JP2550971B2 - Liquid crystal display element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid crystal display device using a specific alignment control film.

(Prior art) A method for obliquely depositing an oxide such as SiO on the surface of a substrate as a parallel alignment treatment method for liquid crystal display, a silane-based or titanium-based coupling agent or carbon, or polyvinyl alcohol, a fluorine resin, or a silicon resin. , A method of applying a solution of polyamide, polyamide-imide, polyimide, etc. to the surface of the substrate, removing the solvent (or curing reaction) by heating and drying, and rubbing (rubbing in a certain direction with a cloth) has been proposed. Although they have been put to practical use, none of them have sufficient characteristics. In addition, recently, using plasma polymerized film,
Although a method using a leon beam or plasma etching has been proposed, it is not practical.

(Problems to be solved by the invention) Although the conventional alignment treatment method of obliquely depositing oxides such as SiO is excellent in reliability and durability when formed into an element, it requires a batch treatment. However, the manufacturing cost of equipment and time is high, which is not realistic. Furthermore, this method is not suitable for the recent trend of large size and colorization. In addition, some polyvinyl alcohol dispersants that have been put to practical use are water-soluble, so that it is possible to print patterns such as offsets and flexo on the substrate surface, and workability is excellent, but moisture resistance when used as an element is high. Since the reliability is poor (especially plastic substrate) and the refractive index of the film is low, there is a problem in that the pattern of the transparent electrode can be seen even when it is not illuminated (mesa appearance).

Further, the polyimide aligning agent which is generally used at present has an excessive quality in terms of heat resistance and has a slight yellowish brown color, so that the display quality is deteriorated. In addition, since heat treatment is performed at 300 ° C or higher for 30 minutes or longer to complete the condensation of the imide ring, plastic cannot be used as the substrate material, and discoloration will occur if a color filter is built in. Furthermore, since high-temperature processing is performed, there are various problems in the process such as warping of the substrate and deformation of the rack. Further, JP-A-55-9518 discloses a liquid crystal display panel using a polymer substance having an amide bond (nylon, etc.) as an alignment treatment film. This method is used to prepare an alignment control film material solution, The work needs to be done at a fairly high temperature, which is not always satisfactory.

Further, JP-A-58-37621 discloses a liquid crystal display element using an aromatic polyether amide as an alignment treatment film. This method is excellent in workability, but the heat resistance of the resin is high. Since it is low and the adhesion to the substrate is poor, there is a problem in reliability and it is not always satisfactory.

Therefore, the present invention solves the above-mentioned problems, enables pattern printing of offset, flexo, etc., and provides an orientation control film having heat resistance if it can be formed even at a low temperature of 200 ° C or less. The present invention has been made for the purpose of providing a liquid crystal display device having the same.

(Means for Solving Problems) In the present invention, an alignment control film of a liquid crystal display device is represented by the general formula (I): [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or halogen, and Ar is a p-phenylene group, an m-phenylene group, a diphenylene group,
Naphthylene group or (Wherein Y is -O -, - SO ₂ -, Or represents CH ₂ —)] and a liquid crystal display device comprising an aromatic polyether amide sulfone polymer having a repeating unit represented by the formula:

The above-mentioned aromatic polyether amide sulfone polymer is insoluble in liquid crystal and water, and this polymer was dissolved in a specific solvent, and this was applied to a substrate having a transparent conductive film such as isodium oxide and dried by heating. After that, rubbing is performed to obtain an orientation control film. A relatively low heating temperature of 100 to 200 ° C is sufficient. By arranging the two substrates having the orientation control film thus formed so as to face each other in parallel and enclosing the liquid crystal therebetween, it is possible to complete a liquid crystal display device having satisfactory characteristics.

The liquid crystal display device of the present invention generally has good liquid crystal orientation and good moisture resistance. Therefore, not only glass but also metal plates such as silicon, aluminum, nickel,
A film or sheet of epoxy acrylate resin, polyethylene terephthalate, or the like having a transparent conductive film can be applied. In addition to this, a film which is insoluble in the liquid crystal or whose surface is not dissolved by the liquid crystal Or sheet (having transparent conductive film)
If it is applicable, it is not particularly limited. Therefore,
Any conventionally known one may be used.

