JP2893672B2 - Liquid crystal alignment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent having good orientation of liquid crystal and a large pretilt angle.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy has a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film made of polyimide or the like, and the major axis of the liquid crystal molecules is continuous at 90 degrees between the substrates. 2. Description of the Related Art A liquid crystal display device (TN display device) having a TN type alignment cell that is twisted in a vertical direction is known. The alignment of the liquid crystal in this TN type display element is formed by a liquid crystal alignment film subjected to a rubbing treatment.

Since the TN type display element is inferior in contrast and viewing angle dependency, recently, SBE (Super Twist) which is a liquid crystal display element excellent in contrast and visual dependency.
isted Birefringency Effect) display element, SH (Supe
r Homeotropic) Display elements have been developed. The SBE display element uses a nematic liquid crystal blended with a chiral agent, which is an optically active substance, as a liquid crystal. The birefringence effect caused by continuously twisting the major axis of the liquid crystal molecules between the substrates by 180 degrees or more is used. To use. In addition, the SH display device is a device in which liquid crystal molecules having a negative dielectric anisotropy in the major axis direction of the liquid crystal molecules are vertically aligned, and the molecules are defeated by applying a voltage to operate by simple matrix driving.

[0004]

SUMMARY OF THE INVENTION However, SBE
When the display element is manufactured using a liquid crystal alignment film made of polyimide or the like, the liquid crystal alignment film has a small pretilt angle, so that the liquid crystal cannot be twisted by 180 degrees or more between the substrates, and a required display function is required. Is difficult to obtain.

For this reason, in the case of the current SBE display element, it is necessary to use a liquid crystal alignment film formed by obliquely depositing silicon dioxide in order to align the liquid crystal, and the manufacturing process is complicated. There is.

The SBE display element uses a substrate on which silicon dioxide is obliquely deposited or treats the substrate with a fluorine-based surfactant or a coupling agent having a long-chain alkyl group in order to vertically align the liquid crystal. It is necessary. As described above, when silicon dioxide is obliquely deposited, the production process is complicated and mass production cannot be performed, and when a surfactant or a coupling agent is used, the reliability is poor.

An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a liquid crystal with good orientation, a large pretilt angle,
An object of the present invention is to provide a liquid crystal aligning agent that can be particularly preferably used for a liquid crystal alignment film of a BE or SH display element.

[0008]

According to the present invention, there are provided, firstly, the following general formula (I):

[0009]

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A tetracarboxylic dianhydride (hereinafter referred to as "compound I") represented by the following general formula (II): H ₂ N--R ² --NH ₂ (II) wherein R ² is divalent A diamine compound represented by the following formula (hereinafter, referred to as “compound II”) and a compound represented by the following general formula (III):

[0011]

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A monoamine compound represented by the formula
A polymer (hereinafter, referred to as “specific polymer I”) and / or an imidized polymer thereof (hereinafter, referred to as “specific polymer II”) obtained by reacting “compound III”),
Second, the general formula (IV)

[0013]

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This is achieved by a liquid crystal aligning agent characterized by containing a polymer having a structural unit represented by the following formula (hereinafter, referred to as “specific polymer III”).

The compound I used in the present invention is represented by the above general formula (I). In the general formula (I), R ¹ is four organic groups. 4
The valence organic group means a residue obtained by removing an acid anhydride group from tetracarboxylic dianhydride.

The tetracarboxylic dianhydride includes, for example, butanetetracarboxylic dianhydride, 1,2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,
2,3,4-cyclopentanetetracarboxylic dianhydride,
2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxy-norbornane-2-acetic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexene dicarboxylic acid 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;
5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,
Aliphatic and alicyclic tetracarboxylic dianhydrides such as 3,5,6-tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic 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-dicarboxyphenoxy) diphenylpropane dianhydride,
3,3 ', 4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl-tetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride Product, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, Aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride can be mentioned. Of these,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and 2,3 , 5
-Tricarboxycyclopentylacetic dianhydride is preferred.

Compound II is represented by the above general formula (II).

In the general formula (II), R ² represents a divalent organic group. The divalent organic group means a residue obtained by removing an amino group from a diamine compound.

Examples of such diamine compounds include paraphenylenediamine, metaphenylenediamine,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone,
4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,
4'-diaminobenzophenone, 2,2-bis [4-
(4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 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-hydro-anthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4 Aromatic diamines such as' -diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl; diaminotetraphenyl Aromatic diamines having a hetero atom such as thiophene;
1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-
Aliphatic or alicyclic diamines such as 4,7-methanoindanylene dimethylene diamine and tricyclo [6,2,1,0 ^2,7 ] -undecylenedimethyl diamine; and the following formula (V)

[0020]

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And the like. Among these, paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane,
2,2-bis (4-aminophenyl) hexafluoropropane and bis [4- (4-aminophenoxy) phenyl] hexafluoropropane are preferred.

