JP2763232B2 - Liquid crystal display element spacer, liquid crystal display element using the same, and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display spacer which can prevent the movement of the spacer and eliminate the abnormal orientation of the liquid crystal at the interface between the liquid crystal and the spacer, and the liquid crystal display using the same. The present invention relates to an element and a method for manufacturing the same.

[0002]

2. Description of the Related Art In a liquid crystal display device, a spacer moves within a substrate gap due to electric or mechanical stress, and thus the substrate gap fluctuates or the spacer concentrates on a specific portion of a display area. Display quality may be degraded. Further, there is a problem that the alignment film formed on the substrate is damaged when the spacer moves. In order to prevent the movement of the spacer, there has been proposed a method of coating the surface of the spacer with an adhesive and fixing the spacer to the substrate. For example, JP-A-1-247155 discloses a method of coating a hot-melt adhesive resin on a spacer.
No. 724 discloses a method of coating a spacer with an epoxy resin. Further, Japanese Patent Application Laid-Open No. Hei.
No. 4 and JP-A-2-20827 disclose that a spacer is dispersed in a resin solution for orientation control and applied on a substrate to prevent the movement of the spacer.

It has been well known in the art that in liquid crystal display devices, the orientation of liquid crystal molecules may be irregular at the interface between the liquid crystal and the spacer, thereby deteriorating the image quality. In particular, in a liquid crystal display device using a super twisted nematic liquid crystal (STN liquid crystal), which is frequently used recently, the above-described liquid crystal alignment abnormal phenomenon is likely to occur. It is also well known that such liquid crystal alignment abnormality (hereinafter referred to as alignment abnormality) can be eliminated when liquid crystal molecules are vertically aligned at the interface between the liquid crystal and the spacer.

[0004] From the above circumstances, several proposals for promoting the vertical alignment of liquid crystal molecules at the interface between the liquid crystal and the spacer (hereinafter referred to as vertical alignment) have been made. For example, Japanese Patent Application Laid-Open No. 54-49155 proposes to promote the vertical alignment by treating the electrode substrate, not the spacer itself, with a special silane coupling agent.
Further, Japanese Patent Application Laid-Open No. 3-293327 proposes that the surface treatment of a spacer with a silane coupling agent or the like lowers the surface tension to promote vertical alignment.

[0005] Further, although vertical orientation is not mentioned, as a method for eliminating abnormal orientation, Japanese Patent Application Laid-Open No. 63-36224 discloses a method.
In Japanese Patent Application Laid-Open No. HEI 23-23317, it is proposed to disperse a spacer in a polyimide solution and apply the spacer on a substrate to disperse the spacer in a polyimide alignment film.

In the method of dispersing the spacers in an alignment film made of polyimide, the spacers are in a state of being coated with polyimide. Therefore, the spacers do not directly contact the liquid crystal, and only the polyimide alignment film comes in contact with the liquid crystal. This can prevent the orientation of the liquid crystal from becoming irregular at the interface between the liquid crystal and the spacer. However, in these methods, first, since it is difficult to sufficiently disperse the spacer in the polyimide solution, the spacer may aggregate in the alignment film. In order to solve this drawback, Japanese Patent Laid-Open No. 23317/1990 proposes to improve the dispersibility by treating the surface of the spacer with a titanium coupling agent or the like. However, even with such a contrivance, in the method of dispersing the spacer in the alignment film, the spacer causes unevenness in the alignment film,
At the time of the rubbing treatment performed as the orientation treatment, a shadow is generated in the rubbing direction, so that there is a possibility that the orientation unevenness occurs. The rubbing treatment here means that the alignment film is made of, for example, synthetic fibers such as nylon, polyester, and polyacrylonitrile, or natural fibers such as cotton, silk, and wool, in order to ensure the alignment of the liquid crystal on the alignment film. Is to rub in a certain direction.

[0007]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned problems, and its object is to not only prevent the spacer from moving, but also to prevent the liquid crystal from being abnormal at the interface between the liquid crystal and the spacer. An object of the present invention is to provide a spacer for a liquid crystal display element capable of eliminating alignment, a liquid crystal display element using the same, and a method for manufacturing the same.

[0008]

The spacer for a liquid crystal display element of the present invention is characterized in that a coating layer comprising a polyimide intermediate is formed on the surface of fine particles, thereby achieving the above object.

