JPH0713137A - Inorganic hollow fine particle containing liquid crystal and liquid crystal display device using that - Google Patents

Abstract

PURPOSE:To provide inorg. hollow fine particles containing a liquid crystal at practical uses of a liquid crystal material in a drop state so that formation or handling of drops is made easy, and to provide a liquid crystal display device using these particles. CONSTITUTION:The inorg. hollow fine particle 1 contains a nematic liquid crystal or mixture of nematic liquid crystal and cholesteric liquid crystal, or cholesteric liquid crystal in the hollow part 3. A dichroic dye stuff may be dissolved in the liquid crystal. The liquid crystal display device consists of a polymer material 10 with dispersion of inorg. hollow fine particles 1 containing a liquid crystal, two supporting substrates 8, 9 having electrodes 6, 7, respectively. The polymer material 10 is a hydrophilic material, or the polymer material 10 consists of a photosetting resin or thermosetting resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to liquid crystal-containing inorganic fine particles which facilitate the formation and handling of liquid droplets in a field of use in which a liquid crystal material is used in the form of small droplets, and a liquid crystal display device using the same. .

[0002]

2. Description of the Related Art In recent years, there has been a remarkable progress in the utilization technology of liquid crystals, which has been used in various applications and put into practical use. Of these, the present invention relates to a technique of using a liquid crystal in the form of small droplets, and a conventional technique will be described below by using an example of a liquid crystal display device and a liquid crystal temperature sensor. First, as an example of the liquid crystal display device, there is a polymer dispersion type liquid crystal display device. It disperses liquid crystal droplets in a polymer matrix,
The refractive index of the liquid crystal is changed depending on the presence or absence of an electric field to control scattering and transmission, thereby obtaining an image display. FIG. 2 is a schematic cross-sectional view showing the structure of such a conventional polymer dispersed liquid crystal display device. In the example shown in the figure, two supporting substrates 21 and 21 having transparent electrodes 20 and 20 on the surface thereof are used as liquid crystal droplets (hereinafter referred to as droplets) 22.
The base material 23 made of a polymer material in which is dispersed is sandwiched. Then, the refractive index of the droplet 22 changes depending on the presence / absence of a voltage between the upper and lower transparent electrodes 20, 20.
When the refractive index of 2 ... And the refractive index of the base material 23 match, each display mode of transmission is obtained, and when they do not match, each display mode of scattering is obtained. An image can be displayed by arranging a large number of such structures vertically and horizontally as a unit pixel and individually controlling the voltage applied to each pixel.

A second example is a liquid crystal temperature sensor. This utilizes the fact that visible light of the same wavelength component as the helical pitch of cholesteric liquid crystal is reflected, and that the temperature change can be recognized as a color change of the reflected light as the helical pitch changes with temperature. Is. Then, in order to form the temperature sensitive portion into various shapes, it may be dispersed as droplets in the base material of the polymer substance.

[0004]

Dispersion of droplets into the polymer substrate can be realized mainly by the following two methods, each of which has its own problems. An example of a display device will be described. First, a liquid crystal material is emulsified in a water-soluble polymer solution serving as a base material, then applied on the electrode side of one of the supporting substrates, and dried while being sandwiched by the other supporting substrate. This method has the advantage that a wide range of liquid crystal materials can be used. In the second method, a mixture of an isotropic monomer serving as a base material and a liquid crystal material is sandwiched between two supporting substrates and polymerized by irradiation with ultraviolet rays or heating. At this time, the polymer and the liquid crystal are separated while forming droplets, and as a result, the droplets are dispersed in the substrate. This method has hitherto been widely used as a polymer dispersed liquid crystal.

In forming such droplets, an organic material is often used as a base material, and since the liquid crystal material is an organic substance, the base material may react with the liquid crystal. Therefore, there is a problem that the liquid crystal materials that can be used are naturally limited. Further, it is preferable that the size of the liquid droplets be the same as much as possible, but it is difficult to obtain liquid droplets having a uniform diameter because it greatly varies depending on the curing conditions of the base material, and it is also possible to control the production conditions. There are considerable difficulties.

