KR20080084696A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent, and a liquid crystal display device using the liquid crystal aligning agent are provided to improve printing property, to increase voltage holding ratio and to enhance electrostatic discharge. A liquid crystal aligning agent comprises a poly(amic acid) prepared by the reaction of a tetracarboxylic dianhydride represented by the formula 1, at least one diamine represented by the formulas 2 to 5 and at least one diamine represented by the formula 6 or 7, and/or its imidation polymer, wherein R1 is a tetravalent organic group; R2 to R5 are a C1-C40 linear, branched or cyclic alkyl group or a C4-C40 linear, branched or cyclic alkenyl group and can be substituted with F; A1 and A2 are independently H or a methyl group; X1 and X2 are independently -O-, -COO- or -OCO-; R6 is a monovalent organic group having a steroid structure; and R7 is a divalent organic group having a steroid structure.

Description

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

This invention relates to the liquid crystal display element which has a liquid crystal aligning agent and a liquid crystal aligning film. More specifically, the liquid crystal alignment is excellent in printability, the amount of charge accumulated in the obtained liquid crystal alignment film is small, has a high voltage retention, and is excellent in electrostatic leakage, and is particularly applicable to vertical liquid crystal display elements. And a liquid crystal display device having high quality display performance.

Currently, as a liquid crystal display element, the liquid crystal aligning film containing polyamic acid, polyimide, etc. is formed in the surface of the board | substrate with which transparent conductive films, such as ITO (indium oxide-tin oxide), are provided, and it is set as the board | substrate for liquid crystal display elements, The two sheets were arranged to face each other to form a layer of nematic liquid crystal having positive dielectric anisotropy in the gap to form a sandwich cell, and the long axis of the liquid crystal molecules was continuously twisted by 90 ° from one substrate to the other substrate. TN type liquid crystal display elements having a so-called TN (Twisted Nematic) type liquid crystal cell are known. In addition, a STN (Super Twisted Nematic) type liquid crystal display device having a higher contrast and less visual dependence than a TN type liquid crystal display device has been developed. The STN type liquid crystal display device uses a blend of nematic liquid crystals with a chiral agent, an optically active substance, as a liquid crystal, and the birefringence effect caused by the long axis of the liquid crystal molecules continuously twisted over 180 ° between the substrates. It is to use.

In recent years, a transverse electric field type liquid crystal display device has been proposed in which two electrodes for driving a liquid crystal are arranged in a comb-tooth shape on one substrate, and an electric field parallel to the substrate surface is generated to control the liquid crystal molecules. This device is generally called an in-plane switching type (IPS type) and is known for its wide viewing angle characteristics. In particular, when the IPS device is used in combination with an optical compensation film, the viewing angle characteristic can be further improved, and a wide viewing angle comparable to the CRT can be obtained without grayscale inversion or color tone change.

In addition to these, a vertically aligned liquid crystal display device called a multi-domain vertical alignment (MVA) method or a patterned vertical alignment (PVA) method in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned to a substrate has been proposed (the following patent) See Document 1 and Non-Patent Document 1). These vertically-aligned liquid crystal display elements are excellent in the viewing angle, contrast, etc., and also in the manufacturing process aspect, such as not having to perform a rubbing process in formation of a liquid crystal aligning film.

By the way, the spread of liquid crystal television is progressing in recent years, and the large line called "seventh generation" is operating. In addition, construction of a larger "eighth generation" line is also planned. The advantage of making the substrate larger by using a large line is that it is possible to obtain several panels from one substrate, so that the process time can be reduced and the cost can be reduced. There are things that can be said. On the other hand, as a disadvantage of the enlargement of the substrate, it is difficult to ensure the uniformity of printing of the liquid crystal aligning agent over a large area, and the problem of the electrical characteristics of the liquid crystal aligning film due to the poor printing of the liquid crystal aligning agent occurs. There is a point.

In the large sized board | substrate manufactured by a large line, in order to manufacture a liquid crystal display element with a high yield, the liquid crystal aligning agent excellent in printability is calculated | required more than ever. Moreover, the demand for the improvement of the display quality in recent years becomes more severe, and the liquid crystal aligning film which has the above characteristic with respect to liquid crystal aligning property and an electrical property especially is calculated | required.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-258605

[Non-Patent Document 1] "Liquid Crystal", Vol. 3 (No. 2), p117 (1999)

This invention is made | formed based on the said situation, The objective is that it is excellent in printability, the product yield in the manufacturing process by a large line can be improved, and the charge accumulation amount of the liquid crystal aligning film obtained shows small high voltage retention. Moreover, it is providing the liquid crystal aligning agent which provides the liquid crystal aligning film excellent in the electrostatic leakage property, and the liquid crystal display element which shows the display quality of high quality.

