JP5360376B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal aligning agent and a liquid crystal display device. The liquid crystal aligning agent can form a liquid crystal aligning film displaying high vertical aligning control force even the liquid crystal aligning agent adopts ODF mode in the manufacturing process for the VA type liquid crystal display element and particularly has a good print performance. The liquid crystal aligning agent comprises at least one polymer in a group unit composed of polyamic acid and its imidization polymer, wherein the polyamic acid is produced by a diamine reacion between tetracarboxylic dianhydride and a specific diamine containing a compound represented by formula (A-10).

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, a liquid crystal aligning agent that provides a liquid crystal alignment film that does not cause ODF unevenness even when a liquid crystal dropping method (ODF method) is adopted in a liquid crystal filling process of manufacturing a liquid crystal display element, and continuous driving for a long time are performed. The present invention also relates to a liquid crystal display element in which display quality does not deteriorate.

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 by 90 ° 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. In addition, an STN (Super Twisted Nematic) type liquid crystal display element capable of realizing a high contrast ratio as compared with a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element with less viewing angle dependency, and a VA (Vertical Alignment). An optically compensated bend (OCB) type liquid crystal display element has been developed that has a small viewing angle dependency and an excellent video screen high-speed response.
As materials for the liquid crystal alignment film in these liquid crystal display elements, polyimide, polyamide, polyester, and the like are conventionally known, but in particular, polyimide has excellent heat resistance, affinity with liquid crystals, mechanical strength, It is used in many liquid crystal display elements.
Incidentally, in recent years, the manufacturing process of liquid crystal display elements has made great progress. In particular, techniques such as a large substrate transfer technique and a liquid crystal dropping method (ODF) that have been adopted along with an increase in the size of a substrate have attracted attention. Of these, the ODF method drops a required amount of liquid crystal on a substrate on which a liquid crystal alignment film is formed, bonds it to the other substrate in a vacuum, and then UV cures a sealing agent for sealing the liquid crystal. This is a method of filling the entire surface of the panel with liquid crystal, and is a technique that can significantly reduce the process time of the liquid crystal filling step as compared with the conventional vacuum injection method. However, when the ODF method is employed in the manufacture of a VA liquid crystal display element having a polyimide-based liquid crystal alignment film, there may be a problem that display unevenness called “ODF unevenness” occurs. This phenomenon is believed to be caused by the lack of the vertical alignment regulating force of the liquid crystal alignment film.
In order to solve this problem in a polyimide-based liquid crystal alignment film, for example, there is a method of using a polyimide obtained using a diamine containing a diamine having a hydrophobic functional group such as a long-chain alkyl group at a high content. (See Patent Documents 1 and 2). Although this technique is an excellent technique in which the effect of increasing the vertical alignment regulating force is recognized, the printability of the liquid crystal aligning agent may be impaired.
Therefore, various required performances required for liquid crystal aligning agents, in particular, liquid crystal aligning agents that give a liquid crystal aligning film that does not cause ODF unevenness without impairing printability, and liquid crystal display elements that are excellent in display quality, especially long-time continuous driving. Therefore, there is a demand for a liquid crystal display element that does not deteriorate the image quality even in such a case.

JP-A-9-241646 JP 2001-305549 A

An object of the present invention is to provide a liquid crystal alignment film exhibiting a high vertical alignment regulating force that does not cause display unevenness even when an ODF method is adopted in the manufacture of a VA liquid crystal display element, and as a liquid crystal aligning agent. An object of the present invention is to provide a liquid crystal aligning agent excellent in various performances required, particularly printability, and a liquid crystal display element excellent in display quality.
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 are as follows.
Tetracarboxylic dianhydride and the following formula (A)

(In the formula (A), R ^I and R ^III are each independently an ether bond, a thioether bond, an ester bond or a thioester bond, provided that R ^II is a methylene group or an alkylene group having 2 to 10 carbon ^{atoms, R IV} is a main styrene group or an ethylene group, X is a monovalent organic group having 17 to 40 carbon atoms having a steroid skeleton.)
It achieves by the liquid crystal aligning agent containing the at least 1 sort (s) of polymer selected from the group which consists of the polyamic acid obtained by making the diamine containing the compound represented by and its imidation polymer react.
The above objects and advantages of the present invention are secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.

The liquid crystal aligning agent of the present invention is selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine containing a compound represented by the above formula (A) and an imidized polymer thereof. Contains at least one polymer.
<Polyamic acid>
The polyamic acid that can be contained in the liquid crystal aligning agent of the present invention can be synthesized by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (A).

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic Acid 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-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic Dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 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, , 3,3a, 4,5,9b-hexahi Dro-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-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride, 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), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6} ] Undecane-3,5,8,10-tetraone The following formulas (TI) and (T-II)

(In the above formula, R ¹ and R ³ each represent a divalent organic group having an aromatic ring, R ² and R ⁴ each represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ² are present. ⁴ may be the same or different.
An aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride such as a compound represented by each of the following:
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, 2 , 2 ′, 3,3′-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 ( Anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate) Retate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate), the following formulas (T-1) to (T-4)

An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. These may be used alone or in combination of two or more.
The tetracarboxylic dianhydride used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention is butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3, 5-Tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1 3-dione, 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), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2 , 6} ] undecane-3,5,8,10-tetraone, pyromelli Butanoic acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,3 ′, 2 , 3′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, among the compounds represented by the above formula (TI), the following formula (T-5) to (T-7)

Of the compounds represented by each of the above and the compounds represented by the above formula (T-II), the following formula (T-8)

It is preferable from the viewpoint that it can exhibit good liquid crystal alignment properties including at least one selected from the group consisting of compounds represented by the following (hereinafter referred to as “specific tetracarboxylic acid (1)”). .
As specific tetracarboxylic acid (1), 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5 , 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane- 2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic anhydride 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3, At least one selected from the group consisting of 5,8,10-tetraone, pyromellitic dianhydride and the compound represented by the above formula (T-5) is preferable.
The tetracarboxylic dianhydride used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention includes the specific tetracarboxylic acid (1) as described above with respect to all tetracarboxylic dianhydrides. Thus, it is preferable to contain 20 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% or more.

