JPH05203952A - Liquid crystal orientating agent - Google Patents

Abstract

PURPOSE:To obtain a liq. crystal orientating agent having satisfactory liq. crystal orientation property and controlling an afterimage at the time of driving by incorporating a specified polymer and/or a polymer obtd. by subjecting the specified polymer to imide formation. CONSTITUTION:This liq. crystal orientating agent contains a polymer obtd. by allowing tetracarboxylic acid dianhydride represented by formula I to react with diamine including a compd. represented by formula II and/or a polymer obtd. by subjecting the polymer to imide formation. In the formula I, R<1> is a tetravalent org. group. In the formula II, each of R<2>-R<4> is-NH-C-(=O)- or -C(=O)-NH-as a divalent org. group and (n) is an integer of 1-100. Butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride or 1,2,3,4-cyclopentenetetracarboxylic acid dianhydride may be used as the tetracarboxylic acid dianhydride. The compd. represented by the formula II is obtd. by allowing a nitro compd. having a specified reactive group to react with a compd. having a specified reactive group and reducing the nitro groups.

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 afterimage when driven, and is particularly useful for TN type liquid crystal display devices.

[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 liquid crystal display element) having a TN type liquid crystal cell which is twisted mechanically. The liquid crystal alignment in this TN type liquid crystal display element is formed by a liquid crystal alignment film that has been subjected to a rubbing treatment, but since electric charges are accumulated on the surface of the alignment film during driving, even if a new drive signal is input, There is a problem that an afterimage of the previous display occurs.

[0003]

An object of the present invention is to provide a liquid crystal aligning agent. Another object of the present invention is to solve the conventional problems described above, to provide good liquid crystal alignment, and to reduce afterimages during driving, and it can be suitably used particularly for a liquid crystal alignment film of a TN type liquid crystal display device. It is to provide a liquid crystal aligning agent. Further objects and advantages of the present invention will be apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are achieved by the following general formula (I):

[0005]

[Chemical 3]

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

[0007]

[Chemical 4]

A compound represented by the following 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.

The tetracarboxylic dianhydride used in the present invention is represented by the above formula (I). In the above formula, R
¹ corresponds to the residue obtained by removing the anhydride group from tetracarboxylic dianhydride.

Examples of the compound I include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride. 2,3,5-Tricarboxycyclopentyl acetic acid dianhydride 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5
-Furantetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3
a, 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-2,3,5,6-tetracarboxylic dianhydrides and other aliphatic and cycloaliphatic tetracarboxylic dianhydrides;

Pyromellitic dianhydride 3,3 ', 4,
4'-benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,
4'-tetraphenylsilane tetracarboxylic acid 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 diphthalic 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, bis (triphenylphthalic acid)
Mention may be made of aromatic tetracarboxylic dianhydrides such as -4,4'-diphenylmethane dianhydride.

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2, 5-Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and the like are preferable.

The compound II is represented by the general formula (II). The compound II is obtained, for example, by reacting a nitro compound having a specific reactive group with a compound having a specific reactive group, and then reducing the nitro group.

That is, in the above general formula (II), R ³ means a residue portion in which a reactive group is excluded from a compound having a specific reactive group described later. R ² and R ⁴ represent a divalent organic group selected from —NH—C (═O) — and —C (═O) —NH—.

Further, n represents an integer of 1 to 100, preferably 1 to 10. As a method for synthesizing compound II, for example, a nitro compound having an acid chloride group and a diamine are reacted in a solvent in the presence of a basic catalyst, and then the reaction product is reduced to convert the nitro group into an amino group. Method, or after reacting a nitro compound having an amino group with a compound having two acid chloride groups in a solvent in the presence of a basic catalyst, the reaction product is reduced to convert the nitro group to an amino group. There is a method.

The solvent used in these reactions is
Examples thereof include ethers such as diethyl ether, methyl ethyl ether and methyl butyl ether, tetrahydrofuran, acetone, toluene and the like. Examples of the basic catalyst include pyridine and triethylamine.

