KR20070115780A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent is provided to form no foam when applied onto a substrate, to ensure good coatability, and to produce liquid crystal aligning films having good liquid crystal aligning properties and electric characteristics. A liquid crystal aligning agent contains (A) a polymer having a repeat unit represented by the following formula 1a and/or a repeat unit represented by the following formula 1b, and (B) an epoxy compound represented by the following formula 2. In the formula 1a, P^1 is a tetravalent organic group and Q^1 is a divalent organic group. In the formula 1b, P^2 is a tetravalent organic group and Q^2 is a divalent organic group. In the formula 2, n is an integer of 1-30 and R1 is an n-valent organic group.

Description

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

[Patent Document 1] Japanese Unexamined Patent Publication No. 6-222366

[Patent Document 2] Japanese Unexamined Patent Publication No. 6-281937

[Patent Document 3] Japanese Patent Application Laid-Open No. 5-107544

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, it relates to the liquid crystal aligning agent excellent in printability, and the liquid crystal display element obtained from this.

Currently, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as a board | substrate for liquid crystal display elements, two of these are opposingly arranged, A so-called TN type (twisted nematic) in which a layer of a nematic liquid crystal having dielectric anisotropy is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other substrate. TN type liquid crystal display elements having a liquid crystal cell are known. In addition, a STN (Super Twisted Nematic) type liquid crystal display element capable of achieving a high contrast ratio compared to a TN type liquid crystal display element or an IPS (In-Plane Switching) type liquid crystal display having low visual dependence A device, a VA (Vertical Alignment) type liquid crystal display device, and an optical compensation bend (OCB) type liquid crystal display device having low visual dependence and excellent high speed response of a video screen have been developed.

As a material of the liquid crystal aligning film in these liquid crystal display elements, although polyimide, polyamide, polyester, etc. are known conventionally, polyimide is especially used for many liquid crystal display elements excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc. . The liquid crystal aligning film containing a polyimide is usually obtained by apply | coating the liquid crystal aligning agent which is a polyamic acid which is a polyimide precursor, and the organic solvent solution of soluble polyimide on a board | substrate, and imidating by heating. In the said liquid crystal aligning agent, the silane coupling agent may be added in order to improve the leveling property with respect to a board | substrate.

However, although the leveling property with respect to a board | substrate improves the liquid crystal aligning agent which added the silane coupling agent, foam | bubble easily arises at the time of application | coating, and this bubble becomes a cause of the pinhole of a liquid crystal aligning film, and the orientation of a liquid crystal and the liquid crystal display element obtained There was a problem that the electrical characteristics are lowered.

An object of the present invention is to provide a liquid crystal aligning agent having good coatability without foaming upon coating to a substrate.

Another object of the present invention is to provide a liquid crystal display device having a liquid crystal alignment film excellent in liquid crystal alignment and electrical properties without pinholes.

Still 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, firstly, (A) a polymer having a repeating unit represented by the formula (1a) and / or a repeating unit represented by the formula (1b), and

(B) Epoxy-containing compound represented by the following formula (2)

It is achieved by the liquid crystal aligning agent containing.

(Wherein, P ¹ is a tetravalent organic group, Q ¹ is a divalent organic group)

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group)

(Wherein n is an integer of 1 to 30 and R ₁ is an n-valent organic group)

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

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

(A) polymer

The polymer used in the present invention has a repeating unit represented by Formula 1a and / or a repeating unit represented by Formula 1b. For example, the imidation polymer which has a structure obtained by carrying out dehydration ring closure (imidization) of a polyamic acid and / or the said polyamic acid is mentioned. In addition, the "imide-ized polymer" in this invention includes the thing in which all the repeating units are imidated, and the thing in which the imidation was partially imidated is included. In addition, some of the imide rings may be isoimide rings.

Preferred polymers in the present invention are polymers having a repeating unit represented by Formula 1a and a repeating unit represented by Formula 1b. As a liquid crystal aligning agent which has such a polymer, the polymer of following (1)-(3) is mentioned, for example.

(1) A liquid crystal aligning agent containing both a polyamic acid and an imidation polymer.

(2) The liquid crystal aligning agent containing the prepolymer which has an amic-acid structure, and the block copolymer obtained from the prepolymer which has an imide structure.