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

According to the present invention, the above object of the present invention firstly,

(a) tetracarboxylic dianhydride represented by the following formula (1),

(b1) at least one selected from diamines represented by the following Chemical Formulas 2 to 5,

(b2) Liquid crystal aligning agent containing the polyamic acid (henceforth "a specific polyamic acid") obtained by reaction with 1 or more types chosen from diamine represented by following formula (6) or (7), and / or its imidation polymer Is achieved by.

(In Formula 1, R ¹ is a tetravalent organic group.)

R <^2> -R <^5> is a C1-C40 linear, branched or cyclic alkyl group, or a C4-C40 linear, branched or cyclic alkenyl group, and R <^2> -R <^5> has a hydrogen atom 1 to 15 of which may be substituted with a fluorine atom, A ¹ and A ² are each independently a hydrogen atom or a methyl group)

(In Formulas 6 and 7, X ¹ and X ² are each independently a divalent group represented by -O-, -COO-, or -OCO-, R ⁶ is a monovalent organic group having a steroid skeleton, and R ⁷ Is a divalent organic group having a steroid skeleton)

The said object of this invention is 2nd achieved by the liquid crystal display element provided with the liquid crystal aligning film obtained from the said liquid crystal aligning agent.

Since the liquid crystal aligning agent of this invention is excellent in printability, it can improve the product yield in the manufacturing process by a large line, and also is excellent in the electrostatic leakage property of the liquid crystal aligning film obtained, It is possible to minimize the occurrence of defects caused by. Moreover, since the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention is excellent in an electrical property, it is suitable for especially applying to the liquid crystal display element of a vertical alignment type.

The liquid crystal display element of this invention can be used suitably as a display apparatus of various apparatuses, for example, a table calculator, a wristwatch, a table clock, a mobile telephone, a counting plate, a word processor, a personal computer, and a liquid crystal television.

The liquid crystal aligning agent of this invention contains said specific polyamic acid and / or its imidation polymer. Hereinafter, the tetracarboxylic dianhydride and diamine used in order to synthesize the polymer contained in the liquid crystal aligning agent of this invention are demonstrated.

<(a) Tetracarboxylic dianhydride>

(A) Tetracarboxylic dianhydride used for the synthesis | combination of specific polyamic acid and / or its imidation polymer is a compound represented by the said General formula (1), For example, aliphatic tetracarboxylic dianhydride, alicyclic tetracarb Acid dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned.

As said aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxyl Acid dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,3-diethyl-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 dianhydride, 3,5,6- Tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuranthratecarboxylic acid dianhydride Water, 1,2,4-carboxy-cyclopentyl-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-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) -naph Earth [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-dioxote Trahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxyl Acid dianhydrides, bicyclo [2.2.2] -oct-4-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6- Tetracarboxylic dianhydride, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-3,4,8,9-tetracarboxylic dianhydride, the following formula (8) or (9)

(8)

(8)

(9)

(9)

(Formula 8 and Formula 9 of, R ⁸ and R ¹⁰ represents a divalent organic group having an aromatic ring, R ⁹ and R ¹¹ represents a hydrogen atom or an alkyl group, a plurality of existing R ⁹ and R ¹¹ is Each may be the same or different)

As said aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Sulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'- Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantheracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy Diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydrides, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetraca Acid 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 (anhydrotrimelitate), propylene glycol-bis (anhydrotri Mellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate) And 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate).

These (a) tetracarboxylic dianhydrides are used individually by 1 type or in combination of 2 or more types.

As (a) tetracarboxylic dianhydride used for synthesis | combination of specific polyamic acid, alicyclic tetracarboxylic dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione and 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5- All tetracarboxylic dianhydrides are selected from the group consisting of dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and one or more tetracarboxylic dianhydrides. It is more preferable to contain 50 mol% or more with respect to it, It is more preferable to contain 70 mol% or more from a viewpoint of the characteristic improvement of the liquid crystal aligning film obtained, It is preferable to contain especially 80 mol% or more.

