (A) 1-2, and (A) -3.

In the above formulas (A) — 1, (A) 1-2, and (A) — 3, R ^{G 2} is a hydrogen atom or a monovalent organic group such as an alkyl group or a phenyl group. It may be a ring structure. R ^{0 2} may combine with the ring-forming carbon of the cyclohexane ring or benzene ring shown in (A) — 1, (A) 1 2 and (A) — 3 to form a ring structure. . R ^{Q 3} is a hydrogen atom or a monovalent organic group such as an alkyl group or a phenyl group, and a plurality of R ^{Q 3} may be different from each other. R ^{Q 2} and R ^{Q 3} may be cross-linked in the same molecule.

Specific examples of such epoxy compounds include N, N-diglycidylcyclohexylamine, N, N-diglycidyl-2-methylcyclohexylamine, N, N-diglycidyl 4-methylcyclohexylamine, N, N-diglycidyl 2, 3-dimethylcyclohexylamine, N, N-diglycidyl 3, 3, 5-trimethylcyclohexyl, N, N-diglycidyl 4-tert-butylcyclohexylamine, N, N-diglycidyl 2-aminonorbornane, N , N-diglycidyl 1-ethynylcyclohexylamine, N, N-diglycy 1-adadamantane methylamine, 1,2,3,4-tetrahydro-1-mononaphthylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidyl-1-adadamantanemethylamine, N, N-diglycidyl _ 1-cyclohexylethylamine, N, N-diglycidyl 1-adamantane 1-ylethylamine, N, N-diglycidylbenzylamine, N, N-diglycidyl _2-methylbenzylamine, N, N —Diglycidylru 3-methylbenzylamine, N, N-diglycidyl_4 monomethylbenzylamine, N, N-diglycidyl2,5-dimethylbenzylamine, N, N-diglycidyl-2-methoxybenzylamine, N, N-diglycidyl-3-methoxybenzylamine, N, N-diglycidyl 4-methoxybenzylamine, N, N-diglyci 1-aminoindane, N, N-diglycidylbenzhydrylamine, N, N-diglycidyl- 1-phenol dilencylamine, N, N-diglycidyl 1 1-phenol 2 1-propaneamine, N, N-diglycidyl 1- (4-methoxyphenyl) ethylamine, N, N-diglycidyl 1- (1 naphthyl) ethylamine, N, N-diglycidyl 1 1- (p-tolyl) ethylamine, N, N-diglycidyl 1 _ phenyl 1 2-( p-tolyl) ethylamine, N, N-diglycidyl triphenylmethylamine and the like. Of these, N, N-diglycidylaminomethylcyclohexane and N, N-diglycidylbenzylamine are preferred as preferred.

<Liquid crystal aligning agent>

 The liquid crystal aligning agent of the present invention comprises at least one selected from the [a] component comprising at least one polymer selected from polyamic acids and imidized polymers thereof, and an epoxy compound represented by the above formula (A). The component [b] composed of seed is dissolved and contained 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, The amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

As the organic solvent for dissolving the [a] component and the [b] component, these can be dissolved. The solvent is not particularly limited as long as it can be used, and examples thereof include the same solvents as exemplified for use in the synthesis of polyamic acid and dehydration ring closure.

 Further, the liquid crystal aligning agent of the present invention may contain a functional silane-containing compound for the purpose of further improving the adhesion to the substrate. Examples of such functional silane-containing compounds include 3-aminomino trimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyl trimethoxysilane,

2-Aminopropyltriethoxysilane, N- (2-Aminoethyl) 1 3-Aminopropyl trimethoxysilane, N_ (2-Aminoethyl) 1 3-Aminopropylmethyldimethoxysilane, 3_Ureidopropyl Methoxysilane, 3-uredopropyltriethoxysilane, N-ethoxycarbonyl tri-aminotrimethoxysilane, N-ethoxycarbonyl 3-aminopropylenetoxisilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene-amine, 10-trimethoxysilyl-1,4- 4,7-triazadecane, 10-triethoxysilyl-1,4-, 7-triazadecane, 9-trimethoxysilyl-1,3, 6-diazanonyl acetate, 9-triethoxysilyl-1,3,6-diazano Nyl acetate, N-benzyl-3 -aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl _ 3-aminopropyl trimethoxysilane, N-phenol 3-methoxyamino卜 Riethoxysilane, N-bis (oxchethylene) 1 3-Aminopropyl trimethoxysilane, N-bis (oxyethylene) 1

Examples thereof include 3-aminopropyltriethoxysilane.