[Diamine]
The diamine used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention is a diamine containing a compound represented by the above formula (A).
R ^I and R ^III in the above formula (A) are preferably each independently an ether bond or an ester bond. The direction of this ester bond does not matter. R ^II is preferably an alkylene group having 2 to 4 carbon atoms. The R ^IV, main styrene group.
The steroid skeleton in X of the above formula (A) refers to a cyclopentano-perhydrophenanthrene skeleton or a skeleton in which one or more of carbon-carbon bonds included in the skeleton is a double bond. Examples of the group X having such a steroid skeleton include the following formulas (X-1) to (X-4):

(X ^I in the above formulas is

("+" In the above formula indicates a bond)
And “*” indicates a bond. )
And groups represented by each of the above. Specific examples of the group X include, for example, the following formula (X-1-1), (X-2-1), (X-3-1) or (X-4-1)

("*" In the above formula indicates a bond)
The group represented by these can be mentioned.
Specific examples of the compound represented by the formula (A) include, for example , formulas (A-3), (A-4), (A-) of the following formulas (A-1) to (A-29) : 9), (A-10), (A-25) and (A-26)

The compound represented by each of these can be mentioned.
These compounds can be synthesized by conventional methods of organic chemistry.
For example, the compound represented by the above formula (A-1), (A-2), (A-7) or (A-8) is obtained by adding succinic anhydride to cholesterol or cholestanol, respectively, The acid chloride is converted into an acid chloride, and the acid chloride is reacted with dinitrophenol in the presence of an equivalent amount of base, followed by reduction with an appropriate reducing agent such as tin chloride. Can do.
The compound represented by the above formula (A-3), (A-4), (A-9) or (A-10) is obtained by adding succinic anhydride to cholesterol or cholestanol, respectively, and then in the presence of potassium carbonate. In this method, after the ester-forming reaction between the adduct and dibenzoyl chloride, the compound can be synthesized by reduction with an appropriate reducing agent such as tin chloride.
The compound represented by the above formula (A-5) or (A-11) includes tosylated cholesterol or tosylated cholestanol obtained by tosylating cholesterol or cholestanol with tosyl chloride, and dinitrobenzoyl chloride. And dinitrobenzoyl monobutanediol ester obtained by reacting excess butanediol in the presence of a base, and then heating the above tosylated cholestanol in a suitable organic solvent to form an ether bond. And can be synthesized by a method of reducing with an appropriate reducing agent such as tin chloride.
The compound represented by the above formula (A-6) or (A-12) is obtained by adding succinic anhydride to cholesterol or cholestanol, respectively, and then converting the carbonyl group of the adduct into a methylene group with lithium aluminum hydride or the like. After the reduction, an ester formation reaction between the reduced form and 2,4-dinitrochlorobenzene in the presence of a base such as t-butoxypotassium, followed by reduction with an appropriate reducing agent such as tin chloride, or the above 1- (4-hydroxybutoxy) obtained by reacting tosylated cholesterol or tosylated cholestanol obtained in the same manner with 2,4-dinitrochlorobenzene and an excess of butanediol in the presence of a base such as t-butoxypotassium. -2,4-dinitrobenzene is heated in a suitable organic solvent to form an ether bond. After, it can be synthesized by a method of reducing an appropriate reducing agent such as tin chloride.
The compound represented by the above formula (A-13) is prepared by, for example, combining tosylated cholestanol obtained in the same manner as described above, 2,4-dinitrochlorobenzene and excess ethylene glycol in the presence of a base such as t-butoxy potassium. 1- (4-Hydroxyethoxy) -2,4-dinitrobenzene obtained by the reaction is heated in an appropriate organic solvent to form an ether bond, and then reduced with an appropriate reducing agent such as tin chloride. It can be synthesized by the method.
The compound represented by the above formula (A-14), (A-15) or (A-16) is represented by the above formula (A-6) except that lanosterol, ergosterol or lumisterol is used as a starting material, respectively. It can be synthesized by a method according to the synthesis of the compound represented.
The compound represented by the above formula (A-17) or (A-18) synthesizes a monoether compound by mesylating cholesterol or cholestanol with methanesulfonic acid chloride and then performing a substitution reaction with excess ethylene glycol. Then, the monoether compound is reacted with 3,5-dinitrobenzoyl chloride in the presence of a base to synthesize a dinitro compound, and then the nitro group is obtained by reduction using an appropriate reducing agent such as palladium carbon. be able to.
The compound represented by the above formula (A-19) or (A-20) is obtained by converting cholesterol or cholestanol into an alkoxide with potassium hydride or the like and then reacting with excess dibromopropane to form an ether bond. After obtaining an intermediate, the above intermediate and 3,5-dinitrobenzoic acid were reacted in the presence of potassium carbonate to synthesize a dinitro form, and then the nitro group was reduced using an appropriate reducing agent such as palladium carbon. Can be obtained.
The compound represented by the formula (A-21) or (A-22) is obtained by adding succinic anhydride to cholesterol or cholestanol, respectively, and then using 3,5- (N, N, N-dicyclohexylcarbodiimide. After reacting with (N-diallyl) aminophenol, it can be obtained by removing the allyl group using 1,3-dimethylbarbituric acid and tetrakistriphenylphosphine palladium.
In the compound represented by the above formula (A-23) or (A-24), succinic anhydride is added to cholesterol or cholestanol, respectively, and then a carbonyl group is reduced using a borane-oxolane complex to form an intermediate as an alcohol. After the product is obtained, the intermediate is reacted with 3,5-dinitrobenzoyl chloride in the presence of a base to synthesize a dinitro compound, and then the nitro group is reduced using an appropriate reducing agent such as palladium carbon. Can be obtained.
The compound represented by the above formula (A-25) or (A-26) is represented by the above formula (A-4) or (A-10), respectively, except that glutaric anhydride is used instead of succinic anhydride. It can be obtained in the same manner as the compound represented.
The compound represented by the above formula (A-27), (A-28) or (A-29) is used after hydrogenating the raw material lanosterol, ergosterol or lumisterol with an appropriate hydrogenation catalyst, Each can be obtained in the same manner as the compound represented by the above formula (A-14), (A-15) or (A-16).