[0006]

The present invention has been completed for the purpose of solving the above-mentioned problems, and in the field of use in which a liquid crystal material is used in the form of droplets, it is easy to form and handle the droplets. The present invention provides a liquid crystal-encapsulated inorganic hollow fine particle and a liquid crystal display device using the same. The gist of the present invention, which has solved the above-mentioned problems, is that, as the inorganic hollow fine particles containing liquid crystal, fine particles having a hollow interior made of an inorganic material are characterized in that the liquid crystal is included in the hollow portion, and the liquid crystal is a nematic liquid crystal. The liquid crystal is a mixture of nematic liquid crystal and cholesteric liquid crystal, the liquid crystal is cholesteric liquid crystal, a dye is dissolved in the liquid crystal, and the dye is a dichroic dye. Each of these can be adopted. Further, as a liquid crystal display device using such liquid crystal-encapsulated inorganic fine particles, a polymer substance in which the aforementioned liquid crystal-encapsulated inorganic hollow fine particles are dispersed is sandwiched between two supporting substrates provided with electrodes on the surface. Since it is considered that the polymer substance is a hydrophilic substance, the polymer substance is a photocurable resin, and the polymer substance is a thermosetting resin. is there.

In the present invention, as the inorganic hollow fine particles, those having excellent heat resistance, water resistance and corrosion resistance are desirable, and alkaline earth metal carbonates, silicates, phosphates, sulfates, metal oxides and metals are preferred. Hydroxides, other metal silicates, other metal carbonates, etc. can be used.
Specifically, the carbonates of alkaline earth metals include calcium carbonate, barium carbonate, and magnesium carbonate, and the silicates of alkaline earth metals include calcium silicate, barium silicate, magnesium silicate, and the like. Examples of the phosphates include calcium phosphate, barium phosphate, magnesium phosphate, and the like, and alkaline earth metal sulfates include calcium sulfate, barium sulfate, magnesium sulfate, and the like.

Further, as metal oxides, silica (silicic anhydride), titanium oxide, iron oxide, cobalt oxide, zinc oxide,
Nickel oxide, manganese oxide, aluminum oxide, etc.
Examples of the metal hydroxide include iron hydroxide, nickel hydroxide, aluminum hydroxide, calcium hydroxide, chromium hydroxide and the like. Other metal silicates include zinc silicate, aluminum silicate, magnesium silicate and the like, and other metal carbonates include zinc carbonate, aluminum carbonate, copper carbonate, magnesium carbonate and the like.

The inorganic hollow fine particles can be produced by the interfacial reaction method already disclosed by the present applicant, and the outline thereof will be described below. First, an inorganic compound (A) selected from alkali metal silicates, carbonates, phosphates, nitrates and halides of alkaline earth metals or other metals.
An aqueous solution containing at least one of the above is prepared. Then, an organic solvent is added to and mixed with this to obtain an oil-in-water type (hereinafter referred to as O / W type) emulsion (B), and the emulsion (B) is added to an organic solvent containing a lipophilic surfactant. An oil-in-water-in-oil type (hereinafter referred to as O / W / O type) emulsion (C) is added and mixed. Finally, an aqueous solution reaction with at least one of an alkaline earth metal halide, an inorganic acid, an organic acid, an ammonium salt of an inorganic acid, an ammonium salt of an organic acid, and carbonic acid or a nitrate of an alkali metal, and the above inorganic compound (A). Inorganic hollow fine particles are obtained by mixing the emulsion (C) with an aqueous solution of a compound (D) capable of forming a water-insoluble precipitate.

The above manufacturing method is described in Japanese Patent Publication No. 5-9133 by the present applicants, the details of which will be described below. First, an aqueous solution containing at least one kind of the above-mentioned inorganic compound (A), preferably its concentration is 0.5
The O / W emulsion (B) is prepared by adding and mixing an organic solvent to an aqueous solution having a mol / l or more, particularly preferably 3.0 mol / l to a saturated concentration. As the organic solvent in this case, any of those which have been generally used in the conventional method can be used, and the preferable one is that it is liquid at room temperature and has a solubility in water of 8% or less and is substantially free from the reaction. What you don't do is better. Specific examples of these include n-
Aliphatic hydrocarbons such as hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, gasoline, petroleum ether, kerosene, benzine, mineral spirits, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclohexene, cyclononane , Benzene, toluene, xylene, ethylbenzene, propylbenzene, cumene, mesitylene, tetralin, aromatic hydrocarbons such as styrene, ethers such as propyl ether, isopropyl ether, methylene chloride, chloroform, ethylene chloride, trichloroethane, trichloroethylene, etc. Halogenated hydrocarbons, acetates, acetic acid-
n-propyl, isopropyl acetate, -n-butyl acetate,
Isobutyl acetate, -n-amyl acetate, isoamyl acetate,
Examples thereof include esters such as butyl lactate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl butyrate. These organic solvents may be used alone or in combination of two or more.