Reduction of the products of the reaction includes, for example, zinc,
Iron, tin, tin (II) chloride, sodium sulfide (Na ₂
Reducing agents such as S, Na ₂ S ₂ , Na ₂ S _x ), sodium hydrosulfide, sodium dithionite, ammonium sulfide, etc. are advantageously used. Also, for example, palladium-
It is also possible to carry out reduction with hydrogen gas, hydrazine, hydrochloric acid or the like using carbon, platinum, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. as a catalyst.

As the solvent for the reduction reaction, for example, alcohols such as ethanol, methanol and 2-propanol,
Ethers such as diethyl ether, methyl ethyl ether, methyl butyl ether, aqueous ammonia, toluene,
Water, tetrahydrofuran, chloroform, dichloromethane and the like are used.

Examples of the nitro compound having an acid chloride group include o-nitrobenzoic acid chloride, m-nitrobenzoic acid chloride and p-nitrobenzoic acid chloride. Of these, m-nitrobenzoic acid chloride and p-nitrobenzoic acid chloride are preferable.

As the nitro compound having an amino group,
For example, o-nitroaniline, m-nitroaniline, p-
Examples include nitroaniline. Of these, m-
Nitroaniline and p-nitroaniline are preferred.

As the diamine, for example, 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-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, 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;

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;

[0023]

[Chemical 5]

(Wherein R represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a cycloalkyl group such as a cyclohexyl group, or a hydrocarbon group having 1 to 12 carbon atoms such as an aryl group such as a phenyl group). , P is 1 to 3 and q is 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, 1,1-metaxylylenediamine, 1,3-propanediamine , Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene Diamine, hexahydro-4,7-methanoindanylene dimethylenediamine, tricyclo [6,
2,1,0 ^2.7] - such undecylenate range methyl diamines are preferred.

Examples of the compound having two acid chloride groups include aliphatic dicarboxylic acid dichlorides such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride and muconic acid dichloride; 1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride,
1,3-cyclopentanedicarboxylic acid dichloride, 1,
3-Cyclohexanedicarboxylic acid dichloride, 1,4
-Cyclohexanedicarboxylic acid dichloride, 1,4-
(2-norbornene) dicarboxylic acid dichloride, 1,
4-Bicyclo [2.2.2] octanedicarboxylic acid dichloride, 2,5-dioxo-1,4-bicyclo [2.2.
2] octane dicarboxylic acid dichloride, 1,3-adamantane dicarboxylic acid dichloride, 4,8-dioxo-1,3-adamantane dicarboxylic acid dichloride, 2,
Alicyclic dicarboxylic acid dichlorides such as 6-spiro [3.3] heptanedicarboxylic acid dichloride;

Isophthalic acid chloride, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid dichloride, 1,5- (9-oxofluorene) dicarboxylic acid dichloride, 1,4-anthracene dicarboxylic acid dichloride, 1,4-anthraquinone dicarboxylic acid Dichloride, 2,5-biphenyldicarboxylic acid dichloride,
1,5-biphenylene dicarboxylic acid dichloride, 4,
4 "-p-terphenyldicarboxylic acid dichloride,
4,4'-Methylenedibenzoic acid dichloride, 4,4'-
Isopropylidene dibenzoate dichloride, 4,4'-
Bibenzyldicarboxylic acid dichloride, 4,4'-stilbenedicarboxylic acid dichloride, 4,4'-transdicarboxylic acid dichloride, 4,4'-carbonyldibenzoic acid dichloride, 4,4'-oxydibenzoic acid dichloride, 4, 4'-sulfonyldibenzoic acid dichloride, 4,4'-dithiodibenzoic acid dichloride, p-phenylene diacetic acid dichloride, 3,3'-p-phenylenedipropionic acid dichloride, 4-carboxycinnamic acid dichloride, 3t, 3 'tp-phenylenediacrylic acid dichloride, 3,3'-[4,4 '-(methylenedi-p-phenylene)] dipropionic acid dichloride,
4,4 '-[4,4'-(oxydi-p-phenylene)]
Dipropionyl dichloride, 4,4 '-[4,4'-
(Oxydi-p-phenylene)] dibutyric acid dichloride,
Aromatic dicarboxylic acid dichlorides such as (isopropylidenedi-p-phenylenedioxy) diacetic acid dichloride and bis (p-carboxyphenyl) dimethylsilane dichloride can be mentioned.