Compound III is represented by the above general formula (III).

In the general formula (III), R ³ represents a divalent organic group, R ⁴ represents a monovalent organic group having a steroid skeleton, and a represents 0 or 1.

Examples of the divalent organic group for R ³ include —C
OO-, -OCO-, -CONH-, -NHCO- and -O- can be exemplified as preferable ones.

The monovalent organic group having a steroid skeleton of R ⁴ will be apparent from the steroid compound described later.

Preferred examples of the compound III include the following compounds. In the above general formula (III), examples of the steroid compound having an amino group when a is 0 include cholesterylamine, β-cholesterylamine, androsterylamine, dehydroepiandrosterylamine, epiandrosterylamine, ergosteriamine Luamine, estolylamine, 11
α-aminomethyltestosterone, 11α-aminoprogesterone, lanosterylamine, mestranylamine, methyltestosterylamine, △ ^{9 (11)} -methyltestosterylamine, norethisterylamine, pregnenylamine, β-sitosterylamine, etc. Can be mentioned. Of these, cholesterylamine and β-cholesterylamine are preferred.

Next, the case where a is 1 in the above general formula (III) will be described. The compound III in the case where R ³ is —COO— is obtained, for example, by reacting a nitro compound having an acid chloride with a steroid compound having a hydroxyl group in a solvent in the presence of a basic catalyst, and then reducing the reaction product. To convert the nitro group into an amino group.

Examples of the nitro compound having an acid chloride group include orthonitrobenzoic acid chloride, metanitrobenzoic acid chloride, paranitrobenzoic acid chloride and the like. Of these, paranitrobenzoic acid chloride is preferred.

Examples of steroid compounds having a hydroxyl group include androsterone, β-cholesterol, cholesterol, corticosterone acetate, dehydroepiandrosterone, epiandrosterone,
Elsterol, estrone, 11α-hydroxymethyltestosterone, 11α-hydroxyprogesterone, lanosterol, mestranol, methyltestosterone, △ ^{9 (11)} -methyltestosterone, norethisterone, pregsterone, β-titosterol, stigmasterol, testosterone and the like. Can be. Of these, cholesterol and β-cholesterol are preferred.

Examples of the solvent used for the reaction between the nitro compound having an acid chloride group and the steroid compound having a hydroxyl group include toluene, benzene, tetrahydrofuran, diethyl ether, methyl ethyl ether, methyl butyl ether and the like. Also,
Examples of the basic catalyst used at this time include pyridine, triethylamine, quinoline, collidine, piperazine, piperidine and the like.

Further, for the reduction reaction of the reaction product, for example, zinc, iron, tin and tin (II) chloride, sodium sulfide (Na ₂ S, Na ₂ S ₂ , Na ₂ Sx), sodium hydrosulfide, and dithionite Reducing agents such as sodium and ammonium sulfide are advantageously used. In addition, for example, palladium-carbon, platinum, Raney-nickel, platinum black, rhodium-alumina, platinum sulfide-carbon, or the like can be used as a catalyst to reduce with hydrogen gas, hydrazine hydrochloride, or the like.

As the solvent used in the above reduction reaction,
For example, ethanol, methanol, 2-propanol, ammonia water, toluene, water, benzene, tetrahydrofuran and the like are used.

In the general formula (III), R ³ is —OC
Compound O in the case of O- is, for example, a nitro compound having a hydroxyl group and a steroid compound having an acid chloride group reacted in a solvent in the presence of a basic catalyst, and the reaction product is reduced to form a nitro group. To an amino group.

Examples of the nitro compound having a hydroxyl group include orthonitrophenol, metanitrophenol,
Paranitrophenol and the like can be mentioned. Of these, paranitrophenol is preferred.

Examples of the steroid compound having an acid chloride group include chenodeoxycholic acid chloride,
Collic acid chloride, deoxycholic acid chloride, dehydrocholic acid chloride, hyodeoxycholic acid chloride, lysocholic acid chloride, ursodesooxycholic acid chloride and the like can be mentioned. Of these, colic chloride and dehydrocholic chloride are preferred.