<Diamine>

The diamine used for the synthesis of the specific polyamic acid and / or the imidized polymer thereof is (b1) at least one selected from the diamines represented by the formulas (2) to (5) (hereinafter referred to as "diamine (b1)") and ( b2) at least one selected from the diamines represented by the above formulas (6) or (7) (hereinafter referred to as "diamine (b2)").

In the diamine (b1) represented by Formula 2 to 5, as the linear alkyl group having 1 to 40 carbon atoms represented by R ² to R ^5, for example, n- hexyl, n- octyl group, n- decyl group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc .;

As the branched alkyl group, for example, 1-methylhexyl group, 1-ethylhexyl group, 2-methylhexyl group, 2-ethylhexyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 1,2-dimethylhexyl group, 1,2-diethylhexyl group, 1,2-dimethyloctyl group, 1,2-diethyloctyl group, 1-methyldecyl group, 1-ethyldecyl group, 2-methyldecyl Practical groups, 2-ethyldecyl group and the like;

Examples of the cyclic alkyl group include hydrogen atoms from cyclic alkanes such as cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornene, bicyclooctane, bicycloundecane, adamantane, cholesterol, and cholestanol. The group obtained by removing a dog is mentioned, respectively.

Examples of the linear, branched or cyclic alkenyl group having 4 to 40 carbon atoms represented by R ² to R ⁵ include groups in which at least one of the carbon-carbon bonds of the alkyl group exemplified above is a double bond.

As diamine (b1), what is represented by the said Formula (2) is preferable, In said Formula (2), R <^2> has a C1-C20 linear, branched or C4-C20 linear form containing 1 or more of unsaturated ring or unsaturated bonds. And diamine which is a branched or cyclic alkenyl group is more preferable. As a preferable specific example of diamine (b1), for example, 1- (3,5-diaminophenyl) -3-octadecylsuccinimide and 1- (3,5-diaminophenyl) -3-dodecylsuccinate are Mead etc. are mentioned.

As a preferable specific example of a diamine (b2), it is a compound represented by the said General formula (6), for example, following General formula (10)-(19)

Compounds represented by such as;

As the compound represented by the formula (7), for example, the following formula (20) or (21)

The compound etc. which are represented by these are mentioned, respectively.

It is preferable to use diamine (b1) in 1 to 60 mol% with respect to the total amount of diamine (b1) and diamine (b2), and it is more preferable to use it in 10 to 50 mol% in range.

<Other diamines>

In the synthesis of the specific polyamic acid, other diamines can be used in addition to the diamine (b1) and the diamine (b2). As another diamine, aromatic diamine, aliphatic or alicyclic diamine, the diamine which has two primary amino groups in a molecule | numerator, and nitrogen atoms other than the said primary amino group etc. are mentioned, for example.

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane and 4,4'-diaminodi. Phenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodi Phenyl 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'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane,

2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3 -Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-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-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4, 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 4 -(4-n-heptylcyclohexyl) phenoxy-2,4-diaminobenzene, having the general formulas (22) to (25)

Compounds represented by such as;

Examples of the aliphatic or alicyclic diamines include 1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nonnamethylene. Diamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene nilenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tri Cyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) and the like;

Examples of the diamine having two primary amino groups and nitrogen atoms other than the primary amino group in the molecule include 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-dimethyl Amino-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-ethoxyacridinlac Tate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6- Amino may Noah acridine, bis (4-aminophenyl) phenylamine, etc., respectively.

These other diamine compounds can be used individually or in combination of 2 or more types.

When using diamine (b1), diamine (b2), and other diamine together in the synthesis | combination of a specific polyamic acid, it is preferable that the use ratio of another diamine is 90 mol% or less with respect to all diamine.

<Synthesis of specific polyamic acid>

Next, the synthesis | combining method of the specific polyamic acid which the liquid crystal aligning agent of this invention can contain is demonstrated.

The specific polyamic acid is the tetracarboxylic dianhydride, the diamine (b1) and the diamine (b2), and optionally other diamines, preferably in an organic solvent, preferably -20 ° C to 150 ° C, more preferably. Preferably, it can synthesize | combine by making it react for 1 to 30 hours, under the temperature conditions of 0-100 degreeC.

As for the usage ratio of the tetracarboxylic dianhydride and diamine provided for the synthesis reaction of a specific polyamic acid, the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.5-2 equivalent with respect to 1 equivalent of amino group of diamine, More preferably, it is the ratio used as 0.7 to 1.2 equivalent.

