JP2006349852A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent which provides a liquid crystal alignment layer having an excellent voltage holding ratio and excellent reliability. <P>SOLUTION: The liquid crystal aligning agent contains at least a kind of polymer selected from a group composed of a polyamic acid which is generated by reacting a tetracarboxylic acid dianhydride containing at least 1 mol% of at least a kind of tetracarboxylic acid dianhydride selected from a group composed of a compound expressed by a formula (A) and a compound formed by substituting a hydrogen atom on a norbornane ring of the compound expressed by the formula (A) with a monovalent organic group, with a diamine compound, and a polyimide obtained by dehydrating and ring-closing the polyamic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display device including a liquid crystal alignment film formed therefrom. More specifically, the present invention relates to a liquid crystal aligning agent that provides a liquid crystal alignment film that has excellent coating properties and provides excellent reliability to a liquid crystal display element, and a liquid crystal display element that includes the liquid crystal alignment film.

Currently, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate. A nematic liquid crystal layer having positive dielectric anisotropy is formed in a cell having a sandwich structure so that the major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. A TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is known.
Further, STN (Super Twisted Nematic) type liquid crystal display elements have been developed that have higher contrast than TN type liquid crystal display elements and have less viewing angle dependency. This STN type liquid crystal display element uses nematic liquid crystal blended with a chiral agent which is an optically active substance as liquid crystal, and the major axis of liquid crystal molecules is continuously twisted over 180 degrees between substrates. The birefringence effect generated by the above is utilized.

Also known is a lateral electric field type liquid crystal display element in which two electrodes for driving a liquid crystal are arranged in a comb-like shape on one side of the base, an electric field parallel to the base is generated, and liquid crystal molecules are controlled. The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to a rubbing treatment.
As a liquid crystal display element different from the above, a liquid crystal display element having a vertical alignment type liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicular to a substrate is known. In such a liquid crystal display element, the alignment of the liquid crystal is usually controlled by a liquid crystal alignment film formed of a liquid crystal alignment agent containing a polymer such as polyamic acid or soluble polyimide.

There are two methods for driving a liquid crystal display element: a thin film transistor (TFT) method and a simple matrix method. A TFT is provided with a thin film transistor in each pixel, and is suitable for high-definition video display. The TN type, lateral electric field type, and vertical alignment type liquid crystal display elements are usually driven by a TFT driving method.
In general, in the TFT driving method, it is necessary to increase the voltage holding ratio. In recent years, it has been desired that a higher voltage holding ratio can be secured even at a high temperature of 60 ° C. to 90 ° C. from the viewpoint of reliability. Therefore, there is a need for a liquid crystal aligning agent for obtaining a liquid crystal aligning film having a higher voltage holding ratio than before.

  The first object of the present invention is to provide a liquid crystal aligning agent having excellent coating properties.

  The second object of the present invention is to provide a liquid crystal aligning agent capable of constituting a liquid crystal display element having an excellent voltage holding ratio.

  A third object of the present invention is to provide a liquid crystal aligning agent that can constitute a liquid crystal display element excellent in reliability.

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

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
The following formula (A)

で表される化合物およびこの化合物のノルボルナン環上の水素原子が１価の有機基で置換された化合物よりなる群から選ばれる少なくとも１種のテトラカルボン酸二無水物を少なくとも１モル％含有するテトラカルボン酸二無水物と、ジアミン化合物とを反応させることにより生成するポリアミック酸およびこのポリアミック酸を脱水閉環させたポリイミドよりなる群から選ばれる少なくとも１種の重合体を含有することを特徴とする液晶配向剤により達成される。

A tetra-containing tetracarboxylic dianhydride selected from the group consisting of a compound represented by the following formula and a compound in which a hydrogen atom on the norbornane ring of the compound is substituted with a monovalent organic group A liquid crystal comprising a polyamic acid produced by reacting a carboxylic dianhydride and a diamine compound, and at least one polymer selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid. This is achieved with an aligning agent.

According to the present invention, the above objects and advantages of the present invention are secondly,
This is achieved by a liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the voltage holding rate is favorable and the liquid crystal aligning agent which gives the liquid crystal aligning film which is excellent in reliability can be provided. Furthermore, the liquid crystal display element having the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention can be effectively used in various devices, for example, a desk calculator, a wristwatch, a table clock, a count display board, a mobile phone, a word processor, a personal computer. It can be suitably used as a display device such as a liquid crystal data projector and a liquid crystal television.