(3) The liquid crystal aligning agent containing the imidation polymer obtained by partially dehydrating and ring-closing a polyamic acid.

Among these, (1) and (2) are preferable and (1) is especially preferable.

Polyamic acid

The polyamic acid used for this invention is obtained by making tetracarboxylic dianhydride and diamine react.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for the synthesis | combination of the said polyamic acid, Butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 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-cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5 -Tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuranthratecarboxylic dianhydride, 1,3,3a , 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3- Ranyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-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-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-hexa Hydro-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-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxy Acid dianhydrides, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides, 5- (2,5-dioxotetrahydro-3-fura Aliphatic and cycloaliphatic tetracarboxylic dianhydrides such as nil) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and compounds represented by the following formulas (I) and (II);

(I)

(I)

(II)

(II)

(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 may be the 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 (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro Trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), the following formulas (1) to Aromatic tetracarboxylic dianhydrides, such as the compound represented by (4), are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride Water, 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, 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, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyrommel Dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, the compound represented by the following formulas (5) to (7) among the compound represented by the formula (I) and the compound represented by the formula (II) represented by the formula (8) The compound to be mentioned is preferable at the point which can express favorable liquid-crystal orientation. As particularly preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 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, a pyromellitic dianhydride, and the compound represented by following General formula (5) are mentioned.

[Diamine]

As a diamine used for the synthesis | combination of the said polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4, 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, 3,3'-dimethyl-4,4'-diaminobiphenyl , 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-ditrifluoromethyl-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'-diaminobenzophenone, 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-diamino Fluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'- Diaminobiphenyl, 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- Trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2 -Trifluoromethyl) phenoxy] -octafluorobiphenyl, N, N'-di (4-aminophenyl) -benzidine, N, N'-di (4-amino Aromatic diamines such as phenyl) -N, N'-dimethyl-benzidine;

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- Diamino-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 , 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Diamines having two primary amino groups and nitrogen atoms other than the primary amino group in the molecule, such as aminocarbazole, N-phenyl-3,6-diaminocarbazole and compounds represented by the following formulas (3) to (6) ;

(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)

(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 phenylenediamines represented by the following formula (5);

(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 or group having 6 to 30 carbon atoms having a group selected from fluoro groups)

Diaminoorganosiloxane represented by the following formula (6);

(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 following General formula (9)-(13) are mentioned. These diamines can be used individually or in combination of 2 or more types.

(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, 2,2'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bis Aniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) Biphenyl, the compound represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , remind Among the compounds represented by the following formula (3), among the compounds represented by the following formula (14), the compounds represented by the following formula (15) among the compounds represented by the formula (4), and the compound represented by the formula (5), dodecaneoxy-2, 4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, dodecaneoxy-2,5- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, N, N'-di (4-amino Phenyl) -benzidine, N, N'-di (4-aminophenyl) -N, N'-dimethyl-benzidine, the compound represented by following General formula (16)-(23) is preferable.

[Synthesis of Polyamic Acid]

The use ratio of the tetracarboxylic dianhydride and the diamine compound provided in the synthesis reaction of the polyamic acid 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 a temperature condition 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, Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphotriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, are mentioned. In addition, it is preferable that the usage-amount (a) of an organic solvent is an amount whose total amount (b) of tetracarboxylic dianhydride and a diamine compound becomes 0.1-30 weight% with respect to whole quantity (a + b) of a reaction solution.

In the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, and the like, which are poor solvents of polyamic acid, can be used in combination without causing precipitation of the resulting 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, diethyl 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, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol 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.

The reaction solution which melt | dissolves a polyamic acid as mentioned above is obtained. Then, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with a evaporator to obtain a polyamic acid. Moreover, a polyamic acid can be refine | purified by dissolving this polyamic acid again in an organic solvent, then depositing with a poor solvent, or distilling off under reduced pressure with an evaporator once or several times.

Imidization  polymer

The imidation polymer used for this invention is obtained by dehydrating and ring-closing the polyamic acid obtained by making tetracarboxylic dianhydride and diamine react.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for the synthesis | combination of the said imidation polymer, the compound similar to tetracarboxylic dianhydride used for the synthesis | combination of the polyamic acid mentioned above is mentioned.