The organic solvent is not particularly limited as long as it can dissolve the specific polyamic acid synthesized. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, can be illustrated. Moreover, it is preferable that the usage-amount ((alpha)) of an organic solvent is an amount which the ratio (monomer concentration) with respect to whole quantity ((alpha) + (beta)) of the total amount ((beta)) of tetracarboxylic dianhydride and a diamine compound becomes 0.1-30 weight%. Do.

In the organic solvent, alcohol, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of specific polyamic acids, may be used in combination without causing specific polyamic acid to be precipitated. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, 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 methoxy propionate, ethyl ethoxy propionate, Diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, di Tylene 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, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.

As described above, a reaction solution obtained by dissolving a specific polyamic acid is obtained. Then, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with a evaporator to obtain a polyamic acid. In addition, the specific polyamic acid can be purified by dissolving the specific polyamic acid again in an organic solvent and then depositing it with a poor solvent, or distilling off and removing the reaction solution under reduced pressure with an evaporator once or several times. .

<The synthesis method of the imidation polymer of specific polyamic acid>

Next, the synthesis | combining method of the imidation polymer of the specific polyamic acid which the liquid crystal aligning agent of this invention can contain is demonstrated.

The imidation polymer of a specific polyamic acid can be synthesize | combined by dehydrating and ring-closing part or all of the amic-acid structure which the said specific polyamic acid has. The imidation polymer which can be used for this invention may be partially dehydrating and ring-closing whose ratio of the repeating unit which has the imide ring in all the repeating units (henceforth "imidization rate") is less than 100%.

It is preferable that it is 50 to 100%, and, as for the imidation ratio of the imidation polymer of a specific polyamic acid, it is more preferable that it is 70 to 100%.

The dehydration ring closure reaction of a specific polyamic acid may be carried out by (i) heating the specific polyamic acid or (ii) dissolving the specific polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring closure catalyst in this solution, and heating as necessary. Is done.

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

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

<End modified polymer>

Certain polyamic acids or imidized polymers thereof used in the present invention may be of terminally modified type with controlled molecular weight. By using a terminal modified polymer, the effect of this invention is not impaired, and the application | coating characteristic of a liquid crystal aligning agent, etc. can be improved. Such a terminal modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, or the like to the reaction system when synthesizing a specific polyamic acid. Here, as an acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride etc. are mentioned, for example. Can be. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eico Silamine etc. are mentioned. As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

<Solution Viscosity of Polymer>

It is preferable that the specific polyamic acid obtained by the above and its imidation polymer have a viscosity of 20-800 mPa * s, and, as for 10% solution, it is more preferable to have a viscosity of 30-500 mPa * s.

In addition, the solution viscosity (mPa * s) of the polymer was measured at 25 degreeC using the E-type rotational viscometer with respect to the solution diluted to 10% of solid content concentration using the predetermined solvent.

<Other polymer>

In the liquid crystal aligning agent of this invention, unless the effect of this invention is impaired, 1 or more types chosen from the group which consists of a part of said specific polyamic acid or its imidation polymer from another polyamic acid and its imidation polymer ( Or "other polymers").

The said other polymer will not be specifically limited if it is a polyamic acid other than the said specific polyamic acid, or its imidation polymer, but the polymer obtained by reaction of the tetracarboxylic dianhydride represented by the said General formula (1) with the other diamine mentioned above Or an imidized polymer thereof. As tetracarboxylic dianhydride used here, alicyclic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride or fatigue is especially preferable. Mellitic dianhydride is preferred. As another diamine used here, aromatic diamine is preferable and 4,4'- diamino diphenylmethane or 4,4'- diamino diphenyl ether is especially preferable.

Synthesis of such another polymer can be performed similarly to the synthesis | combination of a specific polyamic acid and its imidation polymer except using another diamine instead of diamine (b1) and diamine (b2).

When the liquid crystal aligning agent of this invention contains another polymer, the use ratio of another polymer is 90 weight% or less with respect to the total amount of a specific polyamic acid and its imidation polymer, and another polymer, More preferably, 80 It is weight% or less.

<Other ingredients>

Although the liquid crystal aligning agent of this invention contains the said specific polyamic acid and / or its imidation polymer as an essential component, it can contain other components arbitrarily. As such another additive, a functional silane compound, an epoxy compound, etc. are mentioned, for example. These functional silane compounds and an epoxy compound can be added for the adhesive improvement to the board | substrate surface of the liquid crystal aligning film obtained.