  Hereinafter, the present invention will be described in detail.

  The liquid crystal aligning agent in the present invention is a tetracarboxylic acid containing a tetracarboxylic dianhydride which is a compound represented by the formula (A) or a compound in which a hydrogen atom on the norbornane ring is substituted with a monovalent organic group It contains at least one polymer of a polyamic acid obtained by reacting a dianhydride and a diamine compound and a polyimide obtained by dehydrating and ring-closing this polyamic acid.

  The tetracarboxylic dianhydride represented by the formula (A) is 5,5 ′-(1,1,3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3- Dicarboxylic anhydride. In the present invention, a compound in which a hydrogen atom on the norbornane ring of this compound is substituted with a monovalent organic group is also used in the same manner as the compound represented by the above formula (A). Specific examples of the monovalent organic group include alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and alkoxy groups having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, And a fluoroalkyl group and a fluoroalkoxy group in which these alkyl group and alkoxy group are fluorinated. The monovalent organic group may substitute one or more of the hydrogen atoms on the norbornane ring.

The method for obtaining the tetracarboxylic dianhydride represented by the formula (A) and the substituted product thereof as described above is not particularly limited. For example, as described in JP-A-59-501208, 5 -It can be obtained by reacting norbornene-2,3-carboxylic anhydride with silane under a platinum catalyst.
JP-T-59-501208

<Polyamic acid>
[Tetracarboxylic dianhydride]
In the tetracarboxylic dianhydride used to obtain the polyamic acid of the present invention, at least one selected from the group consisting of the tetracarboxylic dianhydride represented by the formula (A) and the substituents thereof as described above Content rate is 1-100 mol%. In order to obtain higher voltage holding characteristics, 5 to 100 mol% is preferable, and 10 to 100 mol% is more preferable. When the content of the tetracarboxylic dianhydride having a skeleton represented by the formula (A) and / or the substituted product thereof does not reach 100 mol%, other tetracarboxylic dianhydrides are used in combination. Other tetracarboxylic dianhydrides are not particularly limited, but if specific examples are given, the following tetracarboxylic dianhydrides may be mentioned.

  Examples of such other tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, and the like. 4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid 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, cis-3,7-dibutylcycloocta-1,5-diene-1 2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-di Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho 1,2-c] -furan-1 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-5 8-Dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxa Bicyclo [3,2,1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), compounds represented by the following formulas (I) and (II), etc. Aliphatic and cycloaliphatic tetracarboxylic dianhydrides;

(In the formula, R ³ and R ⁶ represent a divalent organic group having an aromatic ring, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group, and a plurality of R ⁴ and R ⁵ are the same. But it may be different.)
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (Phthalic acid) phenylphosphine oxide 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 (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate) 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydride) Trimetrate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (1) to (4) An aromatic tetracarboxylic dianhydride such as an aromatic tetracarboxylic dianhydride having a steroid skeleton represented by These may be used alone or in combination of two or more.

Of these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2 , 5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5- (te Lahydro-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, 3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), above Of the compounds represented by the formula (I), those represented by the following formulas (5) to (7) Compound, compound represented by the following formula (8) among compounds represented by the above formula (II), butanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride and the like have good liquid crystal orientation and From the viewpoint that electrical characteristics can be expressed, 2,3,5-tricarboxycyclopentylacetic acid dianhydride is particularly preferable. These may be used alone or in combination of two or more.

[Diamine compound]
Examples of the diamine compound used for the synthesis of the polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diaminodiphenyl sulfide. 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2, 2′-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl)- 1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzof Non, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis ( 4-Aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-di Chloro-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 ′ -Aromatic diamines such as bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl diamine, 4 Aliphatic and cycloaliphatic diamines such as 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-phenylphenanthridine, 1,4-diaminopiperazine, 3, , 6-diaminoacridine, bis (4-aminophenyl) phenylamine, and compounds represented by the following formulas (III) to (IV), etc. A diamine having a nitrogen atom;

(In the formula, 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 May be the same or different.)
Monosubstituted phenylenediamines represented by the following formula (V); diaminoorganosiloxanes represented by the following formula (VI);

(Wherein R ⁷ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁸ represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)

(Wherein 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 to 20) Is an integer.)
Examples 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′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benze 4,4′-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulas (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine 3,6-diaminoacridine, a compound represented by the following formula (14) among the compounds represented by the above formula (III), and a compound represented by the following formula (15) among the compounds represented by the above formula (IV) Of the compounds represented by formula (V), compounds represented by the following formulas (16) to (22) are preferred.