The solvent used for the reaction between the nitro compound having a hydroxyl group and the steroid compound having an acid chloride group, a basic catalyst, and the reduction of the reaction product obtained are the same as those described for the above reaction. Can be

In the general formula (III), R ³ is —CO
Compound III in the case of NH- is obtained by reacting a nitro compound having an acid chloride group with a steroid compound having an amino group in a solvent in the presence of a basic catalyst, and reducing the reaction product to form a nitro group. To an amino group.

As the nitro compound having an acid chloride group, the same compounds as those described above are used.

As the steroid compound having an amino group, the same compounds as those described above are used.

The solvent used for the reaction of the nitro compound having an acid chloride group with the steroid compound having an amino group and the basic catalyst, and the reduction of the reaction product obtained, use the same compounds as described for the above reaction. Used.

In the general formula (III), R ³ is --NH
Compound III in the case of CO- is obtained by reacting a nitro compound having an amino group with a steroid compound having an acid chloride in a solvent in the presence of a basic catalyst, and then reducing the product to convert the nitro group to an amino group. It is obtained by converting to a group.

Examples of the nitro compound having an amino group include:
For example, orthonitroaniline, metanitroaniline, paranitroaniline and the like can be mentioned. Of these, paranitroaniline is preferred.

As the steroid compound having an acid chloride group, the same compounds as those described above are used.

The solvent used in the reaction between the nitro compound having an amino group and the steroid compound having an acid chloride group, a basic catalyst, and the reduction of the obtained product are the same as those described for the above reaction. Can be

In the general formula (III), R ³ is -O-
Compound III is, for example, a nitro compound having a hydroxyl group and a steroid compound having a halogen group are reacted in a solvent in the presence of a basic catalyst, or a nitro compound having a halogen group and a steroid compound having a hydroxyl group. Is reacted in a solvent in the presence of a catalyst, and then reduced by converting the nitro group of the reaction product to an amino group.

As the nitro compound having a hydroxyl group, the same compounds as those described above can be exemplified.

Examples of the steroid compound having a halogen group include cholesteryl chloride, cholesteryl bromide, androsteryl bromide, β-cholesteryl chloride and β-cholesteryl bromide.
Cholesteryl, epiandrosteryl bromide, epiandrosteryl chloride, epigosteryl bromide, ergosteryl chloride, estolyl bromide, estolyl chloride, -11α bromide
-Hydokeoxymethylsteryl, -11α-hydroxymethylsteryl chloride, -11α-progesteryl bromide,
-11α-progesteryl chloride, lanosteryl bromide,
Lanosteryl chloride, melatranyl bromide, melatranyl chloride, melatranyl bromide, methyl methyl testosterol bromide, methyl methyl testosterol chloride, norethisteryl bromide, norethisteryl chloride, pregnenolyl bromide, pregnenolyl bromide, β-bromide -Sitosteryl chloride, β-sitosteryl chloride, stigmasteryl bromide, stigmasteryl chloride, testosteryl bromide, testosteryl chloride, and the like. Of these, cholesteryl chloride, cholesteryl bromide, β-cholesteryl chloride and β-cholesteryl bromide are preferred.

As the solvent used for the reaction between the nitro compound having a hydroxyl group and the steroid compound having a halogen group, for example, toluene, benzene, tetrahydrofuran,
Examples thereof include diethyl ether, methyl ethyl ether, methyl butyl ether, acetone, water, dimethyl sulfoxide, dimethyl formamide, methanol, ethanol, 2-propanol, and n-butanol.

Examples of the basic catalyst used in this case include sodium hydroxide, potassium hydroxide, pyridine, triethylamine, sodium, potassium carbonate, barium oxide, and sodium hydride. For the reduction of the reaction products, the same compounds described for the above reactions are used.

Examples of the nitro compound having a halogen group include orthonitrochlorobenzene, metanitrochlorobenzene, paranitrochlorobenzene, orthonitrobromobenzene, metanitrobromobenzene, paranitrobromobenzene, orthonitrofluorobenzene, and metanitrofluorobenzene. Benzene, paranitrofluorobenzene and the like can be mentioned. Of these, paranitrochlorobenzene, paranitrobromobenzene and paranitrofluorobenzene are preferred.

As the steroid compound having a hydroxyl group, the same compounds as those exemplified above are used.

Examples of the solvent used for the reaction between the nitro compound having a halogen group and the steroid compound having a hydroxyl group include toluene, benzene, acetone, diethyl ether, methyl ethyl ether, methyl butyl ether, and the like.
Tetrahydrofuran, dimethylsulfoxide, dimethylformamide and the like can be mentioned.

The catalyst used at this time is, for example,
Copper and copper powder can be mentioned. Further, the same compounds as described for the above reaction are used for the reduction of the reaction product.