In the present invention, since the specific aromatic polyether amide sulfone polymer solution is applied to the substrate and then the solvent is simply evaporated and dried, the orientation control film can be obtained at low temperature and in a short time. For example, the film thickness to be formed is 200 to 3
Since it is 0000Å, preferably about 500 to 2000Å, and it is very thin, it can be sufficiently dried even below the boiling point. Therefore, compared with the conventional method of obliquely depositing a thin film of SiO ₂ or the like on the substrate (mainly a glass plate) or the method of forming a polyimide film,
An inexpensive liquid crystal display device can be obtained very easily.

The aromatic polyether amide sulfone polymer used in the present invention is produced, for example, as follows.

General formula (II) (Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same as above), and an aromatic diamine represented by the general formula (III) XOC-Ar-COX (III) (where Ar is p -Phenylene group, m-phenylene group, diphenylene ether group, diphenylene sulfone group, diphenylene group or naphthylene group, and the same as other general formula (I), X is chlorine or bromine) It is obtained by reacting an aromatic dicarboxylic acid dihalide by a known method, for example, a solution polymerization method or a method disclosed in JP-A-52-23198.

As the aromatic diamine represented by the general formula (II),
Bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [3-methyl-4- (4-aminophenoxy) phenyl] sulfone, Bis [3-chloro-4 -(4
-Aminophenoxy) phenyl] sulfone, bis [3-
Bromo-4- (4-aminophenoxy) phenyl] sulfone, bis [3-ethyl-4- (4-aminophenoxy) phenyl] sulfone, bis [3-propyl-4-
(4-Aminophenoxy) phenyl] sulfone, bis [3-isopropyl-4- (4-aminophenyloxy) phenyl] sulfone, bis [3-butyl-4- (4-aminophenyloxy) phenyl] sulfone, bis [3-sec-
Butyl-4- (4-aminophenoxy) phenyl] sulfone, bis [3-methoxy-4- (4-aminophenoxy) phenyl] sulfone, bis [3-ethoxy-4-]
(4-Aminophenoxy) phenyl] sulfone, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] sulfone, bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] sulfone, bis [3 , 5-Dibromo-4- (4-aminophenoxy) phenyl] sulfone, bis [3,5-dimethoxy-4- (4-aminophenyloxy) phenyl] sulfone, bis [3-chloro-4-
(4-Aminophenoxy) -5-methylphenyl] sulfone, bis [3-methyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3-chloro-4- (3
-Aminophenoxy) phenyl] sulfone, bis [3-
Bromo-4- (3-aminophenoxy) phenyl] sulfone, bis [3-ethyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3-propyl-4-]
(3-Aminophenoxy) phenyl] sulfone, bis [3-isopropyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3-butyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3-sec-
Butyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3-methoxy-4- (3-aminophenoxy) phenyl] sulfone, bis [3-ethoxy-4-]
(3-Aminophenoxy) phenyl] sulfone, bis [3,5-dimethyl-4- (3-aminophenoxy) phenyl] sulfone, bis [3,5-dichloro-4- (3-aminophenoxy) phenyl] sulfone, bis [3 , 5-Dibromo-4- (3-aminophenoxy) phenyl] sulfone, bis [3,5-dimethoxy-4- (3-aminophenoxy) phenyl] sulfone, bis [3-chloro-4-
(3-aminophenoxy) -5-methylphenyl] sulfone and the like.

As the aromatic dicarboxylic acid dihalide represented by the general formula (III) used in the present invention, all known aromatic dicarboxylic acid dihalides are useful. For example, terephthalic acid dichloride, terephthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, 4,4'-diphenyl ether dicarboxylic acid dichloride, 4,4'-diphenyl ether dicarboxylic acid dibromide, 4,4'-diphenyl Ethyl sulfone dicarboxylic acid dichloride, 4,4'-diphenyl sulfone dicarboxylic acid dibromide, 4,4'-diphenyl dicarboxylic acid dichloride, 4,4'-diphenyl dicarboxylic acid bromide, 4,5-naphthalene dicarboxylic acid dichloride, Alternatively, there is 1,5-naphthalene dicarboxylic acid dibromide and the like, and at least one kind is used.

The orientation ratio of the aromatic diamine and the aromatic dicarboxylic acid dihalide is preferably 1 equivalent of the former and 0.9% of the latter.
It is set in the range of ~ 1.2 equivalents. If the amount is out of the above range, it is difficult to obtain a high molecular weight compound, and only an oligomer-like compound that does not exhibit a resinous property tends to be obtained. Particularly preferably, the latter aromatic dicarboxylic acid halide is in the range of 0.97 to 1.03 equivalents relative to 1 equivalent of the former aromatic diamine. Particularly, in the case of equivalent amounts, the target aromatic polyether amide sulfone resin has the maximum molecular weight.