The liquid crystal display device of the present invention is a liquid crystal display device of the present invention.
Liquid crystal display device obtained using a crystal display element spacer
A polyimide intermediate on the surface of the fine particles.
The spacer on which the coating layer made of polyimide obtained by doping is formed is interposed between the electrode substrates, and the coating layer is adhered between the electrode substrates, thereby achieving the above object. .

[0010] manufacturing process of the liquid crystal display device of the present invention include poly polyimide intermediate spacer for a liquid crystal display device, by heating under pressure at a state of being interposed between the electrode substrates of the <br/> present invention
The method includes a step of imidizing and a step of injecting a liquid crystal between the electrode substrates, whereby the object is achieved.

Hereinafter, the present invention will be described in detail.

The fine particles used in the spacer for a liquid crystal display element of the present invention may be formed of any of a synthetic resin material and an inorganic material, and may be colored.

The above synthetic resin materials include epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, divinylbenzene copolymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylester copolymer, diallyl phthalate, Crosslinkable resins such as allyl isocyanurate polymer and benzoguanamine polymer are exemplified. Particularly preferably, melamine resin,
Divinylbenzene copolymer, divinylbenzene-styrene copolymer, divinylbenzene-acryl ester copolymer, diallyl phthalate polymer and the like.

Examples of the inorganic material include silicate glass, borosilicate glass, lead glass, soda-lime glass, alumina, and alumina silicate. Particularly preferred are silicate glass and borosilicate glass.

The shape of the fine particles is preferably as shown below, but is not limited thereto. For example, there are a true spherical shape, an elliptical spherical shape, a columnar shape and the like. When the fine particles are spherical, the diameter is preferably in the range of 0.1 to 1000 μm, and particularly preferably 1 to 100 μm. When the fine particles have an elliptical sphere, the minor axis is preferably in the range of 0.1 to 1000 μm, and particularly preferably 1 to 100 μm.
It is. The ratio of the major axis to the minor axis is preferably in the range of 1 to 10,
Particularly preferably, it is 1 to 5. When the fine particles have a columnar shape, the diameter is preferably in the range of 0.5 to 1000 μm, and particularly preferably 3 to 100 μm. The length: diameter ratio of the cylinder is preferably in the range of 1 to 50, and particularly preferably 1 to 10.

By coloring the fine particles, colored fine particles can be obtained. As a coloring method, when the fine particles are formed of a synthetic resin material, a method of treating the fine particles with carbon black, a disperse dye, a basic dye, a metal oxide, or the like can be given.

When the fine particles are formed of an inorganic material, an organic film can be formed on the surface of the fine particles in advance, and the fine particles can be colored by being decomposed or carbonized at a high temperature.

If the material forming the fine particles is itself colored, it can be used without any special coloring.

[0019] Polyimide intermediates used in the present invention, port
Preferably those polyimide temperature of 200 ° C. or less, for example, the aromatic polyamic acid having a part of the aliphatic structure represented by the following general formula [I] and the like. This is because, in the present invention, the polyimide intermediate coated on the surface of the fine particles is prepared by first applying the polyimide intermediate to the substrate and heating it (heating at 300 ° C. to 350 ° C.) as in the related art. Instead of a method of forming an alignment film by forming polyimide, a step of forming a liquid crystal cell (a so-called empty cell before liquid crystal injection) by spraying the spacer on a substrate, and then heat-pressing a peripheral sealing material (at 200 ° C. or lower). This is because, during the heating, the spacer is adhered to the substrate at the same time as the polyimide intermediate is converted into a polyimide, thereby exhibiting the function intended by the present invention. Thus, as the polyimide intermediate poly imidization temperature is not preferable to exceed 300 ° C..

[0020]

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(Wherein, R ¹ represents a lower alkylene group such as methylene, ethylene and propylene, and n represents an integer of 1 or more). A method for forming a coating layer comprising the above polyimide intermediate on the surface of fine particles. This will be described below.