The specific polymer I used in the present invention is obtained by reacting compound I, compound II and compound III. Such a reaction is usually performed in an organic solvent at 0 to 150 ° C.
The reaction is preferably performed at a reaction temperature of 0 to 100 ° C.

The use ratio of the above three types of starting compounds is determined by the following formula (1)

[0056]

(Equation 1)

And the following formula (2)

[0058]

(Equation 2)

It is preferable to satisfy the following.

In the above formulas (1) and (2), by changing the number of moles of compound I, compound II and compound III within a range where these formulas are satisfied, a liquid crystal aligning agent giving an arbitrary pretilt angle can be obtained. The specific polymer I can be obtained.

The organic solvents used in the reaction include:
There is no particular limitation as long as the specific polymer I produced by the reaction can be dissolved. Non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like: m-cresol And phenolic solvents such as xylenol, phenol and halogenated phenol.

These organic solvents may be used in combination with poor solvents such as alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons to such an extent that a polymer is not precipitated. Examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol,
Triethylene glycol, ethylene glycol monomethyl ethylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,
Examples thereof include 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, and xylene.

The amount of the organic solvent used is usually such that the total amount of compound I / compound II is 0.1 to 0.1 with respect to the total amount of the reaction solution.
Preferably, it is 30% by weight.

The specific polymer II is the specific polymer I described above.
By heating or in the presence of a dehydrating agent and an imidization catalyst. The reaction temperature in the case of imidization by heating is usually 60 to 200 ° C, preferably 100 to 170 ° C. If the reaction temperature is lower than 60 ° C., the progress of the reaction is delayed, and if it exceeds 200 ° C., the molecular weight of the specific polymer II may be greatly reduced. The reaction for imidization in the presence of a dehydrating agent and an imidization catalyst can be performed in the above-mentioned organic solvent. The reaction temperature is generally 0 to 180 ° C, preferably 60 to 150 ° C.
It is. Acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. Examples of the imidization catalyst include, but are not limited to, tertiary amines such as pyridine, collidine, lutidine, and triethylamine. The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the specific polymer I. The amount of the imidation catalyst used depends on the dehydrating agent used.
The amount is preferably 0.5 to 10 moles with respect to the moles.

The intrinsic viscosity [ηinh = (In ηr) of the specific polymer I and the specific polymer II thus obtained.
el / C, C = 0.5 g / dl, 30 ° C., N-methyl-
The intrinsic viscosity is measured in 2-pyrrolidone under the same conditions below]
Is usually 0.05 to 10 dl / g, preferably 0.05
５5 dl / g.

The specific polymer I used in the present invention and / or
Alternatively, the specific polymer II is suitably used as a liquid crystal aligning agent.

According to the research conducted by the present inventor, it has been clarified that the specific polymer III is suitably used as a liquid crystal aligning agent similarly to the specific polymer I and / or the specific polymer II.

In the general formula (IV), R ⁵ is a tetravalent organic group, and is the same as R 1 in the general formula (I).

In the general formula (IV), R ⁶ is a divalent organic group, and is the same as R 2 in the general formula (II).

In the general formula (IV), R ⁸ and R ¹⁰ are the same or different and are a monovalent organic group having a steroid skeleton or a hydroxyl group. However, at least one of R ⁸ and R ¹⁰ is a monovalent organic group having a steroid skeleton. Examples of the monovalent organic group having a steroid skeleton include the same groups as R ^{4 in} formula (III).

In the general formula (IV), R ⁷ and R ⁹ are divalent organic groups, for example, —O— or —NH—.

In the general formula (IV), b and d are 0 or 1.

The specific polymer III has, for example, the general formula (I)
When R ⁷ and R ⁹ are —O— in V), for example, it can be obtained by reacting a polyamic acid with a steroid compound having a water group in a solvent in the presence of a catalyst.

The catalyst used at this time includes, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid and the like.

As the solvent used at this time, for example, the same solvents as those used for the synthesis of the specific polymer I can be used.

The polyamic acid is prepared by mixing tetracarboxylic dianhydride and diamine in a solvent in the presence of a catalyst at a temperature of 0 to 100.
It can be obtained by reacting at ° C. As the tetracarboxylic dianhydride used in this case, the compound I can be mentioned as a preferable one, and as the diamine, the compound II can be mentioned as a preferable one.

As the steroid compound having a hydroxyl group, the same compounds as those described above are used.

When R ⁷ and R ⁹ in the general formula (IV) are —NH—, the specific polymer III is prepared, for example, by reacting polyamic acid chloride and a steroid compound having an amino group in a solvent in the presence of a catalyst. It is obtained by reacting.