As said functional silane containing compound, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-ben -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimeth Oxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

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, 1,6-hexanediol 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-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N- diglycidyl) aminopropyltrimethoxysilane, N, N- diglycidyl-benzylamine, N, N- diglycidyl-aminomethylcyclohexane, etc. are mentioned. .

The usage-amount of these functional silane compounds or an epoxy compound is 50 weight part or less with respect to 100 weight part of whole polymers (it refers to specific polyamic acid and its imidation polymer, and all other polymers, respectively. Preferably from 0.1 to 30 parts by weight.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is manufactured as a solution state in which the specific polyamic acid and / or its imidation polymer, and the other component added optionally are melt | dissolved in the organic solvent preferably.

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

As an especially preferable organic solvent used for the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether , Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Tate, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, diethylcarbitol, ethylcarbitol Acetate, butyl carbitol, triethylene glycol dimethyl ether, isoamyl isobutyrate, diisopentyl ether, etc. are mentioned. These may be used independently, or may mix and use 2 or more types.

Solid content concentration (the value which divided the total weight of components other than the solvent in a liquid crystal aligning agent by the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is in the range of 1 to 10 weight% in consideration of viscosity, volatility, etc. It is preferred to be selected. Although the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes too small and a favorable liquid crystal aligning film cannot be obtained, while solid content concentration is When it exceeds 10 weight%, the film thickness of a coating film will become large too much and a favorable liquid crystal aligning film may not be obtained, and also the viscosity of a liquid crystal aligning agent may increase and coating characteristics may fall, and it is unpreferable.

On the other hand, the range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, in the case of a spinner method, the range of 1.5 to 4.5 weight% is especially preferable. In the case of the printing method, the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is particularly preferably in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s by this.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention obtained as mentioned above, It is characterized by the above-mentioned.

The liquid crystal display element of this invention can be manufactured by the following process (1) and (2), for example.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by appropriate coating methods, such as an offset printing method, a spin coating method, and the inkjet printing method, and then a coating film is heated by heating a coating surface. Form. As a coating method applied to the liquid crystal aligning agent of this invention, the inkjet printing method is preferable. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone and polycarbonate can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd. USA), an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. The transparent conductive film can be used, and the patterning of these transparent conductive films, the photo-etching method, the method of using a mask when forming a transparent conductive film, etc. are used.

In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. . The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. On the other hand, although the liquid crystal aligning agent of this invention forms the coating film which becomes an alignment film by removing an organic solvent after application | coating, when the liquid crystal aligning agent of this invention contains the polymer which has an amic acid unit, it heats further after coating film formation. The dehydration ring closure of an amic acid unit can also be advanced and it can be set as the more imidized coating film.

The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) Two board | substrates with a liquid crystal aligning film were manufactured as mentioned above, these two board | substrates were opposingly arranged through a gap (cell spacing), the peripheral part of two board | substrates was bonded together using a sealing agent, and the board | substrate surface And filling the liquid crystal into the cell gap partitioned by the sealant, and sealing the injection hole to constitute the liquid crystal cell. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate in the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell. Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and aluminum oxide sphere as a spacer can be used, for example.

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred, and for example, Schiff base liquid crystals, subfamily clock liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, A terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. Moreover, it is sold to these liquid crystals as cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonaate, a cholesteryl carbonate, and brand names "C-15", "CB-15" (made by Merck), for example. It is also possible to add and use a chiral agent. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

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

<Example>

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

Evaluation of the liquid crystal aligning agent manufactured by the following example followed the following method.

[Evaluation of Voltage Retention Rate]

On the ITO electrode of the glass substrate in which the ITO electrode was formed in one surface, the liquid crystal aligning agent manufactured in each Example was apply | coated with a spinner, and it heats at 200 degreeC for 60 minutes, and the glass substrate which has a coating film of 0.08 micrometer in thickness One pair (two pieces) was produced.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer leaving a liquid crystal injection hole in each outer edge which has a liquid crystal aligning film of the said liquid crystal aligning film application board | substrate of a pair of transparent electrode / transparent board | substrate, a liquid crystal aligning film surface They were overlapped and pressed so as to face each other, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (negative type | mold, Merck make, MLC-2038) between a liquid crystal injection opening and a board | substrate, the liquid crystal injection opening is sealed with acrylic photocuring adhesive, and a polarizing plate is bonded to both surfaces of the outer side of a board | substrate, A liquid crystal display device was manufactured.

About this liquid crystal display element, after applying the voltage of 5V at 60 degreeC in 60 microseconds application time and the span of 16.7 milliseconds, the voltage retention after 16.7 milliseconds after application | release cancellation was measured.