Among these, aliphatic dicarboxylic acid dichloride, alicyclic dicarboxylic acid dichloride, isophthalic acid chloride, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5- Biphenylene dicarboxylic acid dichloride, 4,4'-methylene dibenzoic acid dichloride, 4,4'-isopropylidene dibenzoic acid dichloride and 4,4'-bibenzyl dicarboxylic acid dichloride are preferred.

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 1
It is carried out at a reaction temperature of 00 ° C.

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. As the other diamine, the same compounds as those described above are used, and 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 and 2,2-bis (4-aminophenyl) hexafluoropropane are preferred.

The use of such other diamine is usually 0 to 99.9 mol%, preferably 0 to 95 mol% in the total diamine.

The ratio of the compound I and the total diamine 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. 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, an aprotic polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; m- Phenolic solvents such as cresol, xylenol, phenol and halogenated phenol can be mentioned. Usually, the amount of the organic solvent used is preferably such that the total amount of compound I and all diamines 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 polymer which produces a poor solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons or the like does not precipitate. .. Examples of the poor solvent include 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- Examples thereof include dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene and xylene.

The intrinsic viscosity [ηinh = (lnηrel / C, C =
0.5 g / dl, 30 ° C., in N-methyl-2-pyrrolidone, the intrinsic viscosity is measured under the same conditions below] is usually 0.0
It is 5 to 10 dl / g, preferably 0.05 to 5 dl / g.

The liquid crystal aligning agent of the present invention contains the specific polymers I and / or II, and in order to control the molecular weight of these specific polymers and realize the optimum coating property on the substrate,
Monoamine may be added during the reaction.

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 polymer I and / or II and the substrate.

Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3 -Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 1
0-trimethoxyisyl-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 can be mentioned.

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. 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 the temperature of 80 to 200 ° C., preferably 120 to 200 ° C. Heat at temperature to form a coating. This coating is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm.

The formed coating film is made into a liquid crystal alignment film by rubbing it with a roll around which a cloth made of synthetic fiber such as nylon is wound. As the substrate,
For example, glass such as float glass and soda glass; a transparent substrate made of a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, and 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 patterning of these transparent conductive films is performed by a photo-etching method, A method using a mask in advance is used.

In 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 can 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 a spacer 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-
It is also possible to add and use a chiral agent such as that sold as No. 15 (manufactured by Merck). Furthermore, p
Ferroelectric liquid crystals such as-decyloxybenzylidene-p-amino-2-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

[0047]

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 afterimage of the liquid crystal display device was evaluated as 10
After applying a DC voltage of V for 30 minutes, the remaining display when a reverse voltage of 2 V was applied was observed with a microscope. 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 the voltage was turned on and off with a polarizing microscope, and the case where no abnormal domain was observed was considered good.

Synthesis Example 1 44.54 g of p-nitrobenzoic acid chloride and 10.81 g of p-phenylenediamine were dissolved in 500 g of toluene, and 40 g of pyridine was gradually added dropwise to the solution at 1 ° C and 25 ° C.
The reaction was carried out for 0 hours. Then, the reaction solution was washed three times with an aqueous sodium hydrogen carbonate solution, and then the solvent was removed. afterwards,
Recrystallization from ethanol gave a yellow crystalline dinitro compound (yield 82.4%).

Synthesis Example 2 100 g of the dinitro compound obtained in Synthesis Example 1 was dissolved in 1000 g of ethanol, 1 g of Pd / C and 50 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. After cooling to room temperature, the precipitate was separated by filtration and recrystallized from ethanol to obtain a compound IIa having an amide group (yield 5
0.4%).

Synthetic Example 3 44.83 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 69.26 g of compound IIa were dissolved in 1027 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 85.2 g of a specific polymer Ia having an intrinsic viscosity of 1.31 dl / g.