  As the diamine used to synthesize the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention, only the compound represented by the above formula (A) may be used, or the diamine represented by the above formula (A) Other diamines may be used in combination with the compound to be prepared. Here, as other diamine which can be used together with the compound represented by the above formula (A), for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino. Diphenylethane, 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, 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'-diaminodiphenyl ether 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) , 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-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′-dichloro-4,4′- Diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenylene) Isopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino Aromatic diamines such as -2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) Aliphatic diamines and alicyclic diamines such as;
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- Aminopurine, 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, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-di (4-aminophenyl) -benzidine, the following formula (DI)

(In the formula (DI), 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 ¹ represents a divalent organic group. .)
A compound represented by formula (D-II):

(In Formula (D-II), R ⁶ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² represents a divalent organic group, respectively. A plurality of X ² may be the same or different from each other.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁷ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁸ represents a steroid. (A monovalent organic group having a group selected from a skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms.)
A mono-substituted phenylenediamine (excluding the compound represented by the above formula (A));
The following formula (D-IV)

(In the formula (D-IV), R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁹ may be the same or different, and p represents 1 to 3 respectively. And q is an integer of 1 to 20.)
Diaminoorganosiloxanes such as compounds represented by:
The following formulas (D-1) to (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
And the like, and the like.
The aromatic diamine, a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, a mono-substituted phenylenediamine (excluding the compound represented by the above formula (A)) and the above. The benzene ring included in the compounds represented by formulas (D-1) to (D-5) may be substituted with an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).
In synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention, the other diamine used in combination with the compound represented by the above formula (A) is p-phenylenediamine, 4,4 among the above. '-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′-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) hexene Safluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine) ), 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulas (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl- 3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N′-di (4-aminophenyl) Benzidine, formula of the compound represented by the above formula (D-I) (D-6)

Of the compounds represented by formula (D-II), the following formula (D-7)

Of the compounds represented by formula (D-III) and dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene and the following formula (D-8) ~ (D-16)

It is preferable that it contains at least one selected from the group consisting of the compounds represented by each (hereinafter referred to as “other specific diamine”).
The diamine used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention preferably contains 1 mol% or more of the compound represented by the above formula (A) with respect to the total diamine. 2 to 20 mol% is more preferable, and 5 to 10 mol% is particularly preferable.
The diamine used for synthesizing the polyamic acid that can be contained in the liquid crystal aligning agent of the present invention preferably further contains another specific diamine as described above in an amount of 20 to 99 mol% based on the total diamine. More preferably, it is contained in an amount of 50 to 99 mol%, particularly preferably 80 to 99 mol%.

[Synthesis of polyamic acid]
The polyamic acid that can be contained in the liquid crystal aligning agent of the present invention can be obtained by reacting the tetracarboxylic dianhydride as described above with a diamine.
The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 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. The reaction time is preferably 1 to 240 hours, more preferably 2 to 12 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide And aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. In addition, the amount of organic solvent used (a: in the case where an organic solvent and a poor solvent described later are used in combination) refers to the total amount of tetracarboxylic dianhydride and diamine compound (b). However, the amount is preferably 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution.

For the organic solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents for polyamic acid, can be used in combination as long as the polyamic acid to be produced does not precipitate. 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 methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, etc. In That.
When the organic solvent and the poor solvent are used in combination when synthesizing the polyamic acid, the proportion of the poor solvent used is preferably 50% by weight or less, more preferably 10% by weight based on the total of the organic solvent and the poor solvent. % Or less.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

[Imidized polymer]
The imidized polymer that can be contained in the liquid crystal aligning agent of the present invention can be obtained by dehydrating and ring-closing the polyamic acid as described above to imidize.
The tetracarboxylic dianhydride used for the synthesis of the imidized polymer is at least one selected from alicyclic tetracarboxylic dianhydrides (hereinafter referred to as “specific tetracarboxylic dianhydride (2)”). It is preferred to use a tetracarboxylic dianhydride containing. Specific tetracarboxylic dianhydrides (2) include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5) -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3'- (Tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6 -Tricarboxy-2-carboxyno Bornane -2: 3,5: selected from 6-dianhydride and 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10- tetraone group consisting At least one selected from the above is preferred.
The tetracarboxylic dianhydride used for synthesizing the imidized polymer that can be contained in the liquid crystal aligning agent of the present invention includes the specific tetracarboxylic acid (2) as described above, and all tetracarboxylic dianhydrides. On the other hand, it is preferably 20 mol% or more, more preferably 50 mol% or more, and particularly preferably 80 mol% or more.
Examples of the diamine used for the synthesis of the imidized polymer include the same diamine as that used for the synthesis of the polyamic acid described above.