As tetracarboxylic dianhydride used for the synthesis | combination of the imidation polymer of this invention, alicyclic tetracarboxylic dianhydride is preferable. As a particularly preferred embodiment, 2,3,5-tricarboxycyclopentylacetic 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. Moreover, alicyclic tetracarboxylic dianhydride and other tetracarboxylic dianhydride can also be used together.

[Diamine]

As diamine used for the synthesis | combination of the said imidation polymer, the diamine same as the diamine used for the synthesis | combination of the polyamic acid mentioned above is mentioned.

As a diamine used for the synthesis | combination of the imidation polymer of this invention, the diamine represented by the said General formula (5) is preferable. As a preferable specific example, among the compounds represented by the said General formula (5), dodecaneoxy-2, 4- diamino benzene, pentadecaneoxy-2, 4- diamino benzene, hexadecaneoxy-2, 4- diamino benzene, octa Decanoxy-2,5-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy The compound represented by -2, 5- diamino benzene and the said General formula (16)-(23) is mentioned.

Moreover, in the imidation polymer of this invention, the diamine represented by the said General formula (5) and other diamine can also be used together. Preferred among other diamines are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-di aminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodi Phenylether, 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-phenyl Rendiisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( 4-aminophenoxy) biphenyl, a compound represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3 , 6-diaminoacridine, N, N'-di (4-aminophenyl) -benzidine, N, N'-di (4-aminophenyl) -N, N'-dimethyl-benzidine, represented by Formula 3 above The compound represented by the said General formula (15) among the compound represented by the said General formula (14), and the compound represented by the said General formula (4) among these compounds can be mentioned.

In the imidation polymer of this invention, the diamine represented by the said General formula (5) is preferably 0.5 weight% or more, especially preferably 1 weight% or more of all the diamines.

[Synthesis of imidized polymer]

The imidation polymer which comprises the liquid crystal aligning agent of this invention is obtained by dehydrating and ring-closing the said polyamic acid. The dehydration ring closure of the polyamic acid may be achieved by (i) heating the polyamic acid, or (ii) 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, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. 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 these. 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. On the other hand, 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. And the reaction temperature of a dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. 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.

The imidized polymer used in the present invention may be one having a low imidization rate, partially dehydrated. The imidation ratio in the imidation polymer used for this invention becomes like this. Preferably it is 80% or more, More preferably, it is 85% or more. Here, "imidation ratio" shall represent the ratio of the number of repeating units which form an imide ring with respect to the total number of repeating units in a polymer in%. At this time, a part of the imide ring may be this soimide ring. The imidation ratio can be calculated | required by the following method.

[Method of measuring imidation ratio of imidized polymer]

The imidized polymer was dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and was determined by the formula represented by the following formula (2).

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100

(Wherein A ¹ is the peak area (10 ppm) derived from the proton of the NH group,

A ² is the peak area derived from other protons,

α is the ratio of the number of other protons to one proton of the NH group in the precursor (polyamic acid) of the polymer)

Terminally modified polymers

The polyamic acid and the imidized polymer may be terminally modified with molecular weight. Such terminal-modified ones can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Here, as an 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 -Eicosylamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

[Solution viscosity]

The value of the solution viscosity (mPa · S) in the synthesis example was determined by using an E-type rotational viscometer with respect to a solution diluted to a predetermined solid content concentration using N-methyl-2-pyrrolidone or γ-butyrolactone as a solvent. The viscosity was measured at 25 degreeC.

(B) epoxy compound

Examples of the epoxy compound used in the present invention include compounds represented by the following general formula (2).

<Formula 2>

(Wherein n is an integer of 1 to 30 and R ₁ is an n-valent organic group)

Examples of the n-valent organic group represented by R ₁ of Formula 2 include R ₂ , R ₃ (CO) ₂ , R ₄ OR ₅ , and the like, and R ₂ , R ₃ , R ₄ , and R ₅ , respectively. An alkyl group having 1 to 50 carbon atoms, an alkylene group having 1 to 50 carbon atoms, a trivalent aliphatic hydrocarbon group, a tetravalent aliphatic hydrocarbon group, a phenyl group, a phenylene group, and the like, and a part of hydrogen is a hydroxy group, a halogen, a glycidyloxy group, It may be substituted with a cycloalkylene group. On the other hand, these organic groups may or may not be branched. In addition, R ₁ may be composed of a plurality of the organic groups.