A surfactant is usually used in the preparation of the O / W type emulsion (B), and the O / W ratio in this case is particularly limited as long as the obtained emulsion is an oil-in-water type. However, it is preferable that O: W = 1: 10 to 3: 1. And the amount of surfactant used is 10 of organic solvent.
The amount is preferably about 10% by weight or less, and more preferably about 0.01 to 3% by weight.

As this surfactant, any of those which have been generally used can be used. Specific examples of these include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,
Sorbitan fatty acid ester compounds such as sorbitan tristearate, sorbitan monooleate, sorbitan sexooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxy Ethylene sorbitan tristearate,
Polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan stearate and other polyoxyethylene sorbitan fatty acid ester type, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, Polyoxyethylene higher alcohol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene glycol monolaurate, polyoxyethylene glycol monostearate, polyoxyethylene glycol stearate, polyoxyethylene glycol Polyoxyethylene fatty acid ester-based products such as monooleate, stearic acid monoglyceride Ride, as glycerin fatty acid esters such as monoglyceride oleate, those polyoxyethylene Na sorbitol fatty acid esters such as polyoxyethylene sorbit tetraoleate and the like. And these surfactants can also be used 1 type or in mixture of 2 or more types.

Next, the O / W emulsion (B) thus prepared is added to an organic solvent containing a lipophilic surfactant and mixed to prepare an O / W / O emulsion (C). To do. At this time, the organic solvent and the surfactant are appropriately selected from those in the same range as described above. Here, the O / W / O ratio of the emulsion is O: W: O = 1: 1 to 10: 1.
About 50 is preferable.

In the present invention, the O / W / O type emulsion (C) is mixed with an aqueous solution of the compound (D) capable of forming a water-insoluble precipitate by the reaction with the inorganic compound (A). Form a wall material of inorganic hollow particles. This reaction proceeds well at room temperature and atmospheric pressure, but the reaction can be promoted under heating. The concentration of the compound (D) in the aqueous solution is preferably 0.05 mol / l to a saturated concentration, and particularly preferably about 0.1 to 2 mol / l.

For example, in the case of silica (silicic anhydride),
Specifically, the manufacturing conditions are as follows. First, 100 ml of a 2% ethyl acetate solution of polyoxyethylene (n = 10) lauryl ether was added to 500 ml of water glass No. 1 (4 mol / l as SiO ₂ ) and stirred at high speed to prepare an O / W type emulsion. . Then, the mixture is added to 2000 ml of a 3% ethyl acetate solution of polyoxyethylene lauryl ether, and stirred at high speed to prepare an O / W / O type emulsion. The O / W / O emulsion thus obtained was added with 3000 ml of 1 mol / l ammonium sulfate and stirred to react,
After leaving it for about 2 hours and filtering and separating, desired inorganic fine particles are obtained. The inorganic fine particles thus obtained have a diameter of 2 on the wall surface.
It is a porous spherical fine particle having 0 to 300Å fine pores, and finally, the inorganic porous hollow silica fine particle is obtained by evaporating ethyl acetate in the particle.
According to the above conditions, when the particle diameter is 1 to 10 μm, the wall thickness is about 8% of the particle diameter, and the refractive index in the visible light region is about 1.5. Next, the liquid crystal is included in the hollow portion.

At this time, it is also effective to inactivate the surface of the particles, and specific examples thereof include thermosetting silicone oils such as dimethylpolysiloxane and methylhydrogenborosiloxane, silicone emulsions and silicone resins. Silicone resins, silane coupling agents such as methyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, and trimethylcololosilane; cyclic silicones such as dihydrogenhexamethylcyclotetrasiloxane and trihydrogenpentamethylcyclotetrasiloxane Compounds, isopropyl tristearoyl titanate and isopropyl tri (N-
Titanate coupling agents such as aminoethyl-) titanate, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, fluorine silicone coating agents, fluorine coating agents and the like can be exemplified as preferable ones, and some of them The combination of is also possible.

Then, the liquid crystal is impregnated through the fine pores of the porous wall surface so that the liquid crystal is contained in the hollow portion. For this purpose, the inside of the hollow portion is depressurized under reduced pressure, and the liquid crystal in the pressurized state is brought into contact with the particles, so that the liquid crystal can be impregnated through the micropores on the wall surface by utilizing the pressure difference between the inside and outside of the hollow portion. The pressure difference P at this time is given by the following equation. P = (− 4γ cos θ) / d In the above equation, γ is the surface tension of the liquid crystal, θ is the contact angle with the wall surface of the liquid crystal, and d is the diameter of the micropore.

As the liquid crystal introduced into the hollow portion in this manner, nematic liquid crystal, colletic liquid crystal, and a mixture of nematic liquid crystal and colletic liquid crystal are particularly effective in the present invention, but smectic liquid crystal and It is also possible to include a discotic liquid crystal.
Liquid crystal materials, that is, liquids exhibiting optical anisotropy, have been confirmed to be of many types, but among them, in the case of nematic liquid crystals, especially Schiff-based, azoxy-based, cyanobiphenyl-based, cyanophenylcyclohexane-based, Bicyclic compounds such as cyanophenyl ester-based, benzoic acid phenyl ester-based, cyclohexanecarboxylic acid phenyl ester-based, phenylpyrimidine-based, and phenyldioxane-based, and high-temperature liquid crystals having 3 to 4 benzene rings and cyclohexane rings It is also effective to mix a liquid crystal material known as a viscosity reducing agent in order to facilitate penetration into the hollow portion. Such a nematic liquid crystal is particularly effective for a display device.

Next, as the cholesteric liquid crystal, a mixture of cholesterin chloride (E) and cholesterin nonanoate (F) and cholesterin oleate are most representative. In particular, various hue changes can be obtained depending on the combination of the mixing ratio of (E) and (F) and the adsorption solvent, and it is also effective to use together with such an adsorption solvent as needed. Specifically, when (E) is 15% and (F) is 80%, the initial hue is red, and acetone, benzene, or chloroform is selected as the solvent. Next, when (E) is 20% and (F) is 80%, the initial hue is green, blue when benzene or petroleum ether is used as a solvent, red when chloroform or methylene chloride, In the case of trichlorethylene, there is no change and the hue remains green. Furthermore, when (E) is 25% and (F) is 75%, the initial hue is yellow or red, when benzene or trichlorethylene is used as a solvent, a deep red color is obtained, and when chloroform or methylene chloride is used, a red color is obtained. , And, in the case of petroleum ether, a blue color. When (E) is 80% and (F) is 20%, the initial hue is red, and when chloroform or methylene chloride is used as the solvent, deep red is displayed, and in the case of petroleum ether, blue is displayed. It is a thing. On the other hand, in the case of cholesterin oleate, a blue color is produced by using trichlorethylene, methylene chloride and petroleum ether. Such a cholesteric liquid crystal is particularly suitable for use as a liquid crystal temperature sensor because visible light having the same wavelength component as the helical pitch of liquid crystal molecules is reflected and the helical pitch changes with temperature.

For a display device, a chiral nematic liquid crystal obtained by mixing a small amount of cholesteric liquid crystal with the above nematic liquid crystal is also useful.

Further, for a display device, a color display due to the guest-host effect can be obtained by dissolving a dye in the above liquid crystal material. The dye in this case refers to a dichroic dye, which has a large dichroic ratio (8 or more), has good solubility characteristics with respect to liquid crystal, and has high purity and does not affect the electric resistance value of liquid crystal. Basic characteristics such as that are required. Examples of such dye materials include merocyanine-based, styryl-based, azomethine-based, azo-based, benzoquinone-based, naphthoquinone-based, anthraquinone-based, and tetrazine-based materials.

Then, inorganic hollow fine particles in which the desired liquid crystal material is contained in the hollow portion are dispersed in a polymer substance,
A liquid crystal display device can be realized by sandwiching this between two support substrates provided with transparent electrodes on the surface. At this time, an area sandwiched by the upper and lower two electrodes is set as a unit pixel, and an image can be displayed by the aggregate of the unit pixels. At this time, for example, barium borosilicate glass having a low alkali metal content is used as the supporting substrate, and indium tin oxide (hereinafter referred to as IT) is used as the transparent electrode material.
Generally referred to as O). Among the polymer substances in which the liquid crystal-encapsulated inorganic hollow fine particles are dispersed, hydrophilic substances include polyvinyl alcohol type, maleic anhydride copolymer, acrylic type and the like. Further, as the photo-curable resin, a photo-crosslinking type photosensitive resin in which α, β unsaturated carbonyl groups such as cinnamic acid are introduced into a polymer, such as polyvinyl cinnamic acid, an unsaturated polymer or a vinyl monomer is used. It is possible to widely use a photopolymerization type photosensitive resin that utilizes polymerization by light, and a mixture of polyester, epoxy, urethane resin containing acrylate as an unsaturated group and polyfunctional acrylic as a crosslinking agent.
Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furan resin, alkyd resin, unsaturated polyester, diallyl phthalate resin, epoxy resin, silicon resin and polyurethane.