The above polyimide intermediate is dissolved in a suitable solvent, for example, N-methylpyrrolidone, ethyl carbitol, butyl cellosolve, dimethylformamide, γ-butyrolactone, and the like, and fine particles are added and dispersed in the obtained solution. Although the amount of the solvent may be arbitrary, the concentration of the polyimide intermediate in the solution is in the range of 3 to 30% by weight. Preferably, it is in the range of 5 to 20% by weight. If the content is less than 3% by weight, the surface of the fine particles may not be sufficiently covered,
If it exceeds 0% by weight, the viscosity of the solution may be too high to make the operation difficult. Next, the solvent in which the fine particles are dispersed is evaporated by a method such as decompression while stirring, whereby a coating layer comprising the polyimide intermediate is formed on the surface of the fine particles. If a small amount of a precipitant and / or a surfactant that is soluble in the solvent but not soluble in the polyimide intermediate is added to the solution, coalescence and agglomeration of particles likely to occur as the solvent evaporates may occur. Can be prevented.

Examples of the precipitant include water, methanol, ethanol, isopropanol and butanol, and examples of the surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene and polyoxypropylene block polymer. . The content of the above-mentioned precipitant and surfactant is preferably 0.01 to 10% by weight.

The thickness of the coating layer comprising the polyimide intermediate is preferably from 0.01 to 2 μm, particularly preferably from 0.1 to 1 μm. If the thickness of the coating layer is smaller than 0.01 μm, the coating layer is easily peeled off from the surface of the fine particles, and the adhesion of the spacer to the substrate and the vertical alignment of the liquid crystal cannot be expected. The thickness of the coating layer is 2 μm.
If it is thicker, coalescence of the fine particles tends to occur.

In the present invention, in order to improve the adhesiveness between the fine particles and the coating layer comprising the polyimide intermediate and to form a relatively thin coating layer uniformly on the surface of the fine particles, the fine particles and the coating layer are interposed between them. A titanium oxide layer or a silane oxide layer may be formed.

As a method for forming a titanium oxide layer on the surface of the fine particles, for example, the following method can be mentioned.

After dissolving the organic titanate compound in a solvent and applying the resulting solution to the surface of the fine particles, the organic titanate compound is hydrolyzed to form a titanium oxide layer.

As the organic titanate compound, for example, tetraethoxytitanium, tetrapropoxytitanium,
Tetrabutoxytitanium, tetrapentoxytitanium, tetrahexoxytitanium, tetrakis (2-ethylhexoxytitanium), tetradodecylalkoxytitanium, tetrastearoxytitanium, dipropoxybis (triethanolaminato) titanium, dihydroxybis (lactate) Titanium, titanium propoxyoctylene glycolate and the like. Particularly preferred are tetrapropoxytitanium, tetrabutoxytitanium, tetrakis (2-ethylhexoxytitanium), dipropoxybis (acetylacetonato) titanium, dibutoxybis (triethanolanamit) titanium and the like.

The amount of the organic titanate compound used is preferably 0.001 to 0.5 parts by weight based on 1 part by weight of the fine particles.

Examples of the solvent include n-hexane, cyclohexane, benzene, toluene, trichlene, Freon-113 and the like.

As a method of applying the organic titanate compound to the surface of the fine particles, it is preferable to immerse the fine particles in a solution comprising the organic titanate compound and a solvent, sufficiently mix them, and evaporate the solvent. Further, after evaporating the solvent, the fine particles are optionally cooled to 60 ° C to 150 ° C.
It is preferred to heat with.

The use amount of the above solution is preferably 0.5 to 50 parts by weight with respect to 1 part by weight of the fine particles.

By the above operation, the organic titanate compound layer formed on the surface of the fine particles reacts with moisture in the air and is hydrolyzed to form a titanium oxide layer represented by the following formula [II]. It is supposed to do.

[0034]

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(In the formula, n is an integer of 1 or more.) The amount of the titanium oxide layer formed on the surface of the fine particles is preferably 0.01 to 500 mg per 1 m ² of the surface of the fine particles in terms of titanium. preferable. Particularly preferably, 0.1 to 100 mg
It is. When the amount of the titanium oxide layer is less than 0.01 mg, the adhesion between the coating layer formed of the polyimide intermediate and the fine particles is insufficient, and when it exceeds 500 mg, the electric resistance of the obtained spacer is reduced.

The method for forming a silane oxide layer on the surface of the fine particles includes, for example, the following method.

The silane coupling agent is dissolved in a solvent, fine particles are immersed in the solution, heated and filtered.
A silane coupling agent treatment is performed by heating and drying the surface of the fine particles, and then the silane coupling agent is hydrolyzed to form a silane oxide layer.

