JP3265567B2 - Method for manufacturing liquid crystal alignment film and liquid crystal display element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a liquid crystal alignment film and a liquid crystal display device. More specifically, the present invention relates to a method for producing a liquid crystal alignment film, which is characterized by imparting liquid crystal alignment ability by irradiating linearly polarized ultraviolet rays without performing a rubbing treatment, and a liquid crystal display device having the liquid crystal alignment film.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy has a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and a long axis of liquid crystal molecules is continuously twisted by 90 ° or more between the substrates. TN (Twisted Nema)
2. Description of the Related Art A liquid crystal display device having a (tic) type or STN (Super Twisted Nematic) type liquid crystal cell is known.

As means for aligning the liquid crystal in the liquid crystal cell, an organic film is formed on the surface of the substrate, and then the surface of the organic film is rubbed in one direction with a cloth material such as rayon to impart the liquid crystal alignment ability. There is a method of performing a rubbing treatment, a method of obliquely depositing silicon oxide on a substrate surface, and a method of forming a molecular film having a long-chain alkyl group using a Langmuir-Blodgett method (LB method). The size of the substrate to be processed is limited, and the orientation of the liquid crystal by rubbing is generally industrial in terms of processing time and processing cost.

[0004]

However, when the alignment of the liquid crystal is performed by a rubbing treatment, there is a problem that static electricity is easily generated during the process. When static electricity is generated, dust adheres to the surface of the alignment film, causing display defects. In addition, TFT (thin film transister)
In the case of a liquid crystal cell having an element, a circuit of the TFT element is destroyed by the generated static electricity, which causes a reduction in yield. Furthermore, in a liquid crystal display device which is to be further refined in the future, uniformity of the rubbing process becomes a problem because the pixel density is increased. An object of the present invention is to provide a method for producing a liquid crystal alignment film that does not generate static electricity and is excellent in mass productivity, and a liquid crystal display device using the liquid crystal alignment film.

[0005]

Method of manufacturing a liquid crystal alignment film of the present invention SUMMARY OF] is mosquito Rukon (Ben Searle acetophenone) structure, a stilbene structure, the organic film made of polyimide having either anthraquinone structure or a carbazole structure, a straight line A method for producing a liquid crystal alignment film, comprising a step of imparting liquid crystal alignment ability by irradiating polarized ultraviolet light.

Further, a liquid crystal display device according to the present invention is characterized by having the above-mentioned liquid crystal alignment film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Liquid crystal aligning agent The liquid crystal aligning agent forming the liquid crystal aligning film of the present invention contains an organic compound functional to ultraviolet rays. The term “functional” as used herein means that upon irradiation with ultraviolet light, the energy level is increased by a photoexcitation reaction, and then energy is released to return to a stable state. Examples of such organic compounds, mosquito Rukon (Ben Searle acetophenone) structure, stilbene structure, a polyimide having any anthraquinone structure or a carbazole structure is used. Polyimide has excellent heat resistance.

The polyimide is obtained by reacting (a) tetracarboxylic dianhydride with (b) a diamine compound, and via an intermediate polyamic acid. Polyimide used in the present invention, (a) at least one component of the tetracarboxylic dianhydride component and (ii) a diamine component, mosquitoes Le <br/> Con (Ben Searle acetophenone) structure, a stilbene structure, anthraquinone structure Alternatively, a compound having a carbazole structure is used.

[0009] As the tetracarboxylic acid dianhydride with a mosquito Rukon structure, for example 3,3 ', 4,4'-chalcone-tetracarboxylic acid dianhydride. Examples of the tetracarboxylic dianhydride having a stilbene structure include 3,3 ′, 4,4′-stilbene tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride having an anthraquinone structure include 2,3,6,7-
Anthraquinone tetracarboxylic dianhydride is mentioned. Examples of the tetracarboxylic dianhydride having a carbazole structure include 2,3,6,7-carbazole tetracarboxylic dianhydride.

[0010] The diamine compound having a mosquito Rukon structure, for example 3,3'-chalcone, 4,4
Diaminochalcone, 3,4′-diaminochalcone, 3,
4-diaminochalcone and the like. Examples of the diamine compound having a stilbene structure include 3,3′-diaminostilbene, 4,4′-diaminostilbene,
4,4'-diaminostilbene-2,2'-sulfonic acid, 4,4'-bis (4-amino-1-naphthylazo)
-2,2'-stilbenesulfonic acid and the like.
As a diamine compound having an anthraquinone structure,
For example, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone-2,3-dicyano-9,10-anthraquinone and the like can be mentioned. Examples of the diamine compound having a carbazole structure include 3,6-diaminocarbazole.