[0023]

According to the above-mentioned means, the problems in the prior art can be solved by the following operations. First, by enclosing the liquid crystal in the hollow portion of the inorganic fine particles, the size of the liquid droplets is determined by the size of the fine particles. Further, since the liquid crystal and the inorganic substance come into contact with each other, no reaction occurs between the liquid crystal and the fine particles. When the nematic liquid crystal is included, it is suitable for a display device, and when the cholesteric liquid crystal is included, it is suitable for a temperature sensor. Further, since the liquid crystal and the base material made of the polymer substance are separated by the inorganic substance that constitutes the fine particles, there is no reaction between the liquid crystal and the polymer substance. The polymer substance may be selected from a wide range of materials from hydrophilic substances to photocurable substances and thermosetting substances.

Further, by dissolving a dye in the liquid crystal contained therein, the same color display as the conventional one can be realized.

[0025]

EXAMPLE FIG. 1 is a schematic illustration of an example of the present invention. As (a), a cross-sectional view of inorganic porous hollow spherical fine particles containing a liquid crystal is shown as (b) in (a). FIG. 3 is a cross-sectional view of a unit pixel portion of a liquid crystal display device using the inorganic porous hollow spherical fine particles enclosing the liquid crystal. As shown in (a), the present fine particles 1 have a hollow spherical shape having a porous wall surface 2, and a nematic liquid crystal material 4 is included in the hollow portion 3. The outer diameter of the fine particles 1 is 1 to 100 μm, and the thickness of the wall surface 2 is 2 of the particle diameter.
At about 45%, the maximum porosity is about 94%. Innumerable small holes 5 exist on the wall surface 2, and the liquid crystal material 4 is introduced through the small holes 5. The diameter of these small holes 5 ...
It is distributed in the range of 1000Å, and is distributed on average between 20 and 60Å. Further, the liquid crystal material 4 itself has a certain level of surface tension, and the liquid crystal once encapsulated does not exude outside under normal pressure.

Then, as shown in (b), I
Corning 7059 glass 8 and 9 provided with TO electrodes 6 and 7 are used as a supporting substrate, and a polymer substance 10 in which the above-mentioned liquid crystal-encapsulated fine particles 1 are dispersed is sandwiched between two supporting substrates. A device equivalent to a molecular dispersion type liquid crystal display device can be realized. This is because the present fine particles 1 correspond to conventional droplets, and many effects can be obtained as described later. At this time, the size of the droplets, that is, the size of the fine particles 1 containing the liquid crystal is between 1 μm and 100 μm, preferably 10 μm.
μm or less is preferable. The volume ratio of the fine particles 1 is preferably about 60 to 90%. Further, the liquid crystal material used for such display has a refractive index of 1.5 to 5 when a voltage is applied.
It is generally about 1.7, and it is important to match the refractive index of the polymer substance 10. For example, when the polymer material 10 having a refractive index of about 1.5 to 1.7 is used, the refractive index does not match the liquid crystal 4 when a voltage is not applied, and a scattering mode occurs. Since the refractive indexes of the fine particles 1, 7059 glass 8 and 9 are also in this range, the transmission mode is obtained as a result of matching all the refractive indexes. On the contrary, by combining with the liquid crystal material 4, it is possible to set the scattering mode when a voltage is applied.

The gap between the supporting bases is set to several μm to several hundreds μm, and it is optimum depending on the balance between the contrast of the obtained image and the magnitude of the applied voltage capable of controlling both scattering and transmission modes. You can decide the value. That is, if the gap between the supporting bases is reduced, the required applied voltage is reduced, but the contrast is lowered. Conversely, if the gap is increased, a high applied voltage is required but the contrast is improved. Then, by using the fine particles 1 whose particle size is made uniform by classification, the design of these display devices becomes extremely easy and highly accurate.

This liquid crystal display panel can be driven by an active matrix method using thin film transistors and diodes as in the conventional case, and is particularly useful as a projection type full color liquid crystal display device by combining a color filter and a projection optical system. high. Further, by using fine particles containing a liquid crystal material in which a dichroic dye is dissolved, a guest-host type reflective color liquid crystal display device can be constructed. Furthermore, it is possible to use cholesteric liquid crystal as a liquid crystal temperature sensor.

[0029]

The following effects can be obtained by the above operation. First, by enclosing a liquid crystal in the hollow part of the