A part of the aromatic diamine can be replaced with other known aromatic diamine up to 85 mol%. The amount thereof is preferably 50 mol%, particularly preferably 30 mol% from the viewpoint of solvent resistance and colorability (based on the total amount of aromatic diamine).
Should be the upper limit. Examples of other aromatic diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether. Phenyl sulfone, 2,2- (4,4'-diaminodiphenyl) propane,
4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylethane, m-toluenediamine, p-toluenediamine, 3,4'-diaminobenzanilide, 1, 4-diaminonaphthalene, 3,3'-dichloro-4,4'-diaminodiphenyl, benzidine, 4,4'-
Diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, 4,4'-diaminodiphenyl-N-
Phenylamine, 3,3'-diaminodiphenyl sulfone,
There are 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and the like, and at least one of them is used.

Also, known aliphatic diamines such as piperazine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
Decamethylenediamine, p-xylylenediamine, m-xylylenediamine, tetramethylenediamine, dodecamethylenediamine, 4,4'-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 2,1,1-diaminododecal It is also possible to use 1,1,1,2-diaminooctadecane or the like in combination with the aromatic diamine. Further, in order to improve the adhesion to the substrate, a known diamine having a silicon group introduced therein, for example, 1,3-bis (aminopropyl) tetramethyldisiloxane, 1,3-bis (aminopropyl)
Tetraphenyldisiloxane, 1,3-bis (aminopropyl) hexamethyltrisiloxane, etc. may be used in combination with the aromatic diamine. However, since the heat resistance gradually decreases as the blending amount of these is increased, the blending amount should be set so as not to impair the object of the present invention, preferably 30 mol% or less, particularly preferably 10 mol%
It is used together in the following range (based on the total amount of diamine).

When the above-mentioned various diamines are used in combination, the mixing ratio of the total diamine component and the aromatic dicarboxylic acid dihalide can be set on the basis of exactly the same criteria as described above.

In the present invention, the known method used for the reaction between an amine and an acid can be directly used in the reaction, and the various conditions are not particularly limited. For example, it can be achieved by an interfacial polycondensation method, a solution polycondensation method, a melt polycondensation method, or the like. In the interfacial polycondensation reaction, a known water-soluble neutralizing agent described later is used. In the case of the solution polymerization method, a neutralizing agent composed of a known tertiary amine such as triethylamine, pyridine and tributylamine is used. A reaction solvent is used in the interfacial polycondensation method and the solution polymerization method. The solvent must be capable of dissolving at least one of aromatic diamine and aromatic dicarboxylic acid dihalide, if possible. . A representative example of a particularly effective reaction solvent used in the interfacial polycondensation method is cyclohexanone. Other examples of the solvent that can be used include methylene chloride, trichlene, perkrene, ethane dichloride, nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone, acetophenone, p-methylacetophenone and the like.

The reaction solvent used in the solution polymerization method is N, N-
Dimethylformamide, N, N-Dimethylacetamide, N, N
-Diethylformamide, N, N-diethylacetamide,
N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, dimethyl tetramethylene sulfone, 1,3-
Dimethylimidazolidinone and the like are preferable.

If necessary, the reaction solvent should be 2
It is also possible to use a mixture of two or more species. Further, in order to obtain a polymer having a high molecular weight as much as possible, it is advisable to use a more highly dehydrated solvent as the solvent for dissolving the aromatic dicarboxylic acid dihalide. In particular, in the case of solution polycondensation using a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, as a cosolvent, 2 to 10% by weight of lithium chloride or chloride is used. When added with calcium, rhodan calcium, etc., the solubility is significantly increased, which is convenient.

The aromatic polyether amide sulfone polymer of the present invention preferably has a reduced viscosity in a 0.2% by weight dimethylformamide solution at 30 ° C. of 0.3 to 2.0 dl / g. If this reduced viscosity is too small, the solvent resistance will decrease, and if it is too large, the solubility in polar solvents will tend to decrease.

Solvents in which the aromatic polyether amide sulfone polymer is dissolved during the preparation of the orientation control film include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone and cyclohexanone, alone or in combination. It is possible to use a mixed solvent of the above, and a mixture of the above aromatic polyether amide sulfone polymers in a soluble range. For example, a mixed solvent obtained by mixing an appropriate amount of cellosolves, toluene, xylene, etc. may give a better film than the above solvent alone. In addition to the above, an aromatic polyether amide sulfone polymer can be dissolved. It is not particularly limited as long as it is one. In the present invention, other polymers may coexist in order to improve the film forming property.