Specifically, the compound represented by following General formula (24)-(51) is mentioned.

As a commercial item of the epoxy compound which can be used by this invention, Denacol EX611, EX612, EX614, EX622, EX512, EX621, EX411, EX421, EX313, EX314, EX321, EX201, EX211, EX212, EX252, EX911 by Nagase Chemtex , EX941, EX920, EX931, EX111, EX121, EX141, EX146, EX192, EX721, EX203, EX711, EX147, EX221, EM150, Denarex R45EPT, EX810, EX811, EX850, EX851, EX821, EX830, EX832, EX841, EX861 Although EX145, EX171, etc. are mentioned, this invention is not limited to this example.

The said epoxy containing compound can be used individually or in combination of 2 or more types.

The epoxy compound (B) used in the present invention has a molecular weight of preferably 100 to 10,000, more preferably 200 to 5,000.

The compounding ratio of (B) epoxy compound in the liquid crystal aligning agent of this invention is 0.01-2 weight part normally with respect to 100 weight part of (A) polymers, Preferably it is 0.02-1 weight part, More preferably, it is 0.03-0.5 Parts by weight. If it is less than 0.01 weight part, printability improvement effect may become inadequate, and when it exceeds 2 weight part, it may thicken.

LCD Alignment agent

The liquid crystal aligning agent of this invention is comprised by dissolving and containing the said (A) polymer and (B) epoxy containing compound normally in an organic solvent.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of polyamic acid can also be selected suitably, and can be used together.

Solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc. Preferably it is 1 to 10 weight% of range. That is, although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and it is difficult to obtain a favorable liquid crystal aligning film, and solid content When the concentration exceeds 10% by weight, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is also increased, resulting in poor coating properties.

As an organic solvent used for the liquid crystal navigator of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N- dimethylacetamide , 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether , Ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, and the like. These may be used alone or in combination of two or more thereof.

In the aspect which improves the adhesiveness to the surface of a board | substrate, the liquid crystal aligning agent of this invention may contain an epoxy group containing compound. As such an epoxy group containing compound, 1,3,5,6- tetraglycidyl-2,4-hexanediol, N, N, N ', N'- tetraglycidyl-m-xylenediamine, 1, for example , 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-di Glycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, etc. are mentioned as a preferable thing. The compounding ratio of these and an epoxy group containing compound is 40 weight part or less normally with respect to 100 weight part of polymers.

Liquid crystal display element

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

(1) The liquid crystal aligning agent of this invention is apply | coated to one surface of the board | substrate with which the patterned transparent conductive film is provided preferably by methods, such as a printing method, and 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; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd. USA), an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. The method of using a photo-etching method and a preliminary mask is used for patterning these transparent conductive films. In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more 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 formed coating film surface in the fixed direction with the roll which rolled up the cloth which consists of fibers, such as nylon, rayon, and cotton, for example, is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

In addition, ultraviolet rays as disclosed in, for example, Japanese Patent Laid-Open No. 6-222366 or Japanese Patent Laid-Open No. 6-281937 are applied to a liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention. By partially irradiating, a resist film is partially formed on the surface of the liquid crystal aligning film subjected to the treatment such as changing the pretilt angle or the rubbing treatment as disclosed in Japanese Patent Laid-Open No. Hei 5-107544. After the rubbing treatment is performed in a direction different from the rubbing treatment, the resist film is removed to perform a process such as changing the liquid crystal alignment ability of the liquid crystal alignment film, thereby improving the field of view characteristics of the liquid crystal display element.

(3) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, and two board | substrates were opposingly arranged through a clearance gap (cell spacing) so that the rubbing direction in each liquid crystal aligning film might be orthogonal or antiparallel, The periphery of the substrate is bonded using a sealant, the liquid crystal is injected and filled into the cell surface partitioned by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. And the liquid crystal display element is bonded by attaching a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each substrate constituting the liquid crystal cell, so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. Obtained.