As the silane coupling agent, those represented by the following general formula [III] are preferable.

[0039]

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(Wherein m is an integer of 0 to 20, and X represents any one of a chlorine atom, a bromine atom, a methoxy group and an ethoxy group). Alkylsilanes and trialkoxylated alkylsilanes.

Examples of the above trihalogenated alkylsilane include methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, heptyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane. Chlorosilane, dodecyltrichlorosilane, octadecyltrichlorosilane, etc., and methyltribromosilane, ethyltribromosilane, propyltribromosilane, butyltribromosilane, pentyltribromosilane, hexyltribromosilane, heptyltribromosilane, octyltribromo Silane, nonyltribromosilane, decyltribromosilane, dodecyltribromosilane, octadecyltribromo Run, and the like.

Examples of the trialkoxylated alkylsilane include methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane. Silane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane, etc., and methyltrimethoxysilane, ethyltrimethoxysilane,
Propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, etc. Is raised.

In addition, for example, vinyl silane coupling agents such as vinyltriethoxysilane, methacrylic silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, and amino silane coupling agents such as γ-aminopropyltrimethoxysilane Ring agent, amine silane coupling agent such as N-bis [(methyldimethoxysilyl) propyl] amine, amide silane coupling agent such as N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide, γ-glycid A glycidyl silane coupling agent such as xylpropyltrimethoxysilane or a mercapto silane coupling agent such as γ-mercaptopropyltrimethoxysilane may be used.

The amount of the silane coupling agent used for the fine particles is 0.001 to 1 part by weight of the fine spheres.
It is preferably 10 important parts, more preferably 0.005 to 1 part by weight.

The solvent is preferably a solvent which can dissolve the silane coupling agent and has no active hydrogen which reacts with the silane coupling agent. For example, aromatic solvents such as benzene, toluene and xylene and aliphatic solvents such as hexane, heptane, octane, nonane and decane are preferably used. However, as a silane coupling agent, a vinyl silane coupling agent, a methacrylic silane coupling agent, an amino silane coupling agent, an amine silane coupling agent, an amide silane coupling agent, a glycidyl silane coupling agent and When using a mercapto-based silane coupling agent, as a solvent, methanol, ethanol, alcohols such as isopropanol, acetone, ketones such as methyl ethyl ketone, methyl acetate, esters such as ethyl acetate, and dioxane, tetrahydrofuran,
A mixture of water and an organic solvent such as ethers such as methyl cellosolve is used. The mixing ratio of the organic solvent to water is preferably 0.05 to 1 part by weight of water, more preferably 0.05 to 0.5 part by weight of water, based on 1 part by weight of the organic solvent.

The amount of the solvent to be used with respect to the fine particles is preferably 1 to 100 parts by weight, more preferably 3 to 20 parts by weight, based on 1 part by weight of the fine particles.

The conditions of the above heat treatment are as follows: the heating temperature is usually 60 ° C. to 250 ° C., preferably 80 ° C. to 200 ° C., and the heating time is usually 30 minutes to 10 hours, preferably 1 hour.
~ 3 hours.

The silane coupling agent formed on the surface of the fine particles by the above operation reacts with moisture in the air and is hydrolyzed to form a silane oxide layer represented by the following formula [IV]. It is presumed.

[0049]

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(In the formula, n is an integer of 1 or more.) In the liquid crystal display device of the present invention, the fine particles coated on the surface with the polyimide obtained as described above are interposed in the interelectrode substrate, and the liquid crystal display device is prepared by a usual method. Can be created.

[0051]

[Action] coating layer composed of a polyimide intermediate member provided on the surface of the microparticles, after which the spacer is sprayed onto the substrate, causing the polyimide-forming reaction in the thermocompression bonding process, the film of polyimide. Therefore, in the liquid crystal display device, the coating layer of the spacer interposed between the electrode substrates is made of polyimide. As a result, the polyimide layer formed on the spacer surface promotes vertical alignment and eliminates abnormal alignment (ring ring corrosion) generated at the interface between the spacer and the liquid crystal. Further, when the polyimide intermediate is converted into a polyimide , the spacer is firmly adhered to the substrate to prevent the spacer from moving.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

(Preparation of Substrate) An SiO ₂ film is deposited on a pair of 300 mm square glass plates by a CVD method, and then a transparent conductive film ITO is formed on the substrate by a sputtering method. went.

The offset method is applied to both sides of this substrate.
Printing a polyimide intermediate LP-64 manufactured by Toray Co., Ltd.
It was baked at 280 ° C. for 2 hours to form a polyimide alignment film. Then, the twist angle of the liquid crystal is set to 240 °
Rubbing was performed in such a direction that

Example 1 A polyimide intermediate having a solid content of 8% and a viscosity of 185 cps (Sun Ever 100 (081 manufactured by Nissan Chemical Industries, Ltd.)
4)) 5 g was dissolved in 100 ml of a mixed solvent of N-methylpyrrolidone / butyrocellosolve (1: 1). After adding 10 g of divinylbenzene-styrene copolymer fine particles having a particle size of 6.00 μm to the obtained solution and mixing them well, the solvent was evaporated by stirring under reduced pressure (0.1 mmHg, 65 ° C.). . The resulting dried product was completely loosened using a mortar.

The average particle diameter of the thus obtained spacer was 6.20 μm as measured by a Coal Counter ZB / C-1000 type particle diameter measuring apparatus. From this result, it is calculated that the thickness of the coating layer composed of the polyimide intermediate is 0.1 μm.

Place the spacer on the substrate by 1 mm
After spraying at a density of 120 pieces per ² pieces, seal printing was performed around the substrate using Mitsui Toatsu Stract Bond, which is a one-part epoxy resin, as a sealant.

The above substrates were bonded together, and then the epoxy resin was cured by heating and pressing at 180 ° C. for 1 hour. At this point, the coating layer consisting of the polyimide intermediate was polyimided, resulting in a polyimide-coated spacer, which was simultaneously adhered to the substrate. Thereafter, a liquid crystal was injected into the empty cell by a conventional method to form an STN liquid crystal cell.

In this liquid crystal cell, no brilliance (corona phenomenon) of the circumference of the spacer due to abnormal liquid crystal alignment generated at the interface between the spacer and the liquid crystal was observed, and vertical alignment of the liquid crystal occurred at the interface between the liquid crystal and the spacer. It was confirmed that. In addition, it was confirmed that spacer movement was unlikely to occur as follows. With the liquid crystal cell vertical, frequency 3
When the position of the spacer before and after the vibration was applied for 100 hours at 0 Hz and amplitude of 3 mm was measured with an optical microscope, it was confirmed that there was no change in the position of the spacer.

Comparative Example 1 A liquid crystal cell was prepared in the same manner as in Example 1 except that the coating layer comprising the polyimide intermediate was not formed.

In this liquid crystal cell, a corona phenomenon based on the abnormal orientation of the liquid crystal was observed.

Example 2 Instead of the fine particles used in Example 1, the particle size was 8.05 μm.
A spacer was obtained in the same manner as in Example 1, except that 10 g of melamine resin-based fine particles (Univex WA, manufactured by Unitika Ltd.) were used.

The average particle size of the spacer thus obtained was 8.35 μm. From this result, it is calculated that the thickness of the coating layer composed of the polyimide intermediate is 0.15 m.

A liquid crystal cell was prepared in the same manner as in Example 1 using the above spacer. However, the spray density of the spacers was 90 per 1 mm ² , the heating temperature during the polyimide conversion was 160 ° C., and the heating time was 1 hour. In this liquid crystal cell, no corona phenomenon was observed at all, and it was confirmed that the liquid crystal was vertically aligned at the interface between the liquid crystal and the spacer.

Comparative Example 2 A liquid crystal cell was prepared in the same manner as in Example 2 except that the coating layer comprising the polyimide intermediate was not formed.

In this liquid crystal cell, a corona phenomenon based on abnormal liquid crystal orientation was observed.

Example 3 A polyimide intermediate having a solid content of 2.5% and a viscosity of 10 cps (Optomer AL-1251 manufactured by Nippon Synthetic Rubber Co., Ltd.)
10 g was dissolved in 100 ml of a mixed solvent of N-methylpyrrolidone / ethyl carbitol (1: 1). To the obtained solution, 10 g of silica fine particles (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., Seahorster KE-P100) having a particle size of 1.15 μm were added and mixed well, and then heated under reduced pressure (0.1 mmHg,
(70 ° C.) to evaporate the solvent. The resulting dried product was completely loosened using a mortar. The average particle size of the spacer thus obtained is 1.35 μm.
m. From this result, it is calculated that the thickness of the coating layer composed of the polyimide intermediate is 0.1 μm.

Using the above spacer, a liquid crystal cell was prepared in the same manner as in Example 1. However, the spray density of the spacers was 50 per 1 mm ² , the heating temperature during the polyimide conversion was 170 ° C., and the heating time was 1 hour. In this liquid crystal cell, no corona phenomenon was observed at all, and it was confirmed that the liquid crystal was vertically aligned at the interface between the liquid crystal and the spacer.

Comparative Example 3 A liquid crystal cell was prepared in the same manner as in Example 3 except that the coating with the polyimide intermediate was not performed.

In this liquid crystal cell, a corona phenomenon based on abnormal liquid crystal orientation was observed.

Example 4 Tetrabutoxytitanium (Nippon Soda Co., Ltd., B-1)
0.35 g was dissolved in 50 ml of n-hexane. After 10 g of the fine particles used in Example 1 were added to the obtained solution and mixed well, the solvent was evaporated. Thereafter, heat treatment was performed at 80 ° C. for 1 hour. The resulting dried product was completely loosened using a mortar.

A spacer was obtained in the same manner as in Example 1 except that fine particles having a titanium oxide layer thus formed on the surface were used, and a liquid crystal cell was prepared using the spacer. In this liquid crystal cell, no corona phenomenon was observed,
It was confirmed that the liquid crystal was vertically aligned at the interface between the liquid crystal and the spacer.

Example 5 Ethyltrichlorosilane (Toshiba Silicone Co., Ltd., T
SL8226) was dissolved in 50 ml of toluene. 10 g of the fine particles used in Example 2 were added to the obtained solution, and heat treatment was performed at 55 ° C. for 1 hour. This was filtered to obtain fine particles, and the fine particles were further heated at 120 ° C. for 1 hour. The obtained fine particles were completely loosened using a mortar.

A spacer was obtained in the same manner as in Example 2 except that fine particles having a silane oxide layer obtained on the surface thereof were used, and a liquid crystal cell was prepared using the spacer. In this liquid crystal cell, no corona phenomenon was observed,
It was confirmed that the liquid crystal was vertically aligned at the interface between the liquid crystal and the spacer.

Example 6 A solution was prepared by dissolving 0.1 g of γ-aminopropyltrimethoxysilane (A-1100, manufactured by Nippon Unicar Co., Ltd.) in a mixed solution of water / ethanol (1: 9). 10 g of the fine particles used in Example 3 were added to the obtained solution,
The mixture was stirred at room temperature for 3 hours. This is filtered to obtain fine particles,
The fine particles were further heat-treated at 150 ° C. for 2 hours. The obtained fine particles were completely loosened using a mortar.

A spacer was obtained in the same manner as in Example 3 except that fine particles having a silane oxide layer obtained on the surface thereof were used, and a liquid crystal cell was prepared using the spacer. In this liquid crystal cell, no corona phenomenon was observed,
It was confirmed that the liquid crystal was vertically aligned at the interface between the liquid crystal and the spacer.

[0077]

As is apparent from the above description, according to the present invention, it is possible to prevent abnormal alignment of liquid crystal molecules at the interface between the liquid crystal and the spacer and to prevent the movement of the spacer. A spacer is obtained. The spacer can prevent the display quality of the liquid crystal display device from deteriorating.

Claims (3)

(57) [Claims] 1. A spacer for a liquid crystal display element, wherein a coating layer comprising a polyimide intermediate is formed on the surface of fine particles. 2. A space for a liquid crystal display element according to claim 1.
A liquid crystal display device obtained by using a
A spacer on which a coating layer made of polyimide obtained by polyimide of a polyimide intermediate is formed is interposed between the electrode substrates, and the coating layer is adhered to the electrode substrate. Liquid crystal display device. 3. A process according to claim 1 spacer by heating under pressure a in a state in which is interposed between the electrode substrates polyimide intermediates described
A method for producing a liquid crystal display element, which comprises a step of converting the compound into a polyimide, and a step of injecting a liquid crystal between the electrode substrates.