The polyamic acid chloride is prepared by adding thionyl chloride to the polyamic acid solution in an amount of 2 to 2 moles of the polyamic acid.
It is obtained by adding 10 times, preferably 3 to 6 times.

The catalyst used for the reaction between the polyamic acid chloride and the steroid compound having an amino group includes:
For example, nitrogen-containing compounds such as pyridine, triethylamine, quinoline, collidine, piperazine and piperidine can be mentioned.

As the solvent used in this reaction, the same solvent as used in the synthesis of the specific polymer I can be used.

The specific polymer III thus obtained
Has an intrinsic viscosity of usually 0.05 to 10 dl / g, preferably 0.05 to 5 dl / g.

The liquid crystal aligning agent of the present invention comprises specific polymers I to I
II, but in addition to these specific polymers I to III, a functional silane-containing compound can be included for the purpose of improving the adhesion to a substrate.

Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-amino Ethyl) -3-amino-propyltrimethoxysilane, N- (2-aminoethyl) -3-
Amino-propylmethyldimethoxysilane, 3-ureido-propyltrimethoxysilane, 3-ureido-propyltriethoxysilane, N-ethoxycarbonyl-3
-Amino-propyltrimethoxysilane, N-ethoxycarbonyl-3-amino-propyltriethoxysilane, N-trimethoxysilylpropyl-triethylenetriamine, N-triethoxysilylpropyl-triethylenetriamine, 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
-Amino-propyltriethoxysilane, N-phenyl-3-amino-propyltrimethoxysilane, N-phenyl-3-amino-propyltriethoxysilane, N-
Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-amino-propyltriethoxysilane and the like can be mentioned.

A liquid crystal display device obtained by using the liquid crystal aligning agent of the present invention can be manufactured, for example, by the following method.

First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of the substrate provided with the transparent conductive film by a roll coater method, a spinner method, a printing method, or the like, and is applied at 80 to 200 ° C., preferably 120 to 200 ° C. Heat at a temperature of ° C. to form a coating. The thickness of this coating film is usually 0.001-1 μm.
m, preferably 0.005 to 0.5 μm.

The formed coating film is subjected to a rubbing treatment with a roll around which a cloth made of a synthetic fiber such as nylon is wound, thereby forming a liquid crystal alignment film.

As the substrate, for example, a transparent substrate made of glass, such as float glass or soda glass, or a plastic film, such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate, can be used.

As the transparent conductive film, a NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO ₂ and the like can be used. A method using a mask in advance is used.

In applying the liquid crystal aligning agent, a functional silane-containing compound, titanate, or the like is previously applied onto the substrate and the transparent conductive film in order to further improve the adhesion between the substrate and the transparent conductive film. You can also.

The substrates having the liquid crystal alignment film formed thereon are opposed to each other so that the surfaces of the liquid crystal alignment films are orthogonal or antiparallel to the rubbing direction, and the peripheral portion between the substrates is sealed with a sealant. And filling the filling port to form a liquid crystal cell,
A liquid crystal display device is obtained by laminating both surfaces of the substrate such that the polarization directions thereof coincide with or perpendicular to the rubbing direction of the liquid crystal alignment film of the substrate.

As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.

As the above liquid crystal, a liquid crystal which forms a nematic liquid crystal is preferable. For example, a Schiff base liquid crystal,
Azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal,
Biphenylcyclohexane liquid crystal, pyrimidine liquid crystal,
Dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like are used. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate, and cholesteryl carbonate, and chiral agents sold under the trade names C-15 and CB-15 (manufactured by British Drug House) are added. It can also be used. Further, ferroelectric liquid crystals such as p-decyloxybenzylidene-p'-amino-2-methylbutylcinnamate can be used.

As the polarizing plate used outside the liquid crystal cell, a polarizing plate in which a polarizing film called an H film in which polyvinyl alcohol is stretched and oriented and iodine is absorbed by a cellulose acetate protective film or the H film itself is used. And the like.

[0095]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Note that the measurement of the pretilt angle in the examples is described in [TJ Schffer, et al., J. Appl. Phys., 48 , 1].
783 (1977), F. Nakano, et al., JPN., J. Appl. Phy
s., 19 , 2013 (1980)].
This was performed by a crystal rotation method using Ne laser light.

In the evaluation of the orientation of the liquid crystal display element, the presence or absence of abnormal domains in the liquid crystal cell when the voltage was turned on / off was observed with a polarizing microscope, and it was judged that there was no abnormal domain.