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

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type 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 and cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). A chiral agent etc. can also be added and used. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate containing the polarizing plate called H film which absorbed iodine, and extending | stretching polyvinyl alcohol between the cellulose acetate protective films, or the polarizing plate containing H film itself is mentioned. have.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

Synthesis Example 1

As tetracarboxylic dianhydride, 109.06 g (0.5 mol) of pyromellitic dianhydrides, 98.06 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 4, 4- dia as a diamine compound 200.2 g (1.0 mole) of minodiphenyl ether was dissolved in 230 g of N-methyl-2-pyrrolidone and 2060 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours, followed by 1350 g of γ-butyrolactone. Was added to obtain about 3590 g of a solution of polyamic acid having a solution viscosity of 200 mPa · S at a solid content concentration of 10% (referred to as "polyamic acid (A-1)").

Synthesis Example 2

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98.06 g (0.50 mol) as tetracarboxylic dianhydride, 109.06 g (0.50 mol) pyromellitic dianhydride, 4,4'- as a diamine compound 198.27 g (1.0 mol) of diaminodiphenylmethane was dissolved in 230 g of N-methyl-2-pyrrolidone and 2060 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours, followed by 1350 of γ-butyrolactone. g was added to obtain about 3600 g of a solution of polyamic acid having a viscosity of 125 mPa · S at a solid content concentration of 10% (referred to as "polyamic acid (A-2)").

Synthesis Example 3

196.12 g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200.2 g (1.0 mole) of 4,4'-diaminodiphenyl ether as a diamine compound After dissolving in 225 g of N-methyl-2-pyrrolidone and 2021 g of γ-butyrolactone and reacting at 40 ° C. for 4 hours, 1321 g of γ-butyrolactone was added to the solution viscosity at a solid content concentration of 10%. About 3600 g of a 210 mPa · S polyamic acid solution (hereinafter referred to as "polyamic acid (A-3)") was obtained.

Synthesis Example 4

1,2,3,4-cyclobutanetetracarboxylic dianhydride 196.12 g (1.0 mole) as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'-diaminobiphenyl 212.3 as a diamine compound g (1.0 mole) was dissolved in 370 g of N-methyl-2-pyrrolidone and 3300 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours to give a polyamic acid having a solution viscosity of 160 mPa · S (referred to as “polyamic acid (A-4) ") to about 3700 g of the solution.

Synthesis Example 5

224.17 g (1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 200.2 g (1.0 mol) of 4,4'-diaminodiphenyl ether as diamine compound were N-methyl It was dissolved in 240 g of 2-pyrrolidone and 2164 g of γ-butyrolactone, and reacted at 40 ° C for 4 hours to make a polyamic acid having a solution viscosity of 180 mPa · S (this is referred to as "polyamic acid (A-5)"). About 3700 g of solution were obtained.

Synthesis Example 6

11,2,3,5-tricarboxycyclopentylacetic dianhydride 112.1 g (0.5 mol), 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro) as tetracarboxylic dianhydride 157.14 g (0.5 mole) of -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) Mole), 2,2-ditrifluoromethyl-4,4-diaminobiphenyl 32.02 g (0.1 mole), 3,6-bis (4-aminobenzoyloxy) cholestane (indicated by Formula (9) above) 6.43 g (0.01 mol) and 4.04 g (0.015 mol) of octadecaneoxy-2,5-diaminobenzene were dissolved in 960 g of N-methyl-2-pyrrolidone and 9 at 60 ° C. The reaction was time. A small fraction of the obtained polyamic acid solution was added, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The solution viscosity was 58 mPa · S. 2740 g of N-methyl-2-pyrrolidone, 396 g of pyridine, and 409 g of acetic anhydride were added to the obtained polyamic acid solution, and the resultant was dehydrated and closed for 4 hours at 110 ° C. After the imidation reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridine and acetic anhydride used in the imidation reaction in this operation were removed out of the system), so that the solid content concentration was 15.0 wt% and the solid content concentration was 8.0%. A solution viscosity of (γ-butyrolactone solution) was obtained about 2500 g of a solution of an imidized polymer having a viscosity of 31.0 mPa · S and an imidation ratio of about 95% (this is referred to as “imidized polymer (B-1)”).

Synthesis Example 7

112.08 g (0.5 mole) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra as tetracarboxylic dianhydride 157.15 g (0.5 mole) of hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 95.71 g of p-phenylenediamine as a diamine compound ( 0.865 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, and 12.86 g (0.02 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, 8.09 g of N-octadecylamine as monoamine (0.03 mol) was dissolved in 960.0 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. A small amount of the obtained polyamic acid solution was collected, NMP was added thereto, and the viscosity was measured using a solution having a solid content concentration of 10%. The viscosity was 60 mPa · S. Subsequently, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic-acid solution, 396.0 g of pyridine and 409.0 g of acetic anhydride were added, and dehydration ring-closing was carried out at 110 degreeC for 4 hours. After the imidization reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridine and acetic anhydride used in the imidation reaction in this operation were removed from the system), and the solid content concentration was 15.0 wt% and the solid content concentration was 6.0%. Solution Viscosity of (γ-butyrolactone solution) About 2000 g of a solution of imidized polymer having a viscosity of 16.0 mPa · S and an imidation ratio of about 95% (it was referred to as “imidized polymer (B-2)”) was obtained.

Synthesis Example 8

224.17 g (1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 107.06 g (0.99 mol) of p-phenylenediamine as a diamine compound, 3,6-bis (4- 6.43 g (0.01 mol) of aminobenzoyloxy) cholestane was dissolved in 3039 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution having a solution viscosity of about 260 mPa · S. Subsequently, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic-acid solution, 396.0 g of pyridine and 306.0 g of acetic anhydride were added, and dehydration ring-closing was carried out at 110 degreeC for 4 hours. After the imidization reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridine and acetic anhydride used in the imidation reaction in this operation were removed out of the system), and the solid content concentration was about 9.0 wt% and the solid content concentration was 5.0%. About 3000 g of the solution of the imidation polymer (it is called "imidation polymer (B-3))) of 72.0 mPa * S and imidation ratio of about 89% of the solution viscosity of (si-butyrolactone solution) was obtained.

Synthesis Example 9

11,2,3,5-tricarboxycyclopentylacetic dianhydride 112.1 g (0.5 mol), 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro) as tetracarboxylic dianhydride 157.14 g (0.5 mole) of -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 89.21 g of p-phenylenediamine as a diamine compound (0.825) Molar), 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl 32.02 g (0.1 mole), 1- (3,5-diaminobenzoyloxy) -4- (4-trifluoro Romethylbenzoyloxy) -cyclohexane (compound represented by the formula (20), 25.34 g (0.06 mol), octadecaneoxy-2,5-diaminobenzene 4.04 g (0.015 mol) in N-methyl It dissolved in 2175 g of 2-pyrrolidone and reacted at 60 degreeC for 6 hours. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The solution viscosity was 110 mPa · S. 3000 g of N-methyl-2-pyrrolidone was added to 1500 g of the obtained polyamic acid solution, 221.0 g of pyridine and 228.0 g of acetic anhydride were added, and the resultant was dehydrated and closed at 110 ° C for 4 hours. After the imidation reaction, the solvent in the system was solvent-substituted with fresh γ-butyrolactone (pyridine and acetic anhydride used in the imidation reaction in this operation were removed from the system), so that the solid content concentration was about 10.0% by weight and the solid content concentration was 4.5%. About 2000 g of the solution of the imidation polymer (it is called "imidation polymer (B-4)") of about 26 mPa * S and the imidation ratio of about 92% of the solution viscosity of (si-butyrolactone solution) was obtained.

Example 1

100 parts by weight of the imidized polymer (B-1) obtained in Synthesis Example 6 and 0.05 parts by weight of EX-171 (manufactured by Nagase Chemtex Co., Ltd.) as the epoxy-containing compound represented by the formula (2). -Methyl-2-pyrrolidone / butyl cellosolve (71/17/12 (weight ratio)) dissolved in a mixed solvent to a solution having a solid content of 4% by weight, and the solution was filtered using a filter having a pore size of 1 μm. The liquid crystal aligning agent of this invention was manufactured. After apply | coating the said liquid crystal aligning agent to the transparent electrode surface of the glass substrate with a transparent electrode containing ITO using a liquid crystal aligning film printing machine (made by Nippon Shashin Insatsugi Co., Ltd.), and drying for 1 minute on 80 degreeC hotplates, 200 It dried on 10 degreeC hotplate for 10 minutes, and formed the film of average thickness 600 angstroms. When the board | substrate was observed with the microscope of 20 times the magnification, printing nonuniformity and a pinhole were not seen and printability was favorable.