<Polyamic acid>
The ratio of tetracarboxylic dianhydride and diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of tetracarboxylic dianhydride is 0.1 equivalent to 1 equivalent of amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.6 to 1.4 equivalents is more preferable. The synthetic reaction of 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. Here, the organic solvent is not particularly limited as long as it can dissolve both the raw material diamine compound and tetracarboxylic dianhydride and the synthesized polyamic acid, and preferred examples thereof include N-methyl-2-pyrrolidone. Aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidone, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; -Phenol solvents such as cresol, xylenol, phenol, halogenated phenol can be exemplified. The amount of organic solvent used (a) is usually such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. An amount is preferred.

For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene Recall mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl 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, Tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diacetone alcohol, propylene carbonate, propylene glycol Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and the like α- pinene.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. 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 constituting the liquid crystal aligning agent of the present invention can be prepared by dehydrating and ring-closing the polyamic acid. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained 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 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, 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 can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. In addition, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.

<Partially imidized polymer>
The partially imidized polymer used in the present invention has a structure obtained by partially imidizing the polyamic acid, and the imidization ratio in the partially imidized polymer used in the present invention is less than 100%. And preferably 10 to 90%, more preferably 40 to 90%. Here, the “imidation ratio” is the percentage of the number of repeating units that form an imide ring with respect to the total number of repeating units in the polymer. At this time, a part of the imide ring may be an isoimide ring.

As a method of synthesizing a partially imidized polymer, (i) a method of synthesizing by partially dehydrating and ring-closing by heating the polyamic acid, and (ii) dissolving the polyamic acid in an organic solvent, A method in which a dehydrating agent and a dehydrating ring-closing catalyst are added to the mixture and heated as necessary to partially dehydrate and cyclize, (iii) tetracarboxylic dianhydride and diamine compound are mixed, if necessary (Iv) a polyamic acid prepolymer having a reactive group derived from an amino group or tetracarboxylic acid at the molecular end, and an amino group or tetracarboxylic acid derived from the molecular end. A method of reacting and synthesizing a polyimide prepolymer having a different group from any of the polyamic acid prepolymers, Used.
In the method (i), the reaction temperature is preferably 300 ° C. or less, more preferably 100 to 250 ° C. When the reaction temperature exceeds 300 ° C., the molecular weight of the resulting imide group-containing polyamic acid may decrease.

  On the other hand, as the dehydrating agent used in the method (ii), acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.2 to 20 mol with respect to 1 mol of the polyamic acid repeating unit. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but are not limited thereto. Moreover, it is preferable that the usage-amount of an imidation catalyst shall be 0.1-10 mol with respect to 1 mol of dehydrating agents to be used. In addition, as an organic solvent used for reaction of dehydration ring closure, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 60-150 degreeC. Moreover, an imide group containing polyamic acid can be refine | purified by performing operation similar to the purification method of polyamic acid with respect to the reaction solution obtained in this way.

In addition, a catalyst is not particularly required for the reaction (iii), and the reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 160 ° C.
In the above method (iv), the polyamic acid prepolymer and / or polyimide prepolymer is equimolar so that the number of moles is, for example, 1.001 to 2 times the number of moles of tetracarboxylic acid used. By using an excessive amount exceeding the amount, it can be synthesized as a prepolymer having an amino group at the molecular end. Alternatively, by using an excess amount exceeding the equimolar amount so that the molar number of tetracarboxylic acid is, for example, 1.001 to 2 times the molar number of diamine used, it is derived from the carboxylic acid at the molecular end. It can be synthesized as a prepolymer having a reactive group. In the synthesis of the polyimide prepolymer, the polyimide prepolymer having a reactive group derived from an amino group or a tetracarboxylic acid at the molecular end by performing the same imidation treatment as that for producing the above-mentioned imidized polymer. Can be synthesized. A partially imidized polymer can be synthesized by reacting these prepolymers under the same conditions as those for the polyamic acid.