Synthesis Example 4 30.0 g of the specific polymer Ia obtained in Synthesis Example 3 was added to 570
g of γ-butyrolactone, 30.79 g of pyridine and 26.22 g of acetic anhydride were added, and the mixture was mixed at 120 ° C. for 3 days.
The imidization reaction was allowed to proceed for a period of time. Then, the reaction product solution was precipitated in the same manner as in Synthesis Example 1 to give an intrinsic viscosity of 1.35 dl / g.
24.6 g of the specific polymer IIa was obtained.

Synthetic Example 5 In Synthetic Example 3, 69.26 g of compound IIa was added to 4,4 ′.
19.83 g of diaminodiphenylmethane and compound I
A specific polymer Ib was obtained in the same manner as in Synthesis Example 3 except that the amount of Ia was 34.63 g, and the specific polymer Ib was used for imidization reaction in the same manner as in Synthesis Example 4 to give an intrinsic viscosity of 1.16 dl / 22.2 g of the specific polymer IIb was obtained.

Synthesis Example 6 Intrinsic viscosity 1.26 dl / g specific polymer was obtained in the same manner as in Synthesis Example 3 except that the tetracarboxylic dianhydride was changed to 39.2 g of cyclobutanetetracarboxylic dianhydride. Ic36.8g was obtained.

Synthesis Example 7 A dinitro compound was obtained in the same manner as in Synthesis Example 1 except that 11.42 g of 1,4-diaminocyclohexane was used in place of p-phenylenediamine in Synthesis Example 1 (yield 79. 2%), and a reduction reaction was performed in the same manner as in Synthesis Example 2 to obtain a compound IIb having an amide group (yield 46.3).
%).

Synthesis Example 8 In Synthesis Example 3, instead of Compound IIa, Compound II was used.
A specific polymer Id was obtained in the same manner as in Synthesis Example 3 except that b.70.47 g was used, and this specific polymer Id was used to carry out an imidization reaction in the same manner as in Synthesis Example 4 to give an intrinsic viscosity of 1.05 dl. 22.2 g of a specific polymer IId of / g was obtained.

Synthesis Example 9 A dinitro compound was obtained in the same manner as in Synthesis Example 1 except that 22.73 g of 4,4′-diaminobenzanilide was used in place of p-phenylenediamine in Synthesis Example 1. (77.2%), and a reduction reaction was performed in the same manner as in Synthesis Example 2 to obtain a compound IIc having an amide group (yield 47.
3%).

Synthesis Example 10 In Synthesis Example 3, instead of Compound IIa, Compound II was used.
A specific polymer Ie was obtained in the same manner as in Synthesis Example 3 except that c93.09 g was used, and the specific polymer Ie was used to carry out an imidization reaction in the same manner as in Synthesis Example 4 to obtain an intrinsic viscosity of 1.25 dl. 25.2 g of the specific polymer IIe (/ g) was obtained.

Synthesis Example 11 Except that 11.62 g of hexamethylenediamine was used in place of p-phenylenediamine in Synthesis Example 1,
A dinitro compound was obtained in the same manner as in Synthesis Example 1 (yield 8
The reduction reaction was performed in the same manner as in Synthesis Example 2 to obtain the compound IId having an amide group (yield 47.7%).

Synthesis Example 12 Compound II was used instead of compound IIa in synthesis example 3.
A specific polymer If was obtained in the same manner as in Synthesis Example 3 except that d.70.87 g was used, and the specific polymer If was subjected to an imidization reaction in the same manner as in Synthesis Example 4 to give an intrinsic viscosity of 0.89 dl. 20.5 g of the specific polymer IIf of / g was obtained.

Synthesis Example 13 After dissolving 33.15 g of p-nitroaniline and 20.3 g of terephthaloyl dichloride in 500 g of toluene,
40 g of pyridine was gradually added dropwise and reacted at 25 ° C. for 10 hours. Then, the reaction solution was washed three times with an aqueous sodium hydrogen carbonate solution, and then the solvent was removed. Then, recrystallization from ethanol was performed to obtain a yellow crystalline dinitro compound (yield 78.4%).

Synthesis Example 14 100 g of the dinitro compound obtained in Synthesis Example 13 was dissolved in 1000 g of ethanol, 1 g of Pd / C and 50 g of hydrazine monohydrate were added, and the mixture was refluxed for 6 hours. After cooling to room temperature, the precipitate was separated by filtration and recrystallized with ethanol to obtain a compound IIe having an amide group (yield 51.4%).

Synthesis Example 15 In Synthesis Example 3, instead of Compound IIa, Compound II was used.
A specific polymer Ig was obtained in the same manner as in Synthesis Example 3 except that 69.25 g of e was used, and the specific polymer Ig was further subjected to imidization reaction in the same manner as in Synthesis Example 4 to give an intrinsic viscosity of 1.26 dl. 24.5 g of a specific polymer IIg of / g was obtained.

Synthesis Example 16 In Synthesis Example 13, 1,4-cyclohexanedicarboxylic acid dichloride 2 was used instead of terephthaloyl chloride.
A dinitro compound was obtained (yield 81.1%) in the same manner as in Synthesis Example 13 except that 0.7 g was used, and a reduction reaction was performed in the same manner as in Synthesis Example 2 to obtain a compound IIf having an amide group. (Yield 48.7%).

Synthesis Example 17 In Synthesis Example 3, instead of Compound IIa, Compound II was used.
A specific polymer Ih was obtained in the same manner as in Synthesis Example 3 except that f69.25 g was used, and the specific polymer Ih was used to carry out an imidization reaction in the same manner as in Synthesis Example 4 to obtain an intrinsic viscosity of 1.16 dl. 20.5 g of the specific polymer IIh of / g was obtained.

Synthesis Example 18 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 Ii having an intrinsic viscosity of 1.51 dl / g.

Example 1 The polymer Ia obtained in Synthesis Example 3 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.

Then, 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, from the liquid crystal injection port, between the pair of substrates,
Nematic liquid crystal (ZLI-1565, manufactured by Merck)
After filling, the liquid crystal injection port is sealed with an epoxy adhesive, and polarizing plates are attached to both sides on the outside of the substrate so that the polarization direction of the polarizing plate matches the rubbing direction of the liquid crystal alignment film of each substrate. A liquid crystal display element was produced. The orientation of the obtained liquid crystal display device was good, and no afterimage was observed after application of a reverse voltage.

Examples 2 to 9 Synthesis examples 4, 5, 6, 8, 10, 1 in Example 1
Specific polymers IIa, II obtained in 2, 15 and 17
b, Ic, IId, IIe, IIf, IIg and IIh
A liquid crystal display device was produced in the same manner as in Example 1 except that was used, and the orientation of the liquid crystal display device and the afterimage after applying a reverse voltage were measured, and the results are shown in Table 1.

[0070]

[Table 1]

Comparative Example 1 Except that the specific polymer Ii obtained in Synthesis Example 18 was used,
When a liquid crystal display device was prepared and evaluated in the same manner as in Example 1, the liquid crystal alignment was disturbed, and an afterimage was recognized on the screen even 5 minutes after the application of the reverse voltage.

[0072]

EFFECT OF THE INVENTION According to the liquid crystal aligning agent of the present invention, the alignment property is good, and the afterimage when driving the liquid crystal display element is small.
In particular, a liquid crystal alignment film suitable for a TN type liquid crystal display device can be obtained. Further, a liquid crystal display device having a liquid crystal alignment film formed by using the liquid crystal aligning agent of the present invention can be used to select SBE (Super Birefringency Effecec) by selecting a liquid crystal to be used.
It can be suitably used for a t) type liquid crystal display element, an SH (Super Homeotropic) type liquid crystal display element and a ferroelectric liquid crystal display element. Furthermore, a liquid crystal display device having an alignment film formed by using the liquid crystal aligning agent of the present invention is excellent in liquid crystal alignment and reliability, and can be effectively used in various devices. For example, desktop calculators, wrist watches, clocks, and coefficients. It is used for display devices such as display boards, word processors, personal computers, and liquid crystal televisions.

Claims (1)

[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.