The polyimide used in the present invention may be used in combination with other tetracarboxylic dianhydrides and diamine compounds to such an extent that the effects of the present invention are not impaired.

Other tetracarboxylic dianhydrides include:
For example, 2,3,5-tricarboxycyclopentylcarboxylic dianhydride, butanetetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-
2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5
9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural)- 3-methyl-3-cyclohexene-1,
2-dicarboxylic dianhydride, bicyclo [2.2.2]-
Aliphatic and alicyclic tetracarboxylic dianhydrides such as oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;

Pyromellitic dianhydride, 3,3 ', 4
4'-biphenylsulfonetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′,
4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride , 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ',
4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ', 4,4'-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'-diphenyl ether dianhydride, bis (triphenylphthalic acid) A) Aromatic tetracarboxylic dianhydride such as -4,4'-diphenylmethane dianhydride.

Among these, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride Thing, 3,3 ',
4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′ , 4,4'-biphenylethertetracarboxylic dianhydride is preferred. These can be used alone or in combination of two or more.

As other diamine compounds, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,
3′-dimethyl-4,4′-diaminobiphenyl, 4,
4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,
3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1 , 3,3-trimethylindane, 3,4 '
-Diaminodiphenyl ether, 2,2-bis (4-aminophenoxy) propane, 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, , 7-Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4 '-
Diaminobiphenyl, 2,2'-dichloro-4,4'-
Diamino-5,5'-dimethoxybiphenyl, 3,3 '
-Dimethoxy-4,4'-diaminobiphenyl, 1,
4.4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl Hexafluoropropane, 4,4'-diamino-2,2'-
Aromatic diamines such as bis (trifluoromethyl) biphenyl and 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
Aromatic diamine having a hetero atom such as diaminotetraphenylthiophene;

1,1-meta-xylylenediamine, 1,3
-Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclo Fats such as pentadienylenediamine, hexahydro-4,7-methanoindanylenediethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undesylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) Group and alicyclic diamines; diaminoorganosiloxanes such as diaminohexamethyldisiloxane.

Of these, p-phenylenediamine,
4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4 ′
-Diaminodiphenyl ether, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl]
Hexafluoropropane, 4,4'-diamino-2,
2'-bis (trifluoromethyl) biphenyl, 4,
4'-bis [(4-amino-2-trifluoromethyl)
Phenoxy] -octafluorobiphenyl is preferred.
These can be used alone or in combination of two or more.

The polyimide used in the present invention is:
The (a) tetracarboxylic dianhydride component and the (b) diamine component are polycondensed to obtain a polyamic acid, which is then imidized by heating, if necessary, in the presence of a dehydrating agent and an imidization catalyst. It can be obtained by: The reaction temperature in the case of imidization by heating is usually 60 to 300 ° C, preferably 100 to 170 ° C. When the reaction temperature is lower than 60 ° C., the progress of the reaction is delayed, and when it exceeds 300 ° C., the molecular weight of the polyamic acid may be greatly reduced. Also,
The reaction for imidization in the presence of a dehydrating agent and an imidization catalyst can be performed in an organic solvent. The reaction temperature is
It is usually 0 to 180 ° C, preferably 60 to 150 ° C.
Acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. Further, as the imidation catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but are not limited thereto. The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polyamic acid.
The amount of the imidization catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used. The content of the amic acid residue in the polyimide can be adjusted by the amount of the imidization catalyst and the dehydrating agent used.

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

Solvent The liquid crystal aligning agent for forming the liquid crystal aligning film of the present invention comprises a solution of the above-mentioned polyimide functionalized with ultraviolet rays. The solvent used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the polyimide , and can be used alone or in combination of two or more solvents.

Other Additives The liquid crystal aligning agent used in the present invention may contain various thermosetting crosslinking agents for stabilizing the pretilt angle and increasing the strength of the coating film. As the thermosetting crosslinking agent, a polyfunctional epoxy-containing compound is effective, and bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl diamine type Epoxy resins, heterocyclic epoxy resins, epoxy group-containing acrylic resins and the like can be used. Commercial products include, for example, Epolite 400E and 300
2 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Epikote 82
8, 152, and epoxy novolak 180S (manufactured by Yuka Shell Epoxy Co., Ltd.).

Further, when the above-mentioned polyfunctional epoxy-containing compound is used, 1-
A base catalyst such as benzyl-2-methylimidazole can be added.

Further, the liquid crystal aligning agent used in the present invention may contain a functional silane-containing compound for the purpose of improving the adhesion to the substrate. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
-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-trimethoxyisyl-1,1
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.
Further, there can be mentioned a reaction product of a tetracarboxylic dianhydride and an amino group-containing silane compound described in JP-A-63-291922.

Formation of Liquid Crystal Alignment Film The liquid crystal alignment film of the present invention can be manufactured, for example, by the following method. First, on the transparent conductive film side of the substrate provided with the transparent conductive film, the liquid crystal alignment agent is applied by a roll coater method,
Apply by spinner method, printing method, etc., 40-200 ° C
To form a coating film. The thickness of the coating film is usually 0.001 to 1 μm, preferably 0.005 to 0.5
μm.

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

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

In applying the liquid crystal alignment agent, in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film,
On the substrate and the transparent conductive film, a functional silane-containing compound, titanate or the like can be applied in advance.

Next, the coating film is irradiated with a linearly polarized Shibai ray and, if necessary, is further subjected to a heat treatment at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. The ultraviolet light used in the present invention has a wavelength of 150 nm to 450 nm, among which 190 nm to 380 nm.
Is preferred.

As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used.

Liquid Crystal Display Device In the liquid crystal display device of the present invention, two substrates having the liquid crystal alignment film formed thereon are opposed to each other so that the polarization direction of the linearly polarized ultraviolet light irradiated on the liquid crystal alignment film has a predetermined angle. Then, the peripheral portion between the substrates is sealed with a sealant, filled with liquid crystal, and the filling hole is sealed to form a liquid crystal cell. Then, a polarizing plate is stuck on both surfaces of the polarizing plate so that the polarizing direction of the polarizing plate forms a predetermined angle with the polarizing direction of the linearly polarized ultraviolet light irradiated on the liquid crystal alignment film of the substrate, thereby forming a liquid crystal display element. By adjusting the angle between the polarization directions of the irradiated linearly polarized ultraviolet rays and the angles between the respective substrates and the polarizing plates on the two substrates on which the liquid crystal alignment films are formed, TN
A liquid crystal display device having a type or STN type liquid crystal cell can be arbitrarily obtained.

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

As the liquid crystal, a nematic liquid crystal,
A smectic liquid crystal or the like can be used. TN
In the case of a liquid crystal cell, a liquid crystal cell that forms a nematic liquid crystal is preferable. 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, a biphenylcyclohexane liquid crystal, and a pyrimidine liquid crystal. Liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like are used. In the case of an STN-type liquid crystal cell, the liquid crystal is a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonaate or cholesteryl carbonate, or a chiral liquid sold under the trade name C-15 or CB-15 (manufactured by Merck). An agent or the like can be further added and used. Furthermore, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can be used.

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

[0048]

According to the method for producing a liquid crystal alignment film of the present invention, dust does not adhere due to static electricity generated during the conventional rubbing process, and the circuit breakage of the TFT element does not occur.
An alignment film can be manufactured with a high yield.

[0049]

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

[0050]

[0051]

Synthesis Example 1 Polymerization of polyamic acid 22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 4,4′-diaminostilbene
02 g was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate.
Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35.21 g of a polymer Ic. Imidation Reaction To 20.00 g of the obtained polymer Ic, 380 g of N-methyl-2-pyrrolidone, 7.28 g of pyridine and 9.40 g of acetic anhydride were added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the polymer was washed with methanol and dried under reduced pressure for 15 hours to obtain polymer IIc12.6.
1 g was obtained.

Synthesis Example 2 Polymerization of polyamic acid 22.42 g of 2,3,5-tricarboxycyclopentylacetic dianhydride and 4,4'-diaminoanthraquinone 2
3.83 g was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. After that, it is washed with methanol and then reduced under reduced pressure at 40 ° C. for 15 minutes.
After drying for 4 hours, 40.00 g of a polymer Id was obtained. Imidation Reaction To 20.00 g of the obtained polymer Id, 380 g of N-methyl-2-pyrrolidone, 6.84 g of pyridine and 8.83 g of acetic anhydride were added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the polymer was washed with methanol and dried under reduced pressure for 15 hours to obtain a polymer IId16.6.
7 g were obtained.

Synthesis Example 3 Polymerization of polyamic acid 32.22 g of 3,3'4,4'-benzophenonetetracarboxylic dianhydride and 10.8 of p-phenylenediamine
1 g was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate.
Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 36.00 g of a polymer Ie. Imidation Reaction To 20.00 g of the obtained polymer Ie, 380 g of N-methyl-2-pyrrolidone, 6.19 g of pyridine and 7.71 g of acetic anhydride were added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the polymer was washed with methanol and dried under reduced pressure for 15 hours to obtain polymer IIe15.3.
0 g was obtained.

Comparative Synthesis Example 1 Polymerization of Polyamic Acid 22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 10.81 g of p-phenylenediamine
Was dissolved in 300 g of N-methyl-2-pyrrolidone, and 6
The reaction was performed at 0 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 27.44 g of a polymer Ix. Imidation Reaction To 20.00 g of the obtained polymer Ix, 380 g of N-methyl-2-pyrrolidone, 9.52 g of pyridine and 1 part of acetic anhydride were added.
2.29 g was added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the polymer was washed with methanol and dried under reduced pressure for 15 hours to obtain a polymer IIx15.2.
7 g were obtained.

[0056]

Example 1 The polymer (IIc) obtained in Synthesis Example 1 was converted to γ-butyrolact
To a solution having a solid content of 4% by weight.
Is filtered through a filter having a pore size of 1 μm, and a liquid crystal aligning agent is
A solution was prepared. This solution is transferred to a transparent electrode made of ITO film.
A film thickness of 0.1μ on the transparent electrode surface on a glass substrate with electrodes
m using a spinner and at 180 ° C
After drying for 1 hour, a thin film was formed. Hg-Xe on the thin film surface
From the lamp, Gran Laser Prism GLP-0-10
A linearly polarized ultraviolet ray of 0.5 J / cm ² mainly having a wavelength of 365 nm was irradiated with -15-AN (manufactured by Sigma Koki). Next, a pair of linearly polarized ultraviolet rays is irradiated.
The outer edge of each substrate with the liquid crystal alignment film
Epoxy resin adhesive containing 17μm aluminum oxide balls
After screen printing, a pair of substrates is
Surfaces are opposed to each other, and the polarization directions of ultraviolet rays are orthogonal.
Then, the adhesive was cured by overlapping. Next
The nematic type is inserted between the pair of substrates from the liquid crystal injection port.
After filling liquid crystal (Merck, ZLI-1565)
Seal the liquid crystal injection port with an epoxy-based adhesive, and
Polarizing plates on both sides, the polarization direction of the polarizing plate
Laminated to match the direction of polarization of ultraviolet light of the liquid crystal alignment film
When the liquid crystal display device was manufactured,
It was good. When a voltage of 5 V is applied,
Changes in the brightness of the liquid crystal display element in response to the pressure ON-OFF.
Was observed.

Examples 2 and 3 A liquid crystal display device was prepared in the same manner as in Example 1 except that the polymers IId to IIe obtained in Synthesis Examples 2 and 3 were used.
The orientation of the liquid crystal was good. When a voltage was applied under the same conditions as in Example 1, a change in the brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage.

Comparative Example 2 Using the polymer IIx obtained in Comparative Synthesis Example 1, a thin film was formed on a substrate in the same manner as in Example 1 and irradiated with linearly polarized ultraviolet light to form a liquid crystal alignment film. When a liquid crystal display device was prepared using the above, no alignment of liquid crystal was observed.

[0060]

According to the method for manufacturing a liquid crystal alignment film of the present invention, dust does not adhere due to static electricity generated during the conventional rubbing process, and the circuit breakage of the TFT element does not occur, so that the alignment film can be manufactured with a high yield. it can. Further, since the liquid crystal alignment film in the present invention has excellent in-plane uniformity,
When used for display of N type, STN type, etc., a liquid crystal display element having high display quality can be obtained and can be effectively used for various devices. For example, a desk calculator, a wristwatch, a clock, a coefficient display board, a word processor, a personal computer computer,
It is suitably used for a display device such as a liquid crystal television.

Continuing on the front page (72) Inventor Yasuo Matsuki 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Yasumasa Takeuchi 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Stock In-company (56) References JP-A-7-104302 (JP, A) JP-A-7-72483 (JP, A) JP-A-6-95125 (JP, A) JP-A-5-34699 (JP, A) JP-A-8-254705 (JP, A) JP-A-8-122789 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/1337 520

Claims (2)

(57) [Claims] 1. A month Rukon (Ben Searle acetophenone)
Structure, a stilbene structure, an anthraquinone structure or an organic film made of a polyimide having any of a carbazole structure, a liquid crystal alignment film characterized by having a step of imparting liquid crystal alignment capability by irradiating linearly polarized ultraviolet light Production method. 2. A liquid crystal display device having a liquid crystal alignment film obtained by the method according to claim 1.