The imidized polymer may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid as a raw material had, and only a part of the amic acid structure may be dehydrated and cyclized to form an amic acid structure. And a partially imidized product in which an imide ring structure coexists.
The imidized polymer contained in the liquid crystal aligning agent of the present invention preferably has an imidation ratio of 20% or more, and particularly preferably 40 to 80%.
The said imidation rate represents the ratio for which the number of the imide ring structure with respect to the sum total of the number of the amic acid structure of an imidation polymer and the number of imide ring structures is represented by a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation rate was determined by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide) and measuring ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. 1).

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

(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of an imidized polymer ( It is the number ratio of other protons to one NH group proton in the polyamic acid).

The dehydrating ring closure of the polyamic acid for synthesizing the imidized polymer is performed by (i) a method of heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, and the dehydrating agent and the dehydrating ring closure in this solution. It is carried out by a method of adding a catalyst and heating as necessary.
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. The reaction time is preferably 1 to 24 hours, more preferably 2 to 8 hours.
In the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used. . 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. The reaction time is preferably 1 to 24 hours, more preferably 2 to 8 hours.

  The imidized polymer obtained in the above method (i) may be used for the preparation of a liquid crystal aligning agent as it is, or may be used for the preparation of a liquid crystal aligning agent after purifying the obtained imidized polymer. . On the other hand, in the method (ii), a reaction solution containing an imidized polymer is obtained. This reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. After separating, it may be used for preparing a liquid crystal aligning agent, or the isolated imidized polymer may be purified and then used for preparing a liquid crystal aligning agent. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. Isolation and purification of the imidized polymer can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid.

-End-modified polymer-
The polyamic acid or the imidized polymer thereof that can be contained in the liquid crystal aligning agent of the present invention may be of a terminal modified type with a controlled molecular weight. By using the terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing a polyamic acid. Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like.
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 etc. can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, Examples include n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine. it can. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of the synthesis of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. is there.
-Solution viscosity-
The polyamic acid or imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, when it is made into a solution having a concentration of 10% by weight, and preferably has a solution viscosity of 30 to 500 mPa · s. More preferably, it has a solution viscosity.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.

<Other additives>
The liquid crystal alignment film of the present invention contains, as an essential component, at least one polymer selected from the group consisting of the polyamic acid as described above and an imidized polymer obtained by dehydrating and ring-closing the polyamic acid. Other components may be contained. Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), a functional silane compound, and the like.
Examples of the epoxy compound 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′-diame Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - such as aminomethyl cyclohexane may be mentioned as preferred. The blending ratio of these epoxy group-containing compounds is preferably 100 parts by weight with respect to 100 parts by weight of the total amount of polymers (the total amount of polyamic acid and its imidized polymer contained in the liquid crystal aligning agent). It is 40 parts by weight or less, more preferably 0.1 to 30 parts by weight.
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N- Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Examples thereof include oxyethylene) -3-aminopropyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
The blending ratio of these functional silane-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total amount of the polymer.

The liquid crystal aligning agent of the present invention is preferably at least one polymer selected from the group consisting of the above polyamic acid and its imidized polymer, and other additives optionally blended as necessary. Is dissolved and contained in an organic solvent.
As an organic solvent which can be used for 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. Preferred examples of such organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2- Pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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, di Examples include ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether. These can be used alone or in admixture of two or more.

The solid content concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components excluding the organic solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. However, it is preferably in the range of 1 to 10% by weight. That is, when the liquid crystal aligning agent of the present invention is applied to the substrate surface and the organic solvent is removed to form a coating film that becomes a liquid crystal aligning film, the solid content concentration is less than 1% by weight. The film thickness of this coating film may be too small to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by weight, the film thickness of the coating film will be excessive. Similarly, it may be difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics.
The particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
The liquid crystal display element of the present invention can be produced, for example, by the following method.
(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is provided by, for example, a roll coater method, a spinner method, a printing method, an ink jet method, etc. A coating film is formed by heating the surface. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like 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. In order to obtain a patterned transparent conductive film, for example, a method of forming a desired pattern by photo-etching after forming a transparent conductive film without a pattern on a substrate, or having a desired pattern when forming a transparent conductive film A method of directly forming a transparent conductive film patterned using a mask can be used. In applying the liquid crystal aligning agent, for example, a functional silane compound or a functional titanium compound may be applied in advance in order to further improve the adhesion between the substrate surface and the resin film. For the purpose of preventing dripping of the alignment agent applied after application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.1 to 10 minutes, more preferably 0.5 to 3 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent. This post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 1 to 180 minutes, more preferably 10 to 120 minutes.
Although the liquid crystal aligning agent of this invention forms the coating film used as an orientation film by removing an organic solvent after application | coating, the polymer contained in the liquid crystal aligning agent of this invention is a polyamic acid or an imide ring structure, and an amic acid structure. In the case of an imide or a polymer having both of the above, a further imidized coating film may be formed by advancing the dehydration ring-closing reaction by further heating after forming the coating film.
The film thickness of the coating film formed here is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured. Since the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film having excellent vertical alignment, it is possible to obtain a liquid crystal display element that does not cause ODF unevenness even when a VA liquid crystal display element is manufactured by the ODF method. Has the advantage that can.
In any case, it is desirable to remove the flow alignment at the time of injection by heating the liquid crystal cell to a temperature at which the liquid crystal used has an isotropic phase and then slowly cooling it to room temperature.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

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 the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal and the like can be used. In addition, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate, and chiral products such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.) are also included in these liquid crystals. An agent or the like can also be added and used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film in which a polarizing film called “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films or The polarizing plate which consists of H film | membrane itself can be mentioned.