(Examples) Next, the present invention will be described based on Examples, but the present invention is not limited to these.

The orientation of the liquid crystal display element was evaluated by the angle between the major axis direction of the liquid crystal molecule and the substrate surface, that is, the tilt (tilt angle θ) between the major axis of the substrate and the liquid crystal molecule. A tilt angle of 1.0 to 3.0 is desirable for good orientation, which allows the absolute value of the contrast ratio to be increased.
It is possible to reduce defects such as reverse twist.
[The tilt angle and its measurement method are described in the Journal of Applied Physic
s), Vol. 19 (1980), No. 10, 2013-4.

Example 1 10% by weight solution of an acid chloride mixture consisting of 50% by weight of terephthalic acid dichloride and 50% by weight of isophthalic acid dichloride in cyclohexanone and 95% by weight of bis [4- (4-aminophenoxy) phenyl] sulfone and 1,3-bis ( 20% by weight cyclohexanone solution of a diamine mixture consisting of 5% by weight of aminopropyl) tetramethylenedisiloxane is mixed in the presence of 10% by weight sodium hydroxide aqueous solution at a ratio such that acid chloride and diamine are equimolar. The resulting aromatic polyether amide sulfone polymer was isolated by reacting chloride and diamine. This was dissolved again in dimethylformamide, and this was put into methanol to carry out a purification method for isolating the aromatic polyether amide sulfone polymer three times. The reduced viscosity (η _{sp / c} ) of this polymer (dimethylformamide 0.2% by weight solution, measured at 30 ° C., the same hereinafter) was 1.0 dl / g. The glass transition temperature (Tg) of this polymer was measured and found to be 260 ° C. 97 g of a 6: 4 mixture of N-methylpyrrolidone and butyl cellosolve acetate with 3 g of this polymer.
The varnish was dissolved in to prepare a 3% by weight varnish.

The polymer varnish obtained in this way was applied uniformly on a glass plate with a transparent conductive film that had been thoroughly washed at 2000 rpm using a spinner, then dried at 150 ° C for 30 minutes to evaporate the solvent and achieve an orientation of 1000 Å. A control film was formed. This film was rubbed with a felt in a certain direction to prepare a glass substrate having an orientation control film.

The orientation control films of the two glass substrates thus produced were arranged to face each other and sealed with a two-liquid type sealant mixed with a 10 μ glass fiber. (The sealing agent was cured at 120 ° C for 30 minutes.) A phenylcyclohexane-based liquid crystal (Merck, Z
LI-1132) was placed and the orientation of the liquid crystal was investigated between the two orthogonal polarizing plates.
Every time). The cell before placing the liquid crystal prepared in the same way
When the ZLI-1132 liquid crystal was placed in the same way on the one that was heat-treated at 0 ° C for 2 hours, and the alignment of the liquid crystal was examined between the two orthogonal polarizing plates, a good alignment was obtained (tilt angle 2.2 degrees ).

Example 2 A 10% by weight solution of 100% by weight terephthalic acid dichloride in cyclohexanone and a mixture of aromatic diamines consisting of 90% by weight of bis [4- (3-aminophenoxy) phenyl sulfone and 10% by weight of 4,4'-diaminodiphenyl ether. Of 20% by weight cyclohexanone solution was mixed in the presence of 10% by weight aqueous sodium hydroxide solution at a ratio such that the acid chloride and aromatic diamine were equimolar, and the acid chloride and diamine were reacted. A polyetheramide sulfone polymer was isolated. This was dissolved again in dimethylformamide, and this was put into methanol to carry out a purification method for isolating the aromatic polyether amide sulfone polymer three times.

The reduced viscosity of this polymer was 0.7 dl / g. Moreover, the glass transition temperature (Tg) of this polymer was measured.
It was 255 ° C.

3 g of this polymer was dissolved in 97 g of a 6: 4 mixture of dimethylimidazolidinone and phenyl cellosolve to prepare a 3 wt% varnish.

The polymer varnish thus obtained was applied uniformly on a glass plate with a transparent conductive film that had been thoroughly washed at 2000 rpm using a spinner, and then dried at 180 ° C for 30 minutes to evaporate the solvent and achieve an orientation of 900 Å. A control film was formed. This film was rubbed with a felt in a certain direction to prepare a glass substrate having an orientation control film.