The solid concentration (total concentration of [a] component, [b] component and additive) in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc. It is in the range of ~ 20% by weight. When the solid content concentration is less than 0.1% by weight, the coating film (film) becomes too thin to obtain a good liquid crystal alignment film, and the solid content concentration is less than 20% by weight. If it exceeds the upper limit, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating characteristics. There is a match.

LCD device>

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

(1) A liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention on one surface of a substrate on which a patterned transparent conductive film is provided, for example, a roll coater method, a spinner method, a printing method, an ink jet method, etc. Then, the coated surface is formed by heating the coated surface. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film provided on one surface of a substrate, NESA film made of tin oxide (S N_〇 ₂₎ (US PPG registered trademark), oxidation in Jiumu tin monoxide - from _{(ln 2 0 3 S n 0} 2) An ITO film or the like can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, etc. Can also be applied in advance. The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 30 O :, more preferably 120 to 25.50. The liquid crystal aligning agent of the present invention containing a polyamic acid has a force to form a coating film that becomes an alignment film by removing the organic solvent after coating, and further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be a coating film. The film thickness of the coating film to be formed is preferably from 0.01 to 1 m, more preferably from 0.05 to 0.5 m.

(2) A rubbing process is performed in which the surface of the film formed of the liquid crystal aligning agent is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Thereby, the alignment ability of the liquid crystal molecules is imparted to the film to form a liquid crystal alignment film. In addition to the rubbing method, the surface of the resin film is irradiated with polarized ultraviolet rays, ion beams, electron beams, etc. to give alignment ability, uniaxial stretching method, Langmuir- The liquid crystal alignment film can also be formed by a method of obtaining a film by a blow jet method or the like. In order to remove the fine powder (foreign matter) generated during the rubbing process and clean the surface, it is preferable to clean the formed liquid crystal alignment film with isopropyl alcohol or the like. Also, a treatment for changing the pretilt angle by partially irradiating the surface of the formed liquid crystal alignment film with ultraviolet rays, ion beams, electron beams, etc. (for example, Japanese Patent Laid-Open No. 6-2 2 2 3 6 (Kaihei 6-2 8 1 9 3 7), JP 7-1 6 8 1 87, JP 8-2 3 4 2 07), surface of the liquid crystal alignment film formed A resist film is partially formed on the substrate, and a rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed to change the alignment ability of the liquid crystal alignment film (for example, a special The viewing angle characteristics of the manufactured liquid crystal display element can also be improved by performing Kaihei 5- 10 7 5 4 4).

 (3) Two substrates on which the liquid crystal alignment film is formed as described above are produced, and the two substrates are formed so that the alignment treatment direction in each liquid crystal alignment film, that is, the rubbing direction is orthogonal or antiparallel. The two substrates are placed opposite to each other with a gap (cell gap) between them, and the liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealing agent. The holes are sealed to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, the polarizing plate is aligned with the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element can be obtained by bonding them so as to be orthogonal.

 Here, as the sealant, for example, an epoxy resin containing a hardener and aluminum oxide spheres as a spacer can be used.

Examples of liquid crystals include nematic liquid crystals such as Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, and pyrimidine liquid crystals. Liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. In addition, these liquid crystals include, for example, cholestyl chloride, Cholesteryl type liquid crystals such as cholesteryl nonate and cholesteryl carbonate may be used with the addition of chiral agents such as those sold under the trade names “C-15” and “CB-15” (Merck). it can.

 In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between a protective film of roulose acetate or A polarizing plate made of the H film itself can be mentioned.

 As described above, the liquid crystal aligning agent of the present invention is excellent in storage stability, and according to this, it can form a tough film that is not easily damaged by rubbing treatment performed under various conditions. It is possible to form a liquid crystal alignment film having excellent alignment regulating power. For this reason, a liquid crystal display element free from alignment failure can be obtained. The liquid crystal display element of the present invention can be effectively used in various devices, for example, display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be suitably used. Example

 [Liquid crystal orientation]

 Example · The presence or absence of anomalous domains when the voltage was turned on / off (applied / released) in the liquid crystal display element prepared in the comparative example was observed with a polarizing microscope. Table 1 summarizes the results of the evaluation of the liquid crystal alignment for each alignment agent.

 [Voltage holding ratio]

A voltage of 5 V was applied to the liquid crystal display element at an application time of 60 msec and a span of 1667 milliseconds, and the voltage holding ratio was measured after 16 7 milliseconds after the application was released. The measurement device used was VH R-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 90% or higher was judged as good, and the other cases were judged as bad. The results of evaluating the voltage holding ratio for each alignment agent are summarized in Table 1. [Storage stability of liquid crystal alignment agent]

 The liquid crystal aligning agent is allowed to stand at room temperature for one week, and the viscosity of the liquid crystal aligning agent before and after being left is measured using an E-type viscometer. The change rate of the viscosity calculated based on the following formula (ii) is The cases within% were judged as good and the other cases were judged as bad.

 The results of evaluating the storage stability of each alignment agent are summarized in Table 1. Initial viscosity (mPs) — viscosity after 90 days (mPs)

Viscosity reduction rate (%) = (i i) Initial viscosity (mPs) Synthesis example 1

 In a 200 ml three-necked flask equipped with a Dimroth condenser, 12.52 ml (0.16 mo 1) of epichlorohydrin, 18 ml of ethanol and 1.8 ml of pure water were mixed and heated to 50 with stirring. Aminomethylcyclohexane 4.δ 3 g (0.04 mo 1) was added dropwise to this solution while paying attention to the temperature rise of the reaction solution, while adjusting the reaction temperature between 48-53. Thereafter, the mixture was heated and stirred within the same temperature range for 3 hours, the reaction temperature was adjusted to 30, 8 g of 50% NaOH aqueous solution was added dropwise over 45 minutes, and the mixture was further heated and stirred at the same temperature for 3 hours. The deposited salt was removed by filtration, the filtrate was transferred to NASFlasco, and ethanol was removed by evaporation. To the residue, 30 ml of toluene was added, followed by separation and washing four times with 15 ml of pure water and once with 15 ml of a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered. The organic layer was concentrated by evaporation.

The resulting viscous liquid was purified by column chromatography (developing solvent: hexane Z ethyl acetate = 2Z1) to obtain 3.2 g of N, N-diglycidylaminomethylcyclohexane.

 Synthesis example 2

In a 200 ml three-necked flask equipped with a Dimroth condenser, mix 1.25 ml (0.16 mo 1) of epichlorohydrin, 18 ml of ethanol, 1.8 ml of pure water, Warm to 50 with stirring. To this solution, 4.29 g (0.04 mo 1) of benzylamine was added dropwise while keeping the temperature of the reaction solution between 48 and 53 while paying attention to the temperature of the reaction solution. Thereafter, the mixture was heated and stirred for 3 hours within the same temperature range, the reaction temperature was adjusted to 30, 8 g of a 50% NaOH aqueous solution was added dropwise over 45 minutes, and the mixture was further heated and stirred at the same temperature for 3 hours. The precipitated salt was removed by filtration, the filtrate was transferred to an eggplant flask, and ethanol was removed by evaporation. To the residue, 30 ml of toluene was added, followed by separation and washing four times with 15 ml of pure water and once with 15 ml of a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, the magnesium sulfate was filtered, and the organic layer was concentrated by evaporation.

The resulting viscous liquid was purified by column chromatography (developing solvent: hexane Z ethyl acetate = 2Z1) to obtain 5.6 g of N, N-diglycidylbenzylamine.

 Synthesis example 3

2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 224. 17 g (0.5 mol) and 1, 3, 3 a, 4, 5, 9 b —hexahydro-8- Methyl-5- (tetrahydro-1,2,5-dioxone 3-furanyl) mononaphtho [1,2-c] monofuran 1,3-dione 157.14 g (0.5 mol), p as diamine compound —Phenylenediamine, 94.62 g (0.8.75 mol), bisaminopropyltetramethyldisiloxane 24.85 g (0.1 mol) and 3,6-bis (4-aminobenzoyloxy) cholestane 6.4 3 g (0.01 mol) η-aged decadecylamine as a monoamine 8.09 g (0.03 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 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 under reduced pressure for 15 hours to obtain 370 g of polyamic acid having a logarithmic viscosity of 0.82 dlZg. 30 g of the resulting 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, and dehydration ring closure was carried out at 1 10 for 4 hours. Precipitate, wash, decompress, 18.5 g of polyimide with a logarithmic viscosity of 0.77 dlZg (this is called “Polyimide (A_1)”) was obtained.

 Synthesis example 4

 2,3,5-tricarboxycyclopentyl succinic dianhydride as tetracarboxylic dianhydride 224. 17 g (0.5 mol) and 1, 3, 3 a, 4, 5, 9 b —hexahydro —Methyl-5— (Tetrahydro-1,2,5-Dioxo1,3-Frael) One naphtho [1, 2— c] —Furan 1,3-Dione 157. 14 g (0.5 mol), p as diamine compound —Phenylene diamine 93. 27 g (0.8 625 mol), bisaminopropyltetramethyldisiloxane 24. 85 g (0.1 mol) and 4′-cyclohexylene 3,5-diaminobenzene 13. 1 δ g (0.03 mol) and 1.40 g (0.015 mol) of aniline as a monoamine were dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol, and dried at 40 under reduced pressure for 15 hours to obtain 370 g of polyamic acid having a logarithmic viscosity of 0.82 dlZg. 30 g of the resulting polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of succinic anhydride were added, and dehydration and ring closure at 110 at 4 hours. Precipitation, washing, and decompression were performed in the same manner as described above to obtain 18.5 g of a polyimide having a logarithmic viscosity of 0.77 dlZg (hereinafter 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'-diamino as diamine compound Biphenyl 212 g (1.0 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 6 for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. After washing with methyl alcohol and drying for 15 hours at 40 under reduced pressure, polyamic acid with a logarithmic viscosity of 0.90 d lZg (this is called “polyamic acid (B— 1) “)” 360 g was obtained.

 Synthesis example 6

 Pyromellitic dianhydride 109.06 g (0.5 mole) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.5 mole) as tetracarboxylic dianhydride, As the diamine compound, 198.3 g (1.0 mol) of 4,4, -diaminodiphenylmethane was dissolved in 4,500 g of N-methyl-2-pyrrolidone, and reacted at 60 for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. After washing with methyl alcohol and drying at 40 under reduced pressure for 15 hours, 365 g of polyamic acid having a logarithmic viscosity of 0.90 d lZg (referred to as “polyamic acid (B-2)”) was obtained. . Example 1

The polyimide (A-1) obtained in Synthesis Example 3 and the polyamic acid (B-1) obtained in Synthesis Example 5 were mixed so that polyimide: polyamic acid = 20: 80 (weight ratio). Dissolve in 1-ptilolactone-methyl-2-pyrrolidone Z-ptylcetone solvent mixture (weight ratio 70Z20Z10), and further add 10 times the N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 to the polymer. An amount of a part was added to obtain a solution having a solid content of 4% by weight. After sufficient stirring, the solution was filtered using a filter having a pore size of 0.2 to prepare the liquid crystal aligning agent of the present invention. The above liquid crystal aligning agent is applied onto a transparent conductive film made of an ITO film on one side of a 1 mm thick glass substrate using an inkjet printer (rotation speed: 2,000 rpm, application time: 1 And dried at 200 for 1 hour to form a film with a dry film thickness of 0.08 m. A rubbing machine having a roll in which a rayon cloth was wrapped around this film was subjected to a rubbing treatment with a roll rotation speed of 400 rpm, a stage moving speed of 3 cm nosec, and a hair foot indentation length of 0.4 mm. The liquid crystal alignment film coated substrate was immersed in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 for 5 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 // m to each outer edge of the liquid crystal alignment film coated substrate of the pair of transparent electrodes, the liquid crystal alignment film coated substrate. The liquid crystal alignment film surface is opposite The adhesives were cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6221, MLC-6221) is filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarized on both sides of the substrate. The plates were laminated to make a liquid crystal display element. The voltage holding ratio and liquid crystal orientation of the obtained liquid crystal display element were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1. The liquid crystal aligning agent obtained in the present invention was confirmed to have good voltage holding ratio and liquid crystal alignment.

 Example 2

 The polyimide (A-1) obtained in Synthesis Example 3 and the polyamic acid (B-2) obtained in Synthesis Example 6 were mixed so that polyimide: polyamic acid = 20: 80 (weight ratio). -Butyrolactone / N-methyl-2-pyrrolidone-nobutylcetosolve mixed solvent (weight ratio 70Z20-10) and N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 was polymerized. Ten parts by weight were added to one to obtain a solution with a solid content of 4% by weight. After sufficient stirring, this solution was filtered using a filter having a pore size of 0.2 // m to prepare the liquid crystal aligning agent of the present invention. Using the liquid crystal aligning agent thus prepared, a film was formed on the substrate surface in the same manner as in Example 1, and a liquid crystal display element was produced using the substrate on which the liquid crystal aligning film was formed. Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. 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 were mixed so that polyimide: polyamic acid = 20: 80 (weight ratio). Dissolve in propylolactone ZN-methyl-2-pyrrolidone Z-ptylcetosolv solvent (weight ratio 70- 20Z10) and use N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 as a polymer. In contrast, 10 parts by weight was added to obtain a solution having a solid concentration of 4% by weight. After sufficient stirring, this solution was filtered using a filter having a pore size of 0.2 zm to prepare the liquid crystal aligning agent of the present invention. Using the liquid crystal aligning agent thus prepared, a film was formed on the substrate surface in the same manner as in Example 1. And a liquid crystal display element was manufactured using the substrate on which the liquid crystal alignment film was formed. Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.

 Examples 4-6

According to the formulation shown in Table 1 below, polyimides (A-1) to (A-2) and polyamic acids (B-1) to (B-2) obtained in Synthesis Examples 3 to 6 and Synthesis Example 2 were obtained. 10 parts by weight of the obtained N, N-diglycidyl benzylamine with respect to the polymer was added to the alpha-ptyrolactone ZN-methyl-2-pyrrolidone Z-ptylcetosolve solvent mixture (weight ratio 70/200). A liquid crystal aligning agent of the present invention was prepared by dissolving and obtaining a solution having a solid content concentration of 4.0% and filtering this solution through a filter having a pore size of 0.2 / xm. Using each of the thus prepared liquid crystal alignment agents, a film was formed on the substrate surface in the same manner as in Example 1, and a liquid crystal display element was manufactured using the substrate on which the liquid crystal alignment film was formed. . Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.

table 1

 Polymer Polymer mixing ratio Epoxy compound Liquid crystal orientation with respect to polymer Storage stability Voltage holding ratio Weight%

Example 1 A-1 B-1 20/80 N, N-Cyclic aminomethylcyclohexane 10 Good Good Good Example 2 A-1 B-2 20/80 N, N- Quaricyl'laminomethylcyclohexane 10 Good Good Good Example 3 A-2 B-1 20/80 N, N-Silicy's lyaminomethylcyclohexane 10 Good Good Good Example 4 A -1 B-1 20/80 N, N-squeeze to squeeze lumamine 10 Good Good Good Example 5 A-1 B-2 20/80 N, N-squeeze lysyl Example 6 A-2 B-1 20/80 N, N-SiC Rishi-he-Lumin 10 Good Good Good

Claims

The scope of the claims

1. [a] at least one polymer selected from polyamic acid and imidized polymer thereof, and [b] a compound containing two epoxy groups in the molecule represented by the following formula (A) A liquid crystal aligning agent characterized by comprising:

(In the formula, R ^{Q 1} is a hydrogen atom or a monovalent organic group having 6 to 30 carbon atoms bonded to the N atom represented by the above formula and an aliphatic carbon.)

2. The liquid crystal aligning agent according to claim 1, wherein the monovalent organic group of R ^{Q 1 in} the formula (A) contains an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

3. The liquid crystal aligning agent according to claim 1 or 2, wherein the component [b] is represented by each of the following formulas (A) — 1, (A) 1-2 and (A) — 3.

(In the formula, R ^{Q 2} is hydrogen or a monovalent organic group, and when there are a plurality of them, they may be different from each other and may form a ring structure. Also, R ^Q2 is (A) —1, It may combine with the ring-forming carbon of the cyclohexane ring or benzene ring shown in (A) -2 and (A) — 3. R ^Q3 is hydrogen or a monovalent organic group. ^Yes , R ^Q2 and R ^Q3 may be bridged in the same molecule.) The above component [a] 100 parts by weight of the above component [ The liquid crystal aligning agent according to any one of claims 1 to 3, comprising 0.01 to 40 parts of b].

5. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein a tetracarboxylic dianhydride as a raw material monomer of the polymer [a] is 2, 3, 5 monotricarboxycyclopentylacetic acid dianhydride.

6. A liquid crystal display element comprising a liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 5.