<End-modified polymer>
The polyamic acid, the imidized polymer, and the partially imidized polymer may be of a terminal modified type in which the molecular weight is adjusted. By using this terminal-modified polymer, the coating characteristics 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 synthesizing the polyamic acid. Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride. , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

<Logarithmic viscosity of polymer>
The logarithmic viscosity (η _ln ) value of the polyamic acid and imide group-containing polyamic acid obtained as described above is preferably 0.05 to 10 dl / g, more preferably 0.05 to 5 dl / g.
The value of logarithmic viscosity (η _ln ) in the present invention is determined by measuring the viscosity at 30 ° C. for a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. ).

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is usually constituted by dissolving and containing at least one polymer selected from the above polyamic acid, imidized polymer, and partially imidized polymer in an organic solvent. 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 a polyamic acid can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.
The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is It is too small to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent is increased, so that the coating properties tend to be inferior. Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention, Preferably, it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.
The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy compound from the viewpoint of improving the adhesion to the substrate surface within a range that does not impair the intended physical properties. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′, -Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'- Diaminodiphenylmethane, 3- (N-Ariru N Gurishijiru) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) and the like aminopropyltrimethoxysilane.
The blending ratio of these functional silane-containing compounds or epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.

<Liquid crystal display element>
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) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, or a printing method, and then the coated surface is heated. Thus, a coating film is formed. 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 a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. 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, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. In addition, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating, but further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be set as a coating film. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film. Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. A polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element is obtained by pasting together.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent 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, pyrimidine liquid crystals, dioxanes. Type liquid crystal, bicyclooctane type liquid crystal, cubane type liquid crystal and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The evaluation method in each liquid crystal display element produced by the following examples and comparative examples is shown below.

[Imidation rate of polymer]
A polymer or a liquid crystal aligning agent is dried at room temperature under reduced pressure and then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance, and obtained by the formula shown by the following formula (II). It was.
Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (II)
A ¹ : NH group proton-derived peak area (10 ppm)
A ² : Peak area derived from other protons α: Number ratio of other protons to one proton of NH group in polymer precursor (polyamic acid)

[Reliability test of liquid crystal display elements]
In a high temperature and high humidity environment (temperature: 70 ° C., relative humidity: 80%), the liquid crystal display element is driven by a rectangular wave of 5 V and 60 Hz, and the presence or absence of white spot-like display defects after 1500 hours is observed with a polarizing microscope. did.

[80 ° C voltage holding ratio of liquid crystal display element]
The liquid crystal display element was heated to 80 ° C., a voltage of 5 V was applied for 60 microseconds with a span of 167 milliseconds, and the voltage holding ratio after 167 milliseconds from the release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation.

[Printability test of liquid crystal alignment agent]
The polymer was dissolved in a mixed solvent of γ-butyrolactone / N-methylpyrrolidone / butyl cellosolve (70/10/20 (weight ratio)) to obtain a solution having a solid content concentration of 4% by weight, and this solution was filtered using a filter having a pore size of 1 μm. The liquid crystal aligning agent of this invention was prepared by filtering. The liquid crystal aligning agent is applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and then on a hot plate at 80 ° C. for 1 minute. After drying, the film was dried on a hot plate at 180 ° C. for 20 minutes to form a film having an average film thickness of 600 Å. This substrate was observed with a microscope with a magnification of 20 times, and the quality of the printability was determined by the presence or absence of printing unevenness and pinholes.

Synthesis example 1
100.88 g (0.45 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 141.43 g (0.45 mol), 5,5 ′-(1,1, 3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic acid anhydride 46.26 g (0.1 mol), p-phenylenediamine 94.62 g (0 .875 mol) 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl 32.02 g (0.1 mol) and 6.43 g (0.01 mol) of the compound represented by the above formula (9) Aniline as a monoamine 2. 9g (0.03 mol) was dissolved in N- methyl-2-pyrrolidone 4500 g, was reacted for 6 hours at 60 ° C.. 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 ° C. under reduced pressure for 15 hours to obtain 390 g of polyamic acid having a logarithmic viscosity of 0.59 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.5 g of polyimide having a logarithmic viscosity of 0.60 dl / g and an imidization ratio of 95% (this is referred to as “polyimide (A-1)”).

Synthesis example 2
100.88 g (0.45 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 141.43 g (0.45 mol), 5,5 ′-(1,1, 3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic anhydride 46.26 g (0.1 mol), p-phenylenediamine 94.62 g (0) as the diamine compound .875 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 6.43 g (0.01 mol) of the compound represented by the above formula (9), 2.79 g (0. 0.0 Mol) was dissolved in N- methyl-2-pyrrolidone 4500 g, was reacted for 6 hours at 60 ° C.. 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 ° C. under reduced pressure for 15 hours to obtain 380 g of polyamic acid having a logarithmic viscosity of 0.61 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 18.4 g of polyimide having a logarithmic viscosity of 0.65 dl / g and an imidization rate of 94% (this is referred to as “polyimide (A-2)”).

Synthesis example 3
100.88 g (0.45 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 141.43 g (0.45 mol), 5,5 ′-(1,1, 3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic acid anhydride 46.26 g (0.1 mol), p-phenylenediamine 87.05 g (0 .805 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 35.07 g (0.08 mol) of the compound represented by the above formula (22), 2.79 g of aniline as a monoamine 0.03 mol) was dissolved in N- methyl-2-pyrrolidone 4500 g, it was reacted for 6 hours at 60 ° C.. 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 ° C. under reduced pressure for 15 hours to obtain 400 g of a polyamic acid having a logarithmic viscosity of 0.52 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.6 g of polyimide having a logarithmic viscosity of 0.60 dl / g and an imidization ratio of 95% (hereinafter referred to as “polyimide (A-3)”).

Synthesis example 4
100.88 g (0.45 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 141.43 g (0.45 mol), 5,5 ′-(1,1, 3,3-tetramethyl-1,3-disiloxanediyl) -bis-norbornane-2,3-dicarboxylic anhydride 46.26 g (0.1 mol), p-phenylenediamine 105.44 g (0 as diamine compound) 975 mol), 6.43 g (0.01 mol) of the compound represented by the above formula (9), 2.79 g (0.03 mol) of aniline as a monoamine were dissolved in 4500 g of N-methyl-2-pyrrolidone, 6 at 60 ° C It was between reaction. 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 ° C. under reduced pressure for 15 hours to obtain 370 g of polyamic acid having a logarithmic viscosity of 0.83 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.0 g of a polyimide having a logarithmic viscosity of 0.95 dl / g and an imidization rate of 94% (hereinafter referred to as “polyimide (A-4)”).

Synthesis example 5
201.75 g (0.9 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 5,5 ′-(1,1,3,3-tetramethyl-1,3 -Disiloxanediyl) -bis-norbornane-2,3-dicarboxylic anhydride 46.26 g (0.1 mol), p-phenylenediamine 102.73 g (0.95 mol) as the diamine compound and the above formula (16) Was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 350 g of polyamic acid having a logarithmic viscosity of 0.85 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 16.6 g of polyimide having a logarithmic viscosity of 0.89 dl / g and an imidization ratio of 90% (hereinafter referred to as “polyimide (A-5)”).

Synthesis Example 6
201.75 g (0.9 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 5,5 ′-(1,1,3,3-tetramethyl-1,3 -Disiloxanediyl) -bis-norbornane-2,3-dicarboxylic anhydride 46.26 g (0.1 mol), p-phenylenediamine 54.07 g (0.5 mol) as the diamine compound, the above formula (16) 261.41 g (0.5 mol) represented by the following formula was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 500 g of a polyamic acid having a logarithmic viscosity of 0.70 dl / g (referred to as “polyamic acid (B-6)”).

Synthesis example 7
176.50 g (0.9 mol) of cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212.30 g (1.0 mol) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine compound In the same manner as in Synthesis Example 1 except that was used, 370 g of a polyamic acid having a logarithmic viscosity of 1.21 dl / g (referred to as “polyamic acid (B-7)”) was obtained.

Synthesis example 8
A polyimide prepolymer was synthesized in the same manner as in Synthesis Example 1 except that the monoamine aniline was removed in Synthesis Example 1, and dissolved in N-methyl-2-pyrrolidone to obtain a solution having a solid content concentration of 10% by weight. Further, a polyamic acid prepolymer was synthesized in the same manner as in Synthesis Example 6, and similarly dissolved in N-methyl-2-pyrrolidone to obtain a solution having a solid content concentration of 10% by weight. Next, 200 g of the polyimide prepolymer solution and 800 g of the polyamic acid prepolymer were mixed and stirred for 2 hours, and then the reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the polymer was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a partially imidized polymer having a logarithmic viscosity of 0.85 dl / g and an imidization ratio of 19% (hereinafter referred to as “polymer (C-8) 90 g) was obtained.

Comparative Synthesis Example 1
112.09 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 157.14 g (0.5 mol), p-phenylenediamine 105.44 g as the diamine compound (0.975 mol), 6.43 g (0.01 mol) of the compound represented by the above formula (9), and 2.79 g (0.03 mol) of aniline as a monoamine are dissolved in 4500 g of N-methyl-2-pyrrolidone. And reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 410 g of polyamic acid having a logarithmic viscosity of 0.54 dl / g. 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 was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.5 g of polyimide having a logarithmic viscosity of 0.63 dl / g and an imidization ratio of 95% (this is referred to as “polyimide (a-1)”).

Example 1
The polyimide (A-1) obtained in Synthesis Example 1 and the polyamic acid (B-7) obtained in Synthesis Example 7 were mixed with N-methyl so that polyimide: polyamic acid = 20: 80 (weight ratio). It was dissolved in 2-pyrrolidone / γ-butyrolactone / ethylene glycol monobutyl ether mixed solvent (weight ratio 20/70/10) to give a solution having a solid content concentration of 4% by weight. After stirring for 1 hour, this solution was prepared with a pore size of 1 μm. It filtered using the filter and the liquid crystal aligning agent of this invention was prepared. The printability test of this liquid crystal aligning agent was done. The results are shown in Table 1.

  Subsequently, the liquid crystal aligning agent was applied onto a transparent conductive film made of an ITO film provided on one surface of a 1 mm thick glass substrate using a spinner (rotation speed: 2000 rpm, application time: 1 minute), A film having a dry film thickness of 0.05 μm was formed by drying at 200 ° C. for 1 hour. A rubbing machine having a roll in which a rayon cloth was wound around this film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm. The liquid crystal alignment film-coated substrate was dipped in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 ° C. for 5 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film surfaces are relatively The adhesive was cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. Were laminated to prepare a liquid crystal display element. The voltage holding ratio and reliability of the obtained liquid crystal display element were evaluated. The results are also shown in Table 1.

Examples 2 to 6 and Comparative Example 1
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the polyimide, polyamic acid, or partially imidized polymer shown in Table 1 was used, and a liquid crystal display device was prepared and evaluated. The evaluation results are also shown in Table 1.

Example 7
The polyamic acid (B-6) obtained in Synthesis Example 6 was dissolved in an N-methyl-2-pyrrolidone / ethylene glycol monobutyl ether mixed solvent (weight ratio 50/50) to obtain a solid content concentration of 3.5% by weight. The solution was stirred for 1 hour, and then the solution was filtered using a filter having a pore size of 1 μm to prepare the liquid crystal aligning agent of the present invention. The printability of the obtained liquid crystal aligning agent was evaluated. The results are shown in Table 1. Subsequently, the liquid crystal aligning agent is applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner, and temporarily dried on a hot plate at 80 ° C. for 1 minute. And then dried in a clean oven at 200 ° C. for 1 hour to prepare a transparent electrode substrate having a liquid crystal alignment film having a dry film thickness of 0.05 μm. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer edges of the pair of transparent electrodes / transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, a negative type liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) 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 polarizing plates are formed on both sides of the substrate. Were laminated to prepare a vertical alignment type liquid crystal display element, and the voltage holding ratio and reliability of the obtained vertical alignment type liquid crystal display element were evaluated. The results are also shown in Table 1.

Claims (3)

The following formula (A)

A tetra-containing tetracarboxylic dianhydride selected from the group consisting of a compound represented by the following formula and a compound in which a hydrogen atom on the norbornane ring of the compound is substituted with a monovalent organic group A liquid crystal comprising a polyamic acid produced by reacting a carboxylic dianhydride and a diamine compound, and at least one polymer selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid. Alignment agent. The at least one polymer contains a tetracarboxylic dianhydride represented by the formula (A) and 2,3,5-tricarboxycyclopentylacetic acid dianhydride, each containing at least 1 mol%. 2. The liquid crystal aligning agent according to claim 1, which is a polymer selected from the group consisting of a polyamic acid produced by reacting an anhydride with a diamine compound and a polyimide obtained by dehydrating and ring-closing the polyamic acid. A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.