Then, two glass substrates were placed with the orientation control films facing each other, and sealed with a two-sheet type sealant containing 10 μ of glass fiber. (The sealing agent was cured at 120 ° C for 30 minutes.) A phenylcyclohexane liquid crystal (ZLI-1132, manufactured by Merck & Co., Inc.) was placed between the orientation control films of this device, and between the two orthogonal polarizing plates. When the orientation of the liquid crystal was investigated with,
It showed good orientation (tilt angle: 2.0 degrees). A ZLI-1132 liquid crystal was similarly arranged on a cell prepared in the same manner as above, which was heat-treated at 200 ° C. for 2 hours, and the orientation of the liquid crystal was examined between two orthogonal polarizing plates. However, it showed good orientation (tilt angle: 2.0 degrees).

Example 3 10% by weight solution of an acid chloride mixture consisting of 50% by weight of terephthalic acid dichloride and 50% by weight of isophthalic acid dichloride in cyclohexanone and 60% by weight of bis [4- (4-aminophenoxy) phenylsulfone, 4,4'- A 20% by weight cyclohexanone solution of a diamine mixture consisting of 33% by weight of diaminodiphenyl sulfone and 7% by weight of 1,3-bis (aminopropyl) tetramethyldisiloxane was added at a ratio of 10 moles of acid chloride and diamine to give 10 moles.
The resulting aromatic polyether amide sulfone polymer was isolated by mixing the acid chloride and diamine by mixing in the presence of a weight% sodium hydroxide aqueous solution. This was dissolved again in dimethylformamide, and this was put into methanol to carry out a purification method for isolating the aromatic polyether amide sulfone polymer three times.

The reduced viscosity of this polymer was 0.8 dl / g. Moreover, the glass transition temperature (Tg) of this polymer was measured.
The temperature was 260 ° C. 3 g of this polymer was dissolved in 97 g of a 6: 4 mixture of dimethylformamide and ethyl cellosolve acetate to prepare a 3 wt% varnish.

The polymer varnish thus obtained was applied uniformly on a glass plate with a transparent conductive film that had been thoroughly washed using a spinner at 2000 rpm, dried at 120 ° C for 30 minutes to evaporate the solvent, and an orientation of 800 Å was obtained. A control film was formed. This film was rubbed with a felt in a certain direction to prepare a glass substrate having an orientation control film.

The orientation control films of the two glass substrates thus produced were arranged facing each other and sealed with a two-liquid type sealant containing 10 μ of glass fiber. (The sealing agent was cured at 120 ° C for 30 minutes.) A phenylcyclohexane-based liquid crystal (Merck, Z
LI-1132) was placed and the alignment of the liquid crystal was investigated between the two crossed polarizers. The alignment showed good alignment (tilt angle 2.1.
Every time). A cell prepared in the same way and before placing the liquid crystal
When the ZLI-1132 liquid crystal was placed in the same way on the one that had been heat-treated at 200 ° C for 2 hours, and the alignment of the liquid crystal was examined between the two orthogonal polarizing plates, a good alignment was shown (tilt angle 2.1 degrees). ).

Example 4 10% by weight solution of 100% by weight terephthaloyl dichloride in cyclohexanone and 60% by weight of bis [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane 35% by weight
20% by weight cyclohexanone solution of a diamine mixture consisting of 5% by weight of 1,3-bis (aminopropyl) tetramethyldisiloxane and 10% by weight of sodium hydroxide aqueous solution at a ratio such that acid chloride and diamine are equimolar. Mixing in the presence to react the acid chloride with the diamine,
The resulting aromatic polyether amide sulfone polymer was isolated. This was again dissolved in dimethylformamide, and this was added to methanol to carry out a purification method for isolating the aromatic polyether amide sulfone polymer three times. The reduced viscosity of this polymer was 1.1 dl / g. The glass transition temperature (Tg) of this polymer was measured and found to be 250 ° C.

3 g of this polymer was dissolved in 97 g of a 5: 5 mixture of N-methylpyrrolidone and butyl cellosolve acetate to prepare a 3% by weight varnish.

The polymer varnish thus obtained was applied uniformly on a glass plate having a transparent conductive film that had been thoroughly washed at 2000 rpm using a spinner, then dried at 150 ° C for 30 minutes to evaporate the solvent, and an orientation of 1050 Å was obtained. A control film was formed. This film was rubbed with a felt in a certain direction to prepare a glass substrate having an orientation control film.