[Evaluation of Residual Voltage]

For the liquid crystal display device manufactured above, a voltage of 17.0 V DC was applied at an environmental temperature of 100 ° C. for 20 hours, and the mixture was allowed to cool for 15 minutes at room temperature immediately after the DC voltage was cut off, and the voltage remaining in the liquid crystal cell was subjected to the flicker elimination method. It calculated | required as residual DC voltage by this. The case where this value is 1,500 mV or less was made into "good | favorableness."

[Evaluation of Electrostatic Leakage]

For the liquid crystal display device manufactured above, after applying a voltage of 110 V DC for 15 minutes via a glass substrate, the time required to reduce the luminance to 50% of the luminance immediately after voltage removal was determined as the static leakage time. It was investigated whether it corresponds to any of the following five levels.

Level 5: Electrostatic Leakage Time Within 30 Minutes

Level 4: Electrostatic Leak Time> 30 Minutes and Within 1 Hour

Level 3: electrostatic leakage time greater than 1 hour and within 2 hours

Level 2: electrostatic leakage time exceeds 2 hours and within 3 hours

Level 1: Electrostatic Leakage Time Exceeds 3 Hours

Here, in the case of level 5 or 4, it can be said that electrostatic leakage property is favorable.

Synthesis Example

<Synthesis example of diamine (b1)>

Monomer Synthesis Example 1 (Synthesis of 1- (3,5-diaminophenyl) -3-octadecylsuccinimide)

12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 mL of acetic acid were added to a 300 mL three necked flask replaced with nitrogen gas, and the solid was dissolved while stirring while flowing nitrogen gas. To this, 24.64 g (0.07 mol) of octadecylsuccinic anhydride was added and reacted under reflux for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The precipitated solid was separated by filtration, washed with methanol and dried to obtain 30 g of 1- (3,5-dinitrophenyl) -3-octadecylsuccinimide (yield 83%).

Next, 30 g (0.058 mol) of 1- (3,5-dinitrophenyl) -3-octadecylsuccinimide synthesized above in a 500 mL flask substituted with nitrogen gas, 100 mL of ethanol, tetrahydrofuran 100 mL of (THF) and 25 g of reduced catalyst palladium carbon (Pd / C) were added and stirred at 70 ° C. for 1 hour. 42.5 mL (43.75 g) of hydrazine monohydrate was added thereto, and the mixture was reacted by heating under reflux for 6 hours. Pd / C was filtered off and the filtrate was concentrated on a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, cooled, and recrystallized to obtain 14.6 g (0.032 mol) of 1- (3,5-diaminophenyl) -3-octadecylsuccinimide as a target product. , Yield 55%) was obtained.

Monomer Synthesis Example 2 (Synthesis of 1- (3,5-diaminophenyl) -3-dodecylsuccinimide)

1- (3,5-diaminophenyl) -3-dode in the same manner as in Monomer Synthesis Example 1, except that 18.76 g (0.07 mol) of dodecyl succinic anhydride was used instead of 24.64 g (0.07 mol) of octadecylsuccinic anhydride. 11 g (0.030 mol, yield 51%) of silsuccinimides were obtained.

Monomer Synthesis Example 3 (Synthesis of 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide)

31.5 g (0.25 mol) of dimethylmaleic anhydride, 89.0 g (0.5 mol) of N-bromosuccinimide, 1.0 g (4.15 mmol) of benzoyl peroxide and 1,500 mL of carbon tetrachloride were added to a 2,000 mL three-necked flask with nitrogen substitution. Heated to reflux. The reaction solution was cooled to room temperature, left at room temperature overnight, and then filtered. After washing the filtrate with water, the organic layer was concentrated on a rotary evaporator. The crude oily product obtained was distilled under high vacuum (120 to 125 ° C / 2 mmHg) to obtain 20.0 g (0.1 mol, 39% yield) of 3-bromomethyl-4-methylmaleic anhydride as an intermediate.