Example 1 (Synthesis of a compound represented by the above formula (A-10))
A compound represented by the above formula (A-10) (hereinafter referred to as “compound (A-10)”) is represented by the following scheme 1.

Was synthesized according to
(1) Synthesis of Compound (A-10a) In a 5 L three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 389 g of β-cholestanol, 201 g of succinic anhydride, 15 g of N, N-dimethylaminopyridine, triethylamine 170 mL and 2 L of ethyl acetate were charged and reacted at 90 ° C. for 8 hours. After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and 2 L of chloroform was added. The organic layer was washed successively with dilute hydrochloric acid 3 times and then with water 4 times, and then dried over magnesium sulfate. A precipitate formed by concentrating the organic layer was filtered off and the solvent was removed to obtain 223 g of a white powder of the compound (A-10a).
In addition, the synthesis | combination of the compound (A-10a) ensured the required amount in a following example by repeating on the said scale as needed.
(2) Synthesis of Compound (A-10b) In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 223 g of Compound (A-10a) synthesized above, 108 g of 3,5-dinitrobenzyl chloride, 207 g of potassium carbonate, 150 g of sodium iodide and 1,500 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 3 L of chloroform was added and the organic layer obtained was washed 3 times with water and then dried over magnesium sulfate. The organic layer was concentrated and the precipitated solid was collected and washed with ethanol to obtain 280 g of a light yellow powder of the compound (A-10b).
(3) Synthesis of Compound (A-10) In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 200 g of Compound (A-10b) synthesized above, 680 g of tin chloride dihydrate and acetic acid 2 L of ethyl was charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 58 g of pale yellow crystals of the compound (A-10).
Example 2 ( Reference Example, Synthesis of Compound Represented by Formula (A-18) above)
A compound represented by the above formula (A-18) (hereinafter referred to as “compound (A-18)”) is represented by the following scheme 2.

Was synthesized according to
(1) Synthesis of Compound (A-18a) In a 1 L three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introducing tube, 117 g of β-cholestanol, 3.7 g of N, N-dimethylaminopyridine, 400 mL of tetrahydrofuran and triethylamine 55 mL was charged and cooled on ice. A solution consisting of 100 mL of methanesulfonic acid chloride and tetrahydrofuran charged in the dropping funnel was added dropwise over 1 hour, and the reaction was further performed with stirring at room temperature for 3 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of ethyl acetate to the reaction mixture was separated and washed three times with water, and then dried over magnesium sulfate. Subsequently, after concentrating an organic layer to about 300 mL, this was disperse | distributed in 600 mL ethanol, the white precipitation produced | generated was filtered, and it dried and 117g of compounds (A-18a) were obtained.
(2) Synthesis of Compound (A-18b) 46.7 g of the compound (A-18a) obtained above, 155 g of ethylene glycol and 200 mL of 1,4-dioxane were mixed and reacted with heating and stirring at 100 ° C. for 20 hours. Went. After completion of the reaction, 500 mL of water and 500 mL of chloroform were added to the reaction mixture and sufficiently stirred, and then the organic layer was separated and washed successively with 500 mL of a saturated aqueous solution of sodium bicarbonate and twice with 500 mL of water. . The organic layer was dehydrated with magnesium sulfate, filtered and concentrated, added with 500 mL of ethanol, stirred at 0 ° C., and allowed to stand overnight. The white precipitate produced after standing was filtered off, and then the filtrate was concentrated and the solvent was removed, thereby obtaining 26.3 g of a crude product viscous liquid of compound (A-18b).
(3) Synthesis of Compound (A-18c) 26.3 g of the compound (A-18b) obtained above and 14 g of 3,5-dinitrobenzoyl chloride were mixed and stirred at 0 ° C. for 10 minutes in 300 mL of tetrahydrofuran solvent. To this, 8.4 mL of triethylamine was added dropwise over 10 minutes, and then the reaction was performed with stirring at room temperature for 3 hours. After completion of the reaction, the reaction mixture was concentrated, 500 mL of chloroform was added, and the mixture was washed 4 times with 300 mL of water. The organic layer was dehydrated with magnesium sulfate, filtered and concentrated to recover a viscous liquid. The viscous liquid was purified by column chromatography using (developing solvent: chloroform) to obtain 20 g of pale yellow oily compound (A-18c).
(4) Synthesis of Compound (A-18) Under a nitrogen atmosphere, 20 g of (A-18c) obtained above and 78 g of tin (II) chloride dihydrate were mixed, and the mixture was refluxed in 350 mL of ethyl acetate solvent. Stir with heating for hours. Subsequently, 400 mL of 2 mol / L potassium fluoride aqueous solution was added and stirred, and the deposited salt was separated by filtration. The organic layer was washed once with 400 ml of 2 mol / L potassium fluoride and three times with 400 mL of water, dehydrated using magnesium sulfate, filtered and concentrated to obtain a pale yellow powder. The obtained powder was purified by column chromatography (developing solvent: chloroform / ethanol = 95/5 (volume ratio)) to obtain 14 g of white powder (A-18).
Example 3 ( Reference Example, Synthesis of Compound (A-24))
A compound represented by the above formula (A-24) (hereinafter referred to as “compound (A-24)”) is represented by the following scheme 3.