Synthesis Example 1 After dissolving 9.28 g of paranitrobenzoic acid chloride and 19.33 g of cholesterol in 100 g of toluene, 20 g of pyridine was gradually added dropwise and reacted at 25 ° C. for 10 hours.

Next, the reaction solution was washed three times with pure water and recrystallized from ethanol to obtain a nitro compound as white crystals (yield: 86.1%).

Synthesis Example 2 10 g of the nitro compound obtained in Synthesis Example 1 was added to ethanol 1
Then, 0.1 g of Pd / C and 5 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. Then, after cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIIa (yield: 55.1).
%).

Synthesis Example 3 44.83 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride 4,4'-diaminodiphenylmethane 3
9.26 g and 2.09 g of the compound IIIa were dissolved in 776 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours.

Next, the reaction product was poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 68.92 g of a specific polymer Ia having an intrinsic viscosity of 0.71 dl / g.

Synthesis Example 4 25 g of the specific polymer Ia obtained in Synthesis Example 3 was dissolved in 475 g of N-methyl-2-pyrrolidone, and 15.57 g of pyridine and 12.06 g of acetic anhydride were added.
For 3 hours. Next, the reaction product liquid was precipitated in the same manner as in Synthesis Example 3 to obtain 21.2 g of the specific polymer IIa having an intrinsic viscosity of 0.77 dl / g.

Synthesis Example 5 A specific polymer Ib was obtained in the same manner as in Synthesis Example 3 except that p-phenylenediamine 21.63 g was used in place of 4,4'-diaminodiphenylmethane in Synthesis Example 3, and the specific weight was further increased. The reaction was carried out in the same manner as in Synthesis Example 4 using the combined polymer Ib to obtain a specific polymer IIb having an intrinsic viscosity of 0.81 dl / g.
21.1 g were obtained.

Synthesis Example 6 In Synthesis Example 3, instead of 4,4'-diaminodiphenylmethane, 10.81 g of p-phenylenediamine and 2,2 were added.
A specific polymer Ic was obtained in the same manner as in Synthesis Example 3 except that 33.43 g of -bis (4-aminophenyl) hexafluoropropane was used, and a reaction was performed in the same manner as in Synthesis Example 4 using this specific polymer Ic. Performed, intrinsic viscosity 0.74 dl / g
18.9 g of the specified polymer IIc was obtained.

Synthesis Example 7 15.15 g of a nitro compound was obtained in the same manner as in Synthesis Example 1 except that 19.43 g of β-cholesterol was used instead of cholesterol in Synthesis Example 1. Next, Synthesis Example 2
The reaction was carried out in the same manner as in the above to give 5.2 g of compound IIIb.

SYNTHESIS EXAMPLE 8 In Synthesis Example 3, compound II was used in place of compound IIIa.
A specific polymer Id was obtained in the same manner as in Synthesis Example 3 except that 2.10 g of Ib was used, and a reaction was carried out in the same manner as in Synthesis Example 4 using this specific polymer Id, and an intrinsic viscosity of 0.68 dl /
Thus, 21.4 g of the specific polymer IId was obtained.

Synthesis Example 9 A specific polymer Ie was obtained in the same manner as in Synthesis Example 3, except that 38.86 g of 4,4′-diaminodiphenylmethane and 4.17 g of compound IIIa were used. The specific polymer Ie was reacted in the same manner as in Synthesis Example 4 to obtain a specific polymer IIe19 having an intrinsic viscosity of 0.58 dl / g.
2 g were obtained.

Synthetic Example 10 A specific polymer If was obtained in the same manner as in Synthetic Example 3, except that 38.07 g of 4,4'-diaminodiphenylmethane and 8.35 g of compound IIIa were used. The reaction was carried out in the same manner as in Synthesis Example 4 using the united If, and the specific polymer IIf17 having an intrinsic viscosity of 0.46 dl / g was used.
1 g was obtained.

Synthesis Example 11 A specific polymer Ig was obtained in the same manner as in Synthesis Example 3 except that 4,4'-diaminodiphenylmethane was changed to 31.72 g and the compound IIIa was changed to 41.01 g. A reaction was carried out in the same manner as in Synthesis Example 4 using the combined Ig to obtain a specific polymer IIg1 having an intrinsic viscosity of 0.26 dl / g.
4.1 g were obtained.

Synthesis Example 12 After dissolving 6.96 g of paranitrophenol and 21.66 g of cholic acid chloride in 100 g of toluene, 20 g of pyridine was gradually added dropwise and reacted at 25 ° C. for 10 hours.