Next, in a 2,000 mL three-necked flask substituted with argon gas, 16.4 g (80 mmol) of 3-bromomethyl-4-methylmaleic anhydride obtained above, copper iodide 1.52 g (8.0 mmol), diethyl ether 400 mL and 160 mL of HMPA (hexamethyl phosphate triamide) were added and then cooled to -5 to 0 ° C under argon gas flow. While stirring this liquid mixture, the 400 mL solution of 400 mmol diethyl ether of hexadecyl magnesium bromide prepared separately was dripped over about 20 minutes. The mixture was returned to room temperature and stirred for further 8 hours. Thereafter, the mixture was diluted with 600 mL of diethyl ether, and then 600 mL of 4N-sulfuric acid was added to make the solution acidic. The separated aqueous layer was further washed with diethyl ether 600 mL, and the organic layers were combined. The organic layer was washed with water, dehydrated with sodium sulfate, and the solution was concentrated with a rotary evaporator to obtain an oily crude product. This crude product was purified by a silica gel column using a petroleum ether / ethyl acetate (19: 1) mixed solution as a developing solvent, to obtain 14.0 g (0.04 mol, 50% yield of 3-heptadecyl-4-methyl maleic anhydride). )

Next, 6.4 g (0.035 mol) of 3,5-dinitroaniline and 35 mL of acetic acid were added to a 200 mL three-necked flask with nitrogen gas substitution. The solid was dissolved by stirring while flowing nitrogen gas. To this, 12.3 g (0.035 mol) of 3-heptadecyl-4-methylmaleic anhydride obtained above was added and reacted under reflux for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 35 mL of methanol was added and the mixture was allowed to stand overnight. The solid was separated by filtration, washed with methanol and dried to give 14.6 g (0.029 mol, 81% yield) of 1- (3,5-dinitrophenyl) -3-heptadecyl-4-methylmaleimide.

Next, 13.4 g (0.026 mol) of 1- (3,5-dinitrophenyl) -3-heptadecyl-4-methylmaleimide, 50 mL of ethanol, 50 mL of THF and a reduction catalyst were placed in a nitrogen gas substituted 300 mL flask. 12.5 g of Pd / C were added and stirred at 70 ° C for 1 hour. Subsequently, 19 mL (19.6 g) of hydrazine monohydrate was added and reacted by heating under reflux for 6 hours. Pd / C was filtered off and the filtrate was concentrated on a rotary evaporator. The obtained crude product was recrystallized by heating and dissolving with N-methyl-2-pyrrolidone and cooling, to obtain 6.6 g of 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide as the desired product. (0.015 mol, yield 56%) was obtained.

Monomer Synthesis Example 4 (Synthesis of 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide)

12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 mL of acetic acid were added to a nitrogen-substituted 300 mL three-necked flask, followed by stirring while flowing nitrogen gas to dissolve the solid. 14.35 g (0.07 mol) of 3- (bromomethyl) -4-methylmaleic anhydride synthesized in the same manner as the intermediate of Monomer Synthesis Example 3 was added thereto, followed by reacting under reflux for 20 hours under nitrogen. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The solid was separated by filtration, washed with methanol and dried to give 18.9 g (0.051 mol, 73% yield) of 1- (3,5-dinitrophenyl) -3-bromomethyl-4-methylmaleimide.

Next, 18.1 g (0.049 mol) of 1- (3,5-dinitrophenyl) -3-bromomethyl-4-methylmaleimide, and 1-hexadecanol sodium salt 12.9 in the 500 mL three neck flask which carried out the nitrogen substitution. g (0.049 mol) and 100 mL of dimethyl sulfoxide were added, followed by stirring at 100 ° C. for 10 hours. After cooling the reaction solution to room temperature, 70 mL of methanol was added and the mixture was allowed to stand overnight. The solid was separated by filtration, washed with methanol and dried to give 20.8 g (0.039 mol, yield 80%) of 1- (3,5-dinitrophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide.

Next, 13.8 g (0.026 mol) of 1- (3,5-dinitrophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide, 300 mL of ethanol, 50 mL of THF, 12.5 g of reduction catalyst Pd / C were added and stirred at 70 ° C for 1 hour. 19 mL (19.6 g) of hydrazine monohydrate was then added and reacted by heating under reflux for 6 hours. Pd / C was filtered off and the filtrate was concentrated on a rotary evaporator. The obtained crude product was recrystallized by heating and dissolving with N-methyl-2-pyrrolidone and cooling to give 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide 8.2 as the desired product. g (0.018 mol, yield 67%) was obtained.

<Synthesis of polyamic acid and imidized polymer thereof>

Synthesis Examples 1 to 9

To N-methylpyrrolidone, diamine and tetracarboxylic dianhydride are added in this order in the composition shown in Table 1 below to give a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours to contain polyamic acid. A solution was obtained. To each of the obtained polyamic acid solutions, pyridine and acetic anhydride shown in Table 1 were added to the total amount (moles) of the amic acid units in the solution, respectively, and then heated to 110 ° C to perform a dehydration ring closure reaction for 4 hours. It was. The obtained solution was reprecipitated with diethyl ether, and recovered and dried under reduced pressure to obtain (P-1) to (P-9) which were imidized polymers. The imidation ratio of these imidation polymers is shown in Table 1.

Synthesis Examples 10-14

Diamine and tetracarboxylic dianhydride were added to N-methylpyrrolidone in the composition shown in Table 1 in this order, it was set as the solution of 20 weight% of monomer concentration, and it was made to react at 60 degreeC for 4 hours. The obtained solution was reprecipitated with diethyl ether, recovered and dried under reduced pressure to obtain polyamic acid (P-10) to (P-14). On the other hand, in the synthesis examples 10-14, the imidation reaction of polyamic acid was not performed.

In Table 1, the number in parentheses shows the usage ratio (molar ratio) of the monomers for the diamine and tetracarboxylic dianhydride, and the meanings of the symbols in the table are as follows.

<Diamine Compound>

Diamine (b1);

D-1: 1- (3,5-diaminophenyl) -3-octadecylsuccinimide

D-2: 1- (3,5-diaminophenyl) -3-dodecylsuccinimide

D-3: 1- (3,5-diaminophenyl) -3-heptadecyl-4-methylmaleimide

D-4: 1- (3,5-diaminophenyl) -3-hexadecaneoxymethyl-4-methylmaleimide

Diamine (b2);

D-5: the compound represented by general formula (11)

D-6: the compound represented by chemical formula (15)

Other diamine

D-7: p-phenylenediamine

D-8: 4,4'-diaminodiphenylmethane

D-9: 4,4'-diaminodiphenyl ether

Tetracarboxylic dianhydride

T-1: 2,3,5-tricarboxycyclopentyl acetic dianhydride

T-2: 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride

T-3: pyromellitic dianhydride

T-4: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione

T-5: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

Example 1

The imidized polymer (P-1) obtained in the synthesis example 1 was dissolved in (gamma) -butyrolactone / N-methyl- 2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 40/30/30), and an epoxy compound As an example, 20 parts by weight of N, N, N ', N'-tetraglycidyl-4,4'diaminodiphenylmethane was added to 100 parts by weight of the polymer to dissolve to obtain a solution having a solid content of 4% by weight. The liquid crystal aligning agent was manufactured by filtering this solution using the filter of 1 micrometer of pore diameters.

According to the method mentioned above using this aligning agent, voltage retention, residual voltage, and static leakage were evaluated. The results are shown in Table 2 below.

Examples 2 to 22

Except having performed the kind of the polymer mix | blended with the liquid crystal aligning agent as Table 2, it carried out similarly to Example 1, and produced the liquid crystal aligning agent, respectively, and evaluated by the method mentioned above using these aligning agents. . The evaluation results are shown in Table 2.

In addition, in Table 2, the number in parentheses after a polymer name shows the quantity (weight part) of the polymer used.

Claims (3)

(a) tetracarboxylic dianhydride represented by the following formula (1), (b1) at least one selected from diamines represented by the following Chemical Formulas 2 to 5, (b2) The liquid crystal aligning agent containing the polyamic acid obtained by reaction with 1 or more types chosen from the diamine represented by following formula (6) or (7), and / or its imidation polymer. <Formula 1>

(In Formula 1, R ¹ is a tetravalent organic group.) <Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

R <^2> -R <^5> is a C1-C40 linear, branched or cyclic alkyl group, or a C4-C40 linear, branched or cyclic alkenyl group, and R <^2> -R <^5> has a hydrogen atom 1 to 15 of which may be substituted with a fluorine atom, A ¹ and A ² are each independently a hydrogen atom or a methyl group) <Formula 6>

<Formula 7>

(In Formulas 6 and 7, X ¹ and X ² are each independently a divalent group represented by -O-, -COO-, or -OCO-, R ⁶ is a monovalent organic group having a steroid skeleton, and R ⁷ Is a divalent organic group having a steroid skeleton) (B1) Diamine is represented by the formula (2), R ² is a linear, branched carbon having 4 to 20 carbon atoms containing one or more linear, branched or cyclic alkyl groups or unsaturated bonds The liquid crystal aligning agent which is diamine which is a ground or cyclic alkenyl group. The liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 1 or 2 is provided. The liquid crystal display element characterized by the above-mentioned.