The orientation control films of the two glass substrates thus produced were arranged facing each other and sealed with a two-liquid type sealant containing 10 μ of glass fiber. (The sealing agent was cured at 120 ° C for 30 minutes.) A phenylcyclohexane-based liquid crystal (Merck, Z
LI-1132) was placed and the orientation of the liquid crystal was investigated between the two orthogonal polarizers.
Every time). A cell prepared in the same way and before placing the liquid crystal
When the ZLI-1132 liquid crystal was placed in the same way on the one that was heat-treated at 200 ° C for 2 hours, and the alignment of the liquid crystal was examined between the two orthogonal polarizing plates, a good alignment was obtained (tilt angle of 2.0 degrees). ).

Comparative Example 10% by weight solution of an acid chloride mixture of 50% by weight of terephthalic acid dichloride and 50% by weight of isophthalic acid dichloride in cyclohexanone and 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane 100% by weight of 2
The 0% by weight cyclohexanone solution was mixed in the presence of 10% by weight aqueous sodium hydroxide solution at a ratio such that the acid chloride and diamine were equimolar, and the acid chloride and diamine were reacted to isolate the resulting polymer. . This was again dissolved in dimethylformamide, and this was put into methanol, and the purification method of isolating the polymer was carried out three times.

The reduced viscosity of this polymer was 0.9 dl / g. Moreover, the glass transition temperature (Tg) of this polymer was measured.
It was 220 ℃.

3 g of this polymer was dissolved in 97 g of a 6: 4 mixture of N-methylpyrrolidone and butyl cellosolve acetate to prepare a 3% by weight varnish.

The polymer varnish obtained in this way was applied uniformly on a glass plate with a transparent conductive film that had been thoroughly washed at 2000 rpm using a spinner, and then dried at 150 ° C for 30 minutes to evaporate the solvent and achieve an orientation of 900Å film thickness. A control film was formed. This film was rubbed with a felt in a certain direction to prepare a glass substrate having an orientation control film.

The orientation control films of the two glass substrates thus produced were arranged facing each other and sealed with a two-liquid type sealant containing 10 μ of glass fiber. (The sealing agent was cured at 120 ° C for 30 minutes.) A phenylcyclohexane-based liquid crystal (Merck, Z
LI-1132) was placed and the alignment of the liquid crystal was investigated between the two crossed polarizers. The alignment showed good alignment (tilt angle 2.1.
Every time). The cell before placing the liquid crystal prepared in the same way
When the ZLI-1132 liquid crystal was placed in the same way as the one that was heat-treated at 0 ° C for 2 hours and the orientation of the liquid crystal was examined between the two orthogonal polarizing plates, a domain was generated in the vicinity of the sealant and the alignment failure was observed. There was a portion.

(Effect of the Invention) According to the present invention, by using a specific aromatic polyether amide sulfone polymer as an alignment control film material, (1) an alignment control film that can be processed at a low temperature of about 100 to 200 ° C. Since the film of the aromatic polyether amide sulfone polymer can be applied to the substrate material, not only glass but also a resin film or a resin plate can be used. (2) The orientation control film material can be used for water and liquid crystal. Since it is an insoluble resin, a liquid crystal display element having excellent moisture resistance can be obtained. As a result, it is possible to provide a light and thin liquid crystal display element, and it is possible to easily obtain a liquid crystal display element that is cheaper than the conventional method.

The device of the present invention can display a color by arranging a guest-host type liquid crystal. In addition, the device of the present invention
A TFT may be used.

Furthermore, the durability of the liquid crystal display device of the present invention is practically no problem.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiaki Fukushima, 14 Ii Minamikaigan, Ichihara-shi, Goi Plant, Hitachi Chemical Co., Ltd. In the factory (72) Inventor Gaiji Oshima 2-1, 1-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Inside Hitaseikagyo Co., Ltd. (56) Reference JP-A-53-34541 (JP, A) JP-A-61 -200527 (JP, A)

Claims (1)

(57) [Claims] 1. An alignment control film of a liquid crystal display device is represented by the general formula (I): [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or halogen, and Ar is a p-phenylene group, an m-phenylene group, a diphenylene group,
Naphthylene group or (Wherein Y is -O -, - SO ₂ -, -S-, Or represents CH _2- ]]. A liquid crystal display device comprising an aromatic polyether amide sulfone polymer having a repeating unit represented by