Next, the reaction solution was washed three times with pure water, and recrystallized from ethanol to obtain a nitro compound as white crystals (yield: 71.1%).

Synthesis Example 13 10 g of the nitro compound obtained in Synthesis Example 12 was dissolved in 100 g of ethanol, 0.1 g of Pd / C and 5 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. Then, after cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIIc (yield: 50.6%).

SYNTHESIS EXAMPLE 14 In Synthesis Example 3, compound II was used instead of compound IIIa.
Specific polymer I was prepared in the same manner as in Synthesis Example 3 except that Ic was used.
was obtained, and a reaction was carried out in the same manner as in Synthesis Example 4 using this specific polymer Ih to obtain 22.3 g of a specific polymer IIh having an intrinsic viscosity of 1.21 dl / g.

Synthesis Example 15 After 9.28 g of paranitrobenzoic acid chloride and 19.28 g of cholesterylamine were dissolved in 100 g of toluene, 20 g of pyridine was gradually added dropwise, and the mixture was reacted at 25 ° C. for 10 hours.

Next, the reaction solution was washed three times with pure water and recrystallized from ethanol to obtain a nitro compound as white crystals (yield: 90.2%).

Synthesis Example 16 10 g of the nitro compound obtained in Synthesis Example 15 was dissolved in 100 g of ethanol, 0.1 g of P / C and 5 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. Then, after cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIId (yield 46.6%).

Synthesis Example 17 In Synthesis Example 3, compound II was used instead of compound IIIa.
Specific polymer I was prepared in the same manner as in Synthesis Example 3 except that Id was used.
i, and the reaction was carried out using this specific polymer Ii in the same manner as in Synthesis Example 4 to obtain 23.4 g of a specific polymer IIi having an intrinsic viscosity of 0.88 dl / g.

Synthesis Example 18 6.91 g of paranitroaniline and 21.66 g of cholic acid chloride were dissolved in 100 g of toluene, and 20 g of pyridine was gradually added dropwise, followed by reaction at 25 ° C. for 10 hours.

Next, the reaction solution was washed three times with pure water, and recrystallized from ethanol to obtain a nitro compound as white crystals (yield: 89.7%).

Synthesis Example 19 10 g of the nitro compound obtained in Synthesis Example 18 was dissolved in 100 g of ethanol, 0.1 g of Pd / C and 5 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. Then, after cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIIe (yield 43.9).
%).

Synthesis Example 20 In Synthesis Example 3, compound II was used instead of compound IIIa.
Specific polymer I was prepared in the same manner as in Synthesis Example 3 except that Ie was used.
j was obtained, and the specific polymer Ij was reacted in the same manner as in Synthesis Example 4 to obtain 21.6 g of a specific polymer IIj having an intrinsic viscosity of 1.26 dl / g.

Synthesis Example 21 6.96 g of paranitrophenol and cholesteryl bromide 2
0.26 g and potassium hydroxide 4 g, ethanol 400 g
After refluxing for 6 hours, the precipitate was filtered off,
Recrystallization was performed using ethanol to obtain a nitro compound (yield: 70.1%).

Synthesis Example 22 10 g of the nitro compound obtained in Synthesis Example 21 was dissolved in 100 g of ethanol, 0.1 g of Pd / C and 5 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. Then, after cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIIf (yield: 40.5).
%).

Synthesis Example 23 Compound II in Synthesis Example 3 was replaced with Compound II instead of Compound IIIa.
Except that 2.07 g of If was used, a specific polymer Ik was obtained in the same manner as in Synthesis Example 3, and a reaction was carried out in the same manner as in Synthesis Example 4 using this specific polymer Ik, and the intrinsic viscosity was 1.09 dl / g.
Of the specific polymer IIk was obtained.

Synthesis Example 24 A specific polymer Il was obtained in the same manner as in Synthesis Example 3 except that 2.0 g of cholesterylamine was used instead of compound IIIa in Synthesis Example 3. The reaction was carried out in the same manner as in Example 4, and the intrinsic viscosity was 0.58 dl /
Thus, 16.7 g of the specific polymer II was obtained.

Synthesis Example 25 44.83 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 4,4'-diaminodiphenylmethane 3
9.65 g was dissolved in 760 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours.

Next, the reaction product was poured into a large excess of methanol to precipitate the reaction product. Thereafter, it is washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain an intrinsic viscosity of 1.
72.16 g of a polymer Im of 32 dl / g were obtained.

Synthesis Example 26 20 g of the polymer Im obtained in Synthesis Example 24 was
After dissolving in 380 g of 2-pyrrolidone, 1.83 g of cholesterol and 0.5 g of sulfuric acid were added and reacted at 100 ° C. for 8 hours.