The rubbing process was performed by the rubbing machine which has the roll which wound the cloth of nylon type to this film at roll rotation speed 500rpm, stage movement speed 3cm / sec, hairpin indentation length 0.4mm, and formed the liquid crystal aligning film. Next, after immersing the said liquid crystal aligning film formation board | substrate in isopropyl alcohol for 1 minute, it dried on the 100 degreeC hotplate for 5 minutes. Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to each outer edge which has a pair of said liquid crystal aligning film, the liquid crystal aligning film surface was overlapped so as to oppose each other, and the adhesive was hardened | cured. Subsequently, after filling a nematic liquid crystal (MLC-6221 made by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal inlet, the liquid crystal inlet is sealed with an acryl-type photocuring adhesive, and a deflection plate is bonded to both surfaces of a board | substrate outer side, and this invention The liquid crystal display element of was manufactured.

As a result of visual observation of the device by applying a square wave of 30 Hz and 3.0 V having superposed AC 6.0 V (peak-peak) to the obtained liquid crystal display at an environment temperature of 70 ° C. for 500 hours, the display defect of the liquid crystal display device was not seen. Did.

Examples 2 to 23, Comparative Examples 1 and 2

It carried out similarly to Example 1 except having changed the kind and addition amount of an epoxy containing compound, and the drying temperature of a liquid crystal aligning film using the polyamic acid and imidation polymer obtained by the synthesis examples 1-9 and the comparative synthesis examples 1-2. The liquid crystal aligning agent was produced, the film was formed on the board | substrate, the presence of printing nonuniformity and the pinhole was observed, and the liquid crystal display element was further manufactured and the presence or absence of the display defect was observed. In Examples 5 to 23 and Comparative Examples 1 to 2, the polyamic acid and the imidized polymer were used at a ratio of polyamic acid: imidized polymer = 4: 1 (weight ratio). The results are shown in Table 1 together.

C-1: EX-171 (manufactured by Nagase Chemtex Co., Ltd., represented by Chemical Formula (47))

C-2: EX-145 (manufactured by Nagase Chemtex Co., Ltd., represented by Chemical Formula (45))

According to the liquid crystal aligning agent of this invention, when printing-coating on a board | substrate, the liquid crystal aligning film with favorable printability without a printing nonuniformity and a pinhole can be manufactured.

The liquid crystal display element of the present invention can be suitably used for TN type and STN type liquid crystal display elements, and by selecting a liquid crystal to be used, an SH (Super Homeotropic) type, an IPS (In-Plane Switching) type, and an optical compensation bend ( OCB) type, ferroelectric and antiferroelectric liquid crystal display elements, etc. can be used suitably.

Moreover, the liquid crystal display element of this invention can be effectively used for various apparatuses, For example, it is used for display apparatuses, such as a table calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, and a liquid crystal television.

Claims (3)

(A) a polymer having a repeating unit represented by the following Formula 1a and / or a repeating unit represented by the following Formula 1b, and (B) an epoxy compound represented by the following formula (2) It contains, The liquid crystal aligning agent characterized by the above-mentioned. <Formula 1a>

(Wherein, P ¹ is a tetravalent organic group, Q ¹ is a divalent organic group) <Formula 1b>

(Wherein P ² is a tetravalent organic group and Q ² is a divalent organic group) <Formula 2>

(Wherein n is an integer of 1 to 30 and R ₁ is an n-valent organic group) The liquid crystal aligning agent of Claim 1 whose (A) polymer is a polymer which has a repeating unit represented by the said Formula (1a), and a repeating unit represented by the said Formula (1b). The liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 1 is provided, The liquid crystal display element characterized by the above-mentioned.