Was synthesized according to
(1) Synthesis of Compound (A-24b) In a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, 24 g of Compound (A-10a) and 150 mL of tetrahydrofuran were charged and cooled to -18 ° C. To this, 55 ml of a borane-tetrahydrofuran complex / tetrahydrofuran solution having a concentration of 0.9 mol / L was added dropwise over 30 minutes, followed by further reaction at room temperature for 16 hours. After completion of the reaction, the reaction mixture was ice-cooled, and 30 mL of water was slowly added thereto, and then ethyl acetate was added, and the organic layer obtained was separated successively with a saturated aqueous sodium hydrogen carbonate solution twice and with water three times. After washing, the organic layer was dried over magnesium sulfate, concentrated and dried to obtain 17 g of white powder of compound (A-24b).
(2) Synthesis of (A-24c) Into a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, was charged 15 g of the compound (A-24b) obtained above, 4.5 mL of triethylamine and 100 mL of tetrahydrofuran. Ice-cooled. 7.4 g of 3,5-dinitrobenzoyl chloride dissolved in 50 mL of tetrahydrofuran was added dropwise over 1 hour using a dropping funnel, and the reaction was further performed at room temperature for 2 hours. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was separated and washed with a saturated aqueous solution of sodium bicarbonate twice and with water three times, and then the organic layer was dried over magnesium sulfate. Then, after concentration and drying, 10 g of compound (A-24c) was obtained by recrystallization from ethanol.
(3) Synthesis of Compound (A-24) In a 1 L three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer, 10 g of (A-24c) obtained above, 95 mg of 5 wt% palladium carbon powder, 120 mL of ethanol Then, 60 mL of tetrahydrofuran and 3.8 mL of hydrazine monohydrate were added and stirred at room temperature for 1 hour, followed by further stirring at 70 ° C. for 1 hour. After completion of the reaction, the organic layer obtained by adding 300 mL of ethyl acetate to the filtrate obtained by filtering the reaction mixture through Celite was separated and washed three times with water, and then concentrated and dried. The dried product was recrystallized from ethanol to obtain 7 g of Compound (A-24).
Example 4 (Reference Example)
A compound represented by the above formula (A-22) (hereinafter referred to as “compound (A-22)”) is represented by the following scheme 4.

Was synthesized according to
(1) Synthesis of Compound (A-22b) 47 g of Compound (A-10a) and 28 g of 3,5- (N, N-diallyl) diaminophenol were mixed and stirred at 400C in 400 mL of tetrahydrofuran. To this, 25 g of N, N-dicyclohexylcarbodiimide and 2.4 g of N, N-dimethylaminopyridine were added, followed by stirring at 25 ° C. for 4 hours. Thereafter, chloroform was added, and the organic layer was washed with water and concentrated. The concentrate was purified by column chromatography (developing solvent: hexane: ethyl acetate = 8: 1 (volume ratio)) to obtain a crude product of compound (A-22b).
(2) Synthesis of Compound (A-22) 38 g of (A-22b) obtained above, 23 g of 1,3-dimethylbarbituric acid and 1.1 g of tetrakistriphenylphosphine palladium were mixed, and 35 ° C. in 200 mL of dichloromethane. The reaction was carried out with stirring for 7 hours. After completion of the reaction, the reaction mixture was washed successively with a saturated aqueous solution of sodium bicarbonate and water, and then the organic layer was concentrated to remove the rainy season to obtain a brown viscous liquid. The viscous liquid was purified by column chromatography (developing solvent: chloroform: ethanol = 95: 5 (volume ratio)) and then recrystallized from ethanol to obtain 13 g of compound (A-22) as a pale yellow Obtained as a powder.
Example 5
A compound represented by the above formula (A-26) (hereinafter referred to as “compound (A-26)”) is represented by the following scheme 5.

Was synthesized according to
(1) Synthesis of Compound (A-26a) In a 10 L three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 778 g of β-cholestanol, 458 g of glutaric anhydride, 30 g of N, N-dimethylaminopyridine, triethylamine 340 mL and 4 L of ethyl acetate were charged and reacted at 90 ° C. for 8 hours. After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and 2 L of chloroform was added. The organic layer was washed successively with dilute hydrochloric acid 3 times and then with water 4 times, and then dried over magnesium sulfate. A precipitate formed by concentrating the organic layer was filtered off and the solvent was removed to obtain 498 g of a white powder of the compound (A-26a).
(2) Synthesis of Compound (A-26b) In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 254 g of Compound (A-26a) synthesized above, 108 g of 3,5-dinitrobenzyl chloride, 207 g of potassium carbonate, 150 g of sodium iodide and 1,500 mL of N, N-dimethylformamide were charged and reacted at 60 ° C. for 8 hours. After completion of the reaction, 3 L of chloroform was added and the organic layer obtained was washed 3 times with water and then dried over magnesium sulfate. The organic layer was concentrated to recover the precipitated solid, which was washed with ethanol to obtain 305 g of a pale yellow powder of compound (A-26b).
(3) Synthesis of Compound (A-26) In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 228 g of Compound (A-26b) synthesized above, 680 g of tin chloride dihydrate and acetic acid 2 L of ethyl was charged, and the reaction was performed under reflux for 4 hours. After completion of the reaction, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 60 g of pale yellow crystals of compound (A-26).

Example 6 (Synthesis Example 1 of imidized polymer)
65 g (TCA) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 31 g of p-phenylenediamine as diamine compound and 9.2 g of compound (A-10) synthesized in Example 1 above (Corresponding to 0.05 molar equivalent to 1 molar equivalent of TCA) is dissolved in 420 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and a solution containing 20% by weight of polyamic acid is obtained. Obtained. The solution viscosity of this polyamic acid solution was 4,700 mPa · s.
Next, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 23 g of pyridine and 30 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration cyclization reaction are removed outside the system in this operation. The same applies hereinafter). Thus, a solution containing 20% by weight of an imidized polymer (PI-1) having an imidation ratio of about 49% was obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 22 mPa · s.

Example 7 (Synthesis Example 2 of imidized polymer)
60 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 27 g of p-phenylenediamine as diamine compound and 17 g of compound (A-10) synthesized in Example 1 above (TCA) 0.1 mol equivalent to 1 mol equivalent) was dissolved in 420 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of this polyamic acid solution was 3,700 mPa · s.
Next, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 21 g of pyridine and 28 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-2) having an imidization ratio of about 50%. Obtained. A small amount of this solution was collected, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 20 mPa · s.

Example 8 ( Reference Example, Synthesis Example 3 of Imidized Polymer)
2,3,5-tricarboxycyclopentyl acetic acid dianhydride 21 g (TCA) as tetracarboxylic dianhydride, 9.0 g of p-phenylenediamine as diamine compound and compound (A-18) 5 synthesized in Example 2 above .3 g (corresponding to 0.1 molar equivalent with respect to 1 molar equivalent of TCA) is dissolved in 140 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and contains 20% by weight of polyamic acid. A solution was obtained. The solution viscosity of this polyamic acid solution was 3,500 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 15 g of pyridine and 19 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-3) having an imidization ratio of about 78%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 21 mPa · s.

Example 9 ( Reference Example, Synthesis Example 4 of Imidized Polymer)
2,3,5-tricarboxycyclopentylacetic acid dianhydride 20 g (TCA) as tetracarboxylic dianhydride, 8.9 g of p-phenylenediamine as diamine compound and compound (A-24) 5 synthesized in Example 3 above .6 g (corresponding to 0.1 molar equivalent with respect to 1 molar equivalent of TCA) is dissolved in 140 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and contains 20% by weight of polyamic acid. A solution was obtained. The solution viscosity of this polyamic acid solution was 3,600 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 19 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-4) having an imidization ratio of about 80%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 22 mPa · s.

Example 10 ( Reference Example, Synthesis Example 5 of Imidized Polymer)
2,3,5-tricarboxycyclopentylacetic acid dianhydride 20 g (TCA) as tetracarboxylic dianhydride, 8.9 g of p-phenylenediamine as diamine compound and compound (A-22) 5 synthesized in Example 4 above 0.5 g (corresponding to 0.1 molar equivalent with respect to 1 molar equivalent of TCA) is dissolved in 140 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and contains 20% by weight of polyamic acid. A solution was obtained. The solution viscosity of this polyamic acid solution was 3,700 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 19 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of imidized polymer (PI-5) having an imidization ratio of about 79%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 22 mPa · s.

Example 11 (Synthesis Example 6 of imidized polymer)
2,3,5-tricarboxycyclopentylacetic acid dianhydride 20 g (TCA) as tetracarboxylic dianhydride, 8.9 g of p-phenylenediamine as diamine compound and compound (A-26) 5 synthesized in Example 5 above 0.8 g (corresponding to 0.1 molar equivalent with respect to 1 molar equivalent of TCA) is dissolved in 140 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and contains 20% by weight of polyamic acid. A solution was obtained. The solution viscosity of this polyamic acid solution was 3,400 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 19 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-6) having an imidization ratio of about 78%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 21 mPa · s.

Example 12 (Synthesis Example 7 of imidized polymer)
65 g (TCA) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 31 g of p-phenylenediamine as diamine compound and 9.2 g of compound (A-10) synthesized in Example 1 above (Corresponding to 0.05 molar equivalent to 1 molar equivalent of TCA) is dissolved in 420 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and a solution containing 20% by weight of polyamic acid is obtained. Obtained. The solution viscosity of this polyamic acid solution was 4,700 mPa · s.
Next, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 46 g of pyridine and 60 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-7) having an imidization ratio of about 78%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 22 mPa · s.

Example 13 (Example 8 of synthesis of imidized polymer)
60 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 27 g of p-phenylenediamine as diamine compound and 17 g of compound (A-10) synthesized in Example 1 above (TCA) 0.1 mol equivalent to 1 mol equivalent) was dissolved in 420 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of this polyamic acid solution was 3,700 mPa · s.
Next, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 42 g of pyridine and 56 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of an imidized polymer (PI-8) having an imidization ratio of about 80%. Obtained. A small amount of this solution was collected, diluted with N-methyl-2-pyrrolidone, and measured as a solution having a polymer concentration of 6.0% by weight. The solution viscosity was 20 mPa · s.

Comparative Synthesis Example 1 (Comparative synthesis example of imidized polymer)
29 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic anhydride and 11 g of p-phenylenediamine as diamine compound and the following formula (R-1)

9.9 g of the compound represented by the formula (corresponding to 0.2 molar equivalent with respect to 1 molar equivalent of TCA) is dissolved in 450 g of N-methyl-2-pyrrolidone, reacted at 60 ° C. for 6 hours, and polyamic acid. A solution containing 20% by weight was obtained. The solution viscosity of this polyamic acid solution was 3,500 mPa · s.
Next, 500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 10 g of pyridine and 13 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone to obtain a solution containing 20% by weight of the imidized polymer (B-1) having an imidization ratio of about 49%. Obtained. A small amount of this solution was taken, diluted with N-methyl-2-pyrrolidone, and the solution viscosity measured as a solution having a polymer concentration of 6.0% by weight was 19 mPa · s.

Example 14 (Preparation and evaluation of liquid crystal aligning agent)
<Preparation of liquid crystal aligning agent>
(1) Preparation of liquid crystal aligning agent for evaluation of printability N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solution containing the imidized polymer (PI-1) obtained in Example 6 above. A solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 6.0% by weight was obtained. A liquid crystal aligning agent for printability evaluation was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
(2) Preparation of crystal aligning agent for production of liquid crystal display element N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to the solution containing imidized polymer (PI-1) obtained in Example 6 above. In addition, a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 4% by weight was obtained. The solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent for producing a liquid crystal display element.
<Evaluation of liquid crystal aligning agent>
Evaluation was performed by the following method using any of these liquid crystal aligning agents. The evaluation results are shown in Table 1.
(1) Evaluation of printability About the liquid crystal aligning agent for printability evaluation prepared above, the glass substrate with a transparent electrode which consists of an ITO film on the following conditions using a liquid crystal aligning film printer (made by Nissha Printing Co., Ltd.). The film was applied to the transparent electrode surface, heated at 80 ° C. for 1 minute (pre-baked) to remove the solvent, and then heated at 200 ° C. for 60 minutes (post-baked) to form a coating film having a thickness of 60 nm. When this coating film was visually observed for the presence of repellency and coating unevenness, the case where neither printing unevenness nor pinholes were observed was evaluated as “good”.

(2) Evaluation of Vertical Alignment Controlling Force The liquid crystal aligning agent for liquid crystal display device preparation prepared above 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. After removing the solvent by heating (prebaking) at 1 ° C. for 1 minute, a coating film having a thickness of 0.08 μm was formed by heating at 200 ° C. for 60 minutes. Next, the coating film was rubbed with a rubbing machine having a roll around which a rayon cloth was wound at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a hair foot indentation length of 0.4 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 10 minutes, followed by drying in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a rubbing-treated liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film subjected to rubbing treatment.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superposed and pressure-bonded so as to be antiparallel. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, thereby controlling the vertical alignment control force. A liquid crystal cell for evaluation was manufactured.
With respect to this liquid crystal display element, those having a pretilt angle measured by the crystal rotation angle method of 86 ° or more were evaluated as “good” for the vertical alignment regulating force, and those having a pretilt angle of less than 86 ° were evaluated as “poor” for the vertical alignment regulating force.
In addition, it is known that the rubbing process performed above has an effect of reducing the vertical alignment regulating force of the liquid crystal alignment film. When the pretilt angle of 86 ° or more is exhibited even though the rubbing treatment is performed, it can be said that the vertical alignment regulating force is extremely excellent. A liquid crystal aligning agent that gives such a result is an VA type liquid crystal using an ODF method. It has been empirically found that display unevenness does not occur even when used for manufacturing display elements.

(3) Evaluation of voltage holding ratio A liquid crystal cell was produced in the same manner as in (2) Evaluation of vertical alignment regulating force except that rubbing treatment was not performed.
A voltage of 5 V was applied to this liquid crystal cell at 60 ° C. with an application time of 60 microseconds and a span of 16.7 microseconds, and the voltage holding ratio after 16.7 milliseconds after the voltage application was released was measured. did.
(4) Evaluation of heat resistance (substitute evaluation of long-term continuous drive resistance)
For a liquid crystal cell manufactured in the same manner as described above, a voltage of 5 V was first applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The numerical value at this time was defined as the initial voltage holding ratio (VHR _BF ).
After the VHR _BF measurement, the liquid crystal display element was put in an oven at 100 ° C., and thermal stress was applied for 1,000 hours. Next, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature, and then the voltage holding ratio (VHR _AF ) after application of thermal stress was measured under the same conditions as the measurement of the initial voltage holding ratio.
The following mathematical formula (2)
_{△ VHR (%) = ((} VHR BF -VHR AF) ÷ VHR BF) × 100 (2)
Thus, the change rate (ΔVHR) of the voltage holding ratio before and after the application of the thermal stress was obtained, and those having this change rate of less than 5% were evaluated as heat resistance “good” and those having 5% or more as heat resistance “bad”. .
The evaluation results are shown in Table 1.

Examples 15 to 23 and Comparative Example 1 (However, Examples 18 to 20 are reference examples.)
Two types of liquid crystal aligning agents were prepared and evaluated in the same manner as in Example 14 except that the composition of the liquid crystal aligning agent was as shown in Table 1. In Examples 15 and 17 to 23, after adding a predetermined solvent to the polymer solution, the following formula (E-1)

20 parts by weight of the epoxy compound represented by the formula was added to 100 parts by weight of the polymer.
The results are shown in Table 1.

Claims (5)

Tetracarboxylic dianhydride and the following formula (A)

(In the formula (A), R ^I and R ^III are each independently an ether bond, a thioether bond, an ester bond or a thioester bond, provided that R ^II is a methylene group or an alkylene group having 2 to 10 carbon ^{atoms, R IV} is a main styrene group or an ethylene group, X is a monovalent organic group having 17 to 40 carbon atoms having a steroid skeleton.)
A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine containing a compound represented by the formula (I) and an imidized polymer thereof. The group X in the above formula (A) is represented by the following formula (X-1-1) or (X-2-1)

("*" In the above formula indicates a bond)
The liquid crystal aligning agent of Claim 1 which is group represented by these.   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1. Tetracarboxylic acid dianhydride and a polyamic acid or imidized polymer obtained by reacting a diamine containing a compound represented by the following following formula (A).

(In the formula (A), R ^I and R ^III are each independently an ether bond, a thioether bond, an ester bond or a thioester bond, provided that R ^II is a methylene group or An alkylene group having 2 to 10 carbon atoms, R ^IV is a methylene group or an ethylene group, and X is a monovalent organic group having 17 to 40 carbon atoms having a steroid skeleton.) Compound represented by the following following formula (A).

(In the formula (A), R ^I and R ^III are each independently an ether bond, a thioether bond, an ester bond or a thioester bond, provided that R ^II is a methylene group or An alkylene group having 2 to 10 carbon atoms, R ^IV is a methylene group or an ethylene group, and X is a monovalent organic group having 17 to 40 carbon atoms having a steroid skeleton.)