Then, the reaction product was poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 19.2 g of a specific polymer IIIa having an intrinsic viscosity of 0.92 dl / g.

Synthesis Example 27 The same procedure as in Synthesis Example 26 was carried out except that 14.64 g of cholesterol was used, and the intrinsic viscosity was 0.76 d.
18.7 g of 1 / g of the specific polymer IIIb were obtained.

Synthesis Example 28 20 g of the polymer Im obtained in Synthesis Example 25 was
After dissolving in 380 g of 2-pyrrolidone, 1.82 g of cholesterylamine and 10 g of thionyl chloride were added,
For 8 hours.

Next, the reaction product was poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 17.6 g of a specific polymer IIIc having an intrinsic viscosity of 0.84 dl / g.

Synthesis Example 29 In Synthesis Example 28, 14.56 g of cholesterylamine was used.
Except for using it, the intrinsic viscosity was 0.69 in the same manner as in Synthesis Example 28.
15.9 g of dl / g of the specific polymer IIId were obtained.

Example 1 3 g of the specific polymer Ia obtained in Synthesis Example 3 was converted to N-methyl-
Dissolved in 72 g of 2-pyrrolidone to obtain a solid concentration of 4% by weight
And a solution having a pore size of 1 μm was filtered to prepare a liquid crystal aligning agent solution.

This solution was applied on a transparent electrode surface on a glass substrate with a transparent electrode made of an indium oxide-tin oxide film at a rotation speed of 3,000 rpm for 3 minutes using a spinner, dried at 180 ° C. for 1 hour, and dried. A coating film having a thickness of 0.05 μm was formed.

A rubbing machine having a roll in which a nylon cloth was wound around the coating film was subjected to a rubbing treatment at a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm is screen-printed and applied to the outer edge of each of the pair of rubbed substrates on the side having the liquid crystal alignment film. The adhesives were cured by overlapping them so that the surfaces faced each other and the rubbing directions were antiparallel.

Next, between the pair of substrates by the liquid crystal injection port,
After filling a nematic type liquid crystal (ZLI-1565 or 2293, manufactured by Merck), the liquid crystal injection port is sealed with an epoxy-based adhesive, a polarizing plate is provided on both outer surfaces of the substrate, and the polarizing directions of the polarizing plate are respectively adjusted. The substrates were bonded together so as to match the rubbing direction of the liquid crystal alignment film on the substrate, thereby producing a liquid crystal display device.

The orientation of the obtained liquid crystal display device was good, and the pretilt angle when the liquid crystal was changed to ZLI-1565 or 2293 was 4.6 ° and 5.8 °, respectively.

Examples 2 to 17 In Example 1, Synthesis Examples 4, 5, 6, 8, 9, 10, 1
1, 14, 17, 20, 23, 24, 25, 26, 27
Specific polymers IIa, IIb, II obtained in and 28
c, IId, IIe, IIf, IIg, IIh, II
i, IIj, IIk, IIl and specific polymer III
A liquid crystal display device was prepared in the same manner as in Example 1 except that a, IIIb, IIIc, and IIId were used, and the orientation and pretilt angle of the liquid crystal display device were measured.
It was shown to.

[0142]

[Table 1]

Comparative Example 1 A liquid crystal display device was prepared and evaluated in the same manner as in Example 1 except that the polymer Im obtained in Synthesis Example 25 was used. The liquid crystal was evaluated as ZLI-1565 or 2293. And the pretilt angles are 1.8 ° and 1.9 °, respectively.
Met.

[0144]

According to the liquid crystal aligning agent of the present invention, the alignment property is good, and the liquid crystal aligning agent is 2 to 90% depending on the introduced amount of the steroid skeleton.
And a liquid crystal alignment film suitable for STN or SH display devices can be obtained.

A liquid crystal display device having a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be suitably used for a ferroelectric display device by selecting a liquid crystal to be used.

Further, a liquid crystal display device having a liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention is excellent in liquid crystal alignment and reliability, and can be effectively used for various devices. , Clocks, coefficient display boards, word processors, personal computers, and liquid crystal televisions.

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I) A tetracarboxylic dianhydride represented by the following general formula (II): H ₂ N—R ² —NH ₂ ... (II) wherein R ² represents a divalent organic group; The following general formula (III): A liquid crystal aligning agent comprising a polymer obtained by reacting a monoamine compound represented by the formula and / or an imidized polymer thereof. 2. The following general formula (IV): A liquid crystal aligning agent comprising a polymer having a structural unit represented by the formula: