JPH05263077A - Agent for aligning liquid crystal - Google Patents

Abstract

PURPOSE:To obtain an agent having a high ability to align a liquid crystal and can give a liquid crystal cell suppressed in the buildup of charges when a voltage is applied thereto by using a polymer obtained by reacting a tetracarboxylic acid dianhydride and a specified diamine. CONSTITUTION:This agent comprises a polymer obtained by reacting a tetracarboxylic acid dianhydride of formula I (wherein R<1> is a tetravalent organic group) with a diamine containing a compound of formula II (wherein (n) is 2-10) and/or its imide. This agent can give an aligned liquid crystal film desirable especially as a TN-type liquid crystal display element. A liquid crystal display element containing the liquid crystal film formed by using this agent is desirably used as SBE, SH or a ferroelectric display element. The liquid crystal display element can be used as, e.g. a display of, for example, a desk calculator, a wrist watch, a clock, a count display, a word processor, a personal computer or a liquid crystal television.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent which has good liquid crystal orientation and has a small amount of accumulated charge in a liquid crystal cell when a voltage is applied, and is particularly useful for a TN type liquid crystal display device.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy is sandwiched by a substrate with a transparent electrode having a liquid crystal alignment film made of polyimide or the like, and the long axis of liquid crystal molecules is continuous at 90 degrees between the substrates. There is known a liquid crystal display element (TN type display element) having a TN type liquid crystal cell which is twisted mechanically. The liquid crystal alignment in this TN type display element is formed by a liquid crystal alignment film that has been subjected to a rubbing treatment. However, since electric charges are accumulated on the surface of the alignment film during driving, even if a new drive signal is input, the original There is a problem that it cannot respond to the input drive signal.

[0003]

An object of the present invention is to provide a novel liquid crystal aligning agent. Another object of the present invention is to provide a liquid crystal aligning agent that provides a liquid crystal display device with a small amount of accumulated charge by using a sulfide-containing polyimide exhibiting high crystallinity.

Still another object of the present invention is to solve the above-mentioned conventional problems and to provide a liquid crystal alignment film for a TN type liquid crystal display device which has a good liquid crystal alignment and has a small amount of accumulated charge in a liquid crystal cell when a voltage is applied. Another object is to provide a liquid crystal aligning agent that can be suitably used.

Further objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are, firstly, the following general formula (I):

[0006]

[Chemical 4]

A tetracarboxylic dianhydride represented by the formula (hereinafter referred to as "compound I") and the following general formula (II)

[0008]

[Chemical 5]

A compound represented by the formula (hereinafter referred to as "compound II")
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 with a diamine containing It is achieved by the liquid crystal aligning agent.

Secondly, the above objects and advantages of the present invention are, secondly, the specific polymer I and the following general formula (III):

[0011]

[Chemical 6]

The amine represented by (hereinafter referred to as "compound II
I)) (hereinafter, referred to as “specific polymer III”).

The compound I used in the present invention is represented by the above formula (I). In the above formula, R ¹ corresponds to a residue obtained by removing the anhydride group from tetracarboxylic dianhydride.
Examples of the compound I include an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride, and an aliphatic or alicyclic tetracarboxylic dianhydride is preferable.

Specific examples of the aliphatic or alicyclic tetracarboxylic dianhydride of the compound I include, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2, Three, four,
5-tetrahydrofuran tetracarboxylic 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 acid dianhydride, bicyclo [2,2
Mention may be made of aliphatic and cycloaliphatic tetracarboxylic dianhydrides such as 2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dicarboxylic acid dianhydride Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride and 1,3,3
a, 4,5,9b-hexahydro-5-tetrahydro-2,
5-dioxo-3-furanyl) -naphtho [1,2-c]
Furan-1,3-dione is preferred, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride is particularly preferred.

Specific examples of the aromatic tetracarboxylic dianhydride of compound I include pyromellitic dianhydride,
3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-
Dimethyldiphenylsilane tetracarboxylic 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) diphenyl sulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4 , 4 '-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p -Phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride And bis (triphenyl phthalic acid) -4,4'-diphenylmethane diaromatic such anhydrides tetracarboxylic dianhydride.

Among these, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride , 4,4 '-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride and 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferred.

The compound II is a diamine having a sulfide bond represented by the general formula (II). n is 2-10
Is an integer, preferably 2-5.

In addition to compound II, other diamines can be used in combination to the extent that the effects of the present invention are not lost. Examples of other diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-
Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-
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, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-amino Phenyl) 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, 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 Aromatic diamines such as 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenylenediisopropylidene) bisaniline and 4,4 ′-(m-phenylenediisopropylidene) bisaniline ;

Aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octa Methylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenemethylenediamine, tricyclo [ 6, 2,
1,0 ^2.7 ] -aliphatic or alicyclic diamine such as undecylenedimethyldiamine; the following general formula (IV)

[0020]

[Chemical 7]

(Here, R represents a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a cycloalkyl group such as a cyclohexyl group, or an aryl group such as a phenyl group. , P is 1 to 3, q
Represents an integer of 1 to 20) and the like. Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4 -Aminophenyl)
Fluorene 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,
Preferred are 4 '-(p-phenylenediisopropylidene) bisaniline and 4,4'-(m-phenylenediisopropylidene) bisaniline. These alone or 2
A combination of two or more species can be used.

The use of such other diamine is usually 0 to 99.9 mol%, preferably 0 to 95 mol% in the total diamine. The specific polymer I used in the present invention is obtained by reacting the compound I with the compound II. Such a reaction is usually carried out in an organic solvent at 0 to 150 ° C., preferably 0 to 10 ° C.
It is carried out at a reaction temperature of 0 ° C.

The proportion of the compound I and the total diamine compound used is preferably 0.2 to 2 equivalents of the acid anhydride group of the compound I, more preferably 0 equivalent to 1 equivalent of the amino group in the total diamine compound. It is 0.3 to 1.2 equivalents.

The organic solvent used in the reaction includes
There is no particular limitation as long as it can dissolve the specific polymer I produced in the reaction. For example, N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone,
Aprotic polar solvents such as tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenols. Usually, the amount of the organic solvent used is preferably such that the total amount of the compound I and all the diamine compounds is 0.1 to 30% by weight based on the total amount of the reaction solution.

The specific polymer II used in the present invention is obtained by heating or imidizing the specific polymer I described above in the presence of a dehydrating agent and an imidization catalyst. The reaction temperature for imidization by heating is usually 6
The temperature is 0 to 200 ° C, preferably 100 to 170 ° C. If the reaction temperature is less than 60 ° C, the reaction progresses slowly,
If the temperature exceeds ℃, the molecular weight of the specific polymer II may be largely reduced. In addition, the reaction in the case of imidization in the presence of a dehydrating agent and an imidization catalyst can be carried out in the above-mentioned organic solvent. The reaction temperature is generally 0 to 180 ° C, preferably 60 to 150 ° C. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. Further, as the imidization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but the imidization catalyst is not limited thereto. The amount of the dehydrating agent used is 1.6 to 20 with respect to 1 mol of the repeating unit of the specific polymer I.
It is preferably molar. Further, the amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent used.

The organic solvent may be used in combination to such an extent that a poor solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbon-forming polymers is not deposited. As such a poor solvent,
For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, 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,
4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can be mentioned.

The intrinsic viscosity [ηinh = (lnηrel / C, C =
0.5 g / dl, 30 ° C., in N-methyl-2-pyrrolidone), and the intrinsic viscosity is measured under the same conditions].
05-10 dl / g, preferably 0.05-5 dl / g
Is.

The specific polymer III is a mixture of the specific polymer I and the compound III. In the formula of compound III, R
² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Alkyl groups such as tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, triacontyl group; cycloalkyl groups such as cyclohexyl group; phenyl group ,
Aryl groups such as biphenyl group and naphthyl group; perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group , A perfluorononyl group,
Perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, perfluorotridecyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorohexadecyl group, perfluoroheptadecyl group, perfluorooctadecyl group Examples thereof include halogenated alkyl groups.

Examples of such compound III include N, N
-Dimethylhexane, N, N-dimethylheptane, N, N
-Dimethyloctane, N, N-dimethylnonane, N, N-
Dimethyldecane, N, N-Dimethylundecane, N, N-
Dimethyl dodecane, N, N-dimethyl tridecane, N, N
-Dimethyltetradecane, N, N-dimethylpentadecane, N, N-dimethylhexadecane, N, N-dimethylheptadecane, N, N-dimethyloctadecane and the like can be mentioned as preferable ones.

The addition of the compound III to the specific polymer I is carried out by directly adding the compound III to the solution containing the specific polymer I.
Or by mixing a solution of compound III dissolved in an organic solvent that can be used for the synthesis of specific polymer I. The temperature at this time is usually 0 to 150 ° C., preferably 0 to 100 ° C.

The amount of the compound III used in this addition is usually 0.1 to 5 mol%, preferably 0.2 to 3 mol% based on 1 mol of the repeating unit of the specific polymer I.

The solution containing the specific polymer III is prepared by using a solvent similar to that used in the synthesis reaction of the specific polymer I, and usually has a concentration of 0.1 to 10 mmol / L, preferably 0.1 to 6 m.
It can be prepared and used as a mol / L solution.

The liquid crystal aligning agent of the present invention comprises the specific polymers I to I.
Although containing I, a monoamine may be added at the time of reaction in order to control the molecular weight of these specific polymers and realize the optimum coatability to a substrate.

Examples of monoamines used in this case 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 -Eicosyl amine etc. can be mentioned.

Further, the liquid crystal aligning agent of the present invention may contain a functional silane-containing compound for the purpose of improving the adhesion between the specific polymers I, II and III and the substrate.
Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl -3-Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxyysilyl-1 , 4,7-Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate,
9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane , N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

The 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. In the case of the specific polymers I and II, 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 then 80 to 200. The coating film is formed by heating at a temperature of 120 ° C., preferably 120 to 200 ° C. The thickness of this coating is
Usually, 0.001 to 1 μm, preferably 0.005 to 0.5 μm.
It is 5 μm.

Further, since the specific polymer III has a hydrophilic carboxylic acid amine salt and a hydrophobic alkyl moiety in the same molecule, a liquid crystal alignment film can be formed by the Langmuir-Blodgett method. First, the solution of the specific polymer III is poured onto the water surface, and the specific polymer II is poured onto the water surface.
Form a monolayer of I. The surface pressure of the monolayer formed next is usually 5 to 40 dyne / cm, preferably 10
While maintaining at ~ 35 dyne / cm, the substrate used for the liquid crystal display device is immersed perpendicularly to the water surface on which the monomolecular layer is formed, at a constant speed, usually 0.5 to 100 mm /
By repeatedly pulling up and down at a speed of min, preferably 1 to 30 mm / min, a monomolecular layer or a cumulative film of the specific polymer III is formed on the surface of the substrate. The cumulative number of formed monomolecular layers can be set to a desired value by appropriately selecting the number of times the substrate is pulled up and pulled down. The monomolecular layer made of the specific polymer III or a monomolecular layer cumulative film is, for example, in order to suitably function as a liquid crystal alignment film, the monomolecular layer is usually accumulated 1 to 400 times, preferably 1 to 300 times. It is preferable that the film is a film. The monomolecular layer or the monomolecular layer of the specific polymer III formed as described above can be used as it is as a liquid crystal alignment film.
Good liquid crystal orientation is exhibited even when heat-treated at 0 to 300 ° C. or imidized using the above-mentioned dehydrating agent and imidization catalyst.

The coating film formed as described above is treated as a liquid crystal alignment film by rubbing it with a roll around which a cloth made of synthetic fiber such as nylon is wound. However,
In the case of the specific polymer III, good liquid crystal alignment may be obtained without rubbing treatment.

As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, 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 or the like can be used. The transparent conductive film is patterned by a photo-etching method, A method using a mask in advance is used. When applying the liquid crystal aligning agent,
In order to further improve the adhesiveness between the substrate and the transparent conductive film and the coating film, a functional silane-containing compound, titanate or the like may be applied in advance on the substrate and the transparent conductive film.

The substrates on which the liquid crystal alignment film is formed are made to face each other so that the rubbing directions of the liquid crystal alignment films are orthogonal or antiparallel, and the peripheral portion between the substrates is sealed with a sealant to fill the liquid crystal. Then, the filling hole is sealed to form a liquid crystal cell, and the liquid crystal cell is formed by adhering both sides of the liquid crystal cell so that the polarization directions thereof are the same or orthogonal to the rubbing direction of the liquid crystal alignment film of the substrate.

As the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as spacers can be used. The liquid crystal is preferably a nematic liquid crystal, a smectic liquid crystal, among which a nematic liquid crystal is formed. For example, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals and the like are used. In addition to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate, and trade names C-15 and CB-
No. 15 (Merck Ltd.), and a chiral agent or the like as sold may be added.
Furthermore, p-decyloxybenzylidene-p-amino-2
Ferroelectric liquid crystals such as methylbutyl cinnamate can also be used.

The polarizing plate used on the outside of the liquid crystal cell is a polarizing plate in which a polarizing film called an H film absorbing iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films, or the H film itself. And a polarizing plate made of

[0044]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation of the residual charge of the liquid crystal display element is
After applying a direct current voltage of 10 V for 30 minutes, the voltage remaining in the liquid crystal cell was measured. In addition, the orientation of the liquid crystal cell was evaluated by observing the presence or absence of an abnormal domain in the liquid crystal cell when a voltage was turned on and off with a polarizing microscope, and judged that there was no abnormal domain.

Synthesis Example 1 44.83 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and the following formula (V)

[0046]

[Chemical 8]

64.89 g of the compound IIa represented by the formula: was dissolved in 988 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Then, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a specific polymer Ia 80.2 having an intrinsic viscosity of 1.44 dl / g.
g was obtained.

Synthesis Example 2 30.0 g of the specific polymer Ia obtained in Synthesis Example 1 was added to 570
It was dissolved in g-γ-butyrolactone, 21.6 g of pyridine and 16.74 g of acetic anhydride were added, and the imidization reaction was allowed to proceed at 120 ° C. for 3 hours. Then, the reaction product solution was precipitated in the same manner as in Synthesis Example 1 to obtain 24.0 g of the specific polymer IIa having an intrinsic viscosity of 1.35 dl / g.

Synthesis Example 3 A specific polymer Ib was prepared in the same manner as in Synthesis Example 1 except that the diamine was changed to 10.81 g of p-phenylenediamine and 32.45 g of the compound IIa, and the specific polymer Ib was obtained. Was used to carry out an imidization reaction in the same manner as in Synthesis Example 2 to obtain 22.2 g of a specific polymer IIb having an intrinsic viscosity of 1.16 dl / g.

Synthetic Example 4 Intrinsic viscosity 1.26 dl / g in the same manner as in Synthetic Example 1 except that 39.22 g of cyclobutanetetracarboxylic dianhydride was used as the tetracarboxylic dianhydride.
70.5 g of the specific polymer Ic was obtained.

Synthesis Example 5 Instead of the compound IIa in Synthesis Example 1, the following general formula (VI) was used.

[0052]

[Chemical 9]

A specific polymer Ie was obtained in the same manner as in Synthesis Example 1 except that 86.53 g of the compound IIb represented by ## STR6 ## was used, and the imidization reaction was performed in the same manner as in Synthesis Example 2 using this specific polymer Ie. Performed, intrinsic viscosity 1.05 dl / g
21.2 g of the specific polymer IIe of

Synthesis Example 6 N-N-dimethylacetamide / toluene (80/2
(0, weight ratio) The specific polymer Ia was dissolved in the mixed solution to prepare a solution having a concentration of 1 mmol / L. A 1 mmol / L solution of N, N-dimethyl-n-hexadecylamine dissolved in the same mixed solution as described above was added to this solution in an amount of 2 mol per 1 mol of repeating units of the specific polymer Ia. Mixing was performed so as to have a double molar ratio to prepare a solution containing the specific polymer IIIa. This solution was poured onto ion-exchanged water (25 ° C) filled in a water tank, and the surface pressure in the water tank was adjusted to 25
While maintaining the dyne / cm, the substrate was immersed vertically to the water surface and moved up and down to form a monomolecular cumulative film of 10 monolayers on the surface of the substrate. The substrate used had a SiO ₂ layer with a thickness of 500 Å formed by applying a coating solution of SiO ₂ on soda glass and baking it, and had a surface electrode made of an ITO film.
The substrate was pulled up and pulled down at a speed of 5 mm / min, and after forming a cumulative film, it was dried under reduced pressure at 40 ° C. for 2 hours to prepare a substrate A.

Synthesis Example 7 The substrate prepared in Synthesis Example 6 was treated with 21.6 g of pyridine and 1
500 g of toluene solution added with 6.74 g of acetic anhydride
And was imidized at 120 ° C. for 3 hours. The substrate was thoroughly washed with toluene and dried under reduced pressure at 40 ° C. for 2 hours to prepare a substrate B.

Synthesis Example 8 A substrate was prepared in the same manner as in Synthesis Example 6 except that the amine added in Synthesis Example 6 was N, N-dimethyloctadecylamine, and imidization treatment was carried out in the same manner as in Synthesis Example 7. ,
Substrate C was produced.

Synthetic Example 9 A substrate was prepared in the same manner as in Synthetic Example 6 except that the specific polymer Ic was used in place of the specific polymer Ia in Synthetic Example 6, and imidization treatment was carried out in the same manner as in Synthetic Example 7. Substrate D was produced.

Synthesis Example 10 43.62 g of pyromellitic dianhydride and 40.04 g of 4,4'-diaminodiphenyl ether were added to N-methyl-2.
-Dissolved in 753 g of pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Then, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 75.2 g of a specific polymer If having an intrinsic viscosity of 1.51 dl / g.

Example 1 The polymer Ia obtained in Synthesis Example 1 was converted into γ-butyrolactone 7
It was dissolved in 2 g to prepare a solution having a solid content concentration of 4% by weight, and this solution was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent solution. This solution was spun on a transparent electrode surface on a glass substrate with a transparent electrode made of an ITO film at a rotation speed of 3000.
It was applied using a spinner for 3 minutes at rpm and dried at 180 ° C. for 1 hour to form a coating film having a dry film thickness of 0.05 μm. The number of rotations of the roll is 500r by a rubbing machine having a roll in which a nylon cloth is wound around this coating film.
The rubbing treatment was performed at pm and a stage moving speed of 1 cm / sec.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm was applied by screen printing to the outer edges of the pair of rubbing-treated substrates having the liquid crystal alignment film, and then the pair of substrates was placed on the liquid crystal alignment film surface. And the rubbing directions were orthogonal to each other, and they were stacked and pressure-bonded to cure the adhesive. Next, after filling a nematic liquid crystal (ZLI-1565, manufactured by Merck & Co., Inc.) between the pair of substrates through the liquid crystal inlet, the liquid crystal inlet is sealed with an epoxy adhesive, and a polarizing plate is provided on both sides of the substrate. Were laminated so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film of each substrate, to manufacture a liquid crystal display element. The orientation of the obtained liquid crystal display device was good, and the accumulated charge 10 seconds after the voltage application was 0.1V.

Examples 2 to 9 Except that the specific polymers IIa, IIb, Ic, IIe obtained in Synthesis Examples 2 to 9, Substrate A, Substrate B, Substrate C and Substrate D were used in Example 1, A liquid crystal display device was produced in the same manner as in Example 1, the orientation of the liquid crystal display device and the accumulated charge after voltage application were measured, and the results are shown in Table 1.

[0062]

[Table 1]

COMPARATIVE EXAMPLE 1 Except that the specific polymer If obtained in Synthesis Example 10 was used.
When a liquid crystal display device was produced and evaluated in the same manner as in Example 1, the liquid crystal alignment was disturbed, and the accumulated charge 10 seconds after the voltage application was 3.2 V.

[0064]

EFFECTS OF THE INVENTION According to the liquid crystal aligning agent of the present invention, the alignment property is good and the accumulated charge after voltage application is small, especially T
A liquid crystal alignment film suitable for an N-type liquid crystal display device can be obtained. Further, a liquid crystal display device having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, by selecting the liquid crystal to be used, SBE (Super Birefringency Effect),
It can also be suitably used for SH (Super Homeotropic) and ferroelectric display elements. Furthermore, a liquid crystal display device having an alignment film formed using the liquid crystal aligning agent of the present invention,
The liquid crystal has excellent orientation and reliability, and can be effectively used in various devices, and is used for display devices such as desk calculators, wrist watches, table clocks, coefficient display boards, word processors, personal computers, and liquid crystal televisions.

Claims (2)

[Claims] 1. The following general formula (I): And a tetracarboxylic dianhydride represented by the following general formula (II) A liquid crystal aligning agent comprising a polymer obtained by reacting with a diamine containing a compound represented by and / or an imidized polymer thereof. 2. A polymer obtained by reacting a tetracarboxylic acid dianhydride represented by the above general formula (I) and a diamine containing a compound represented by the above formula (II) and the following general formula (III): [Chemical 3] A liquid crystal aligning agent comprising a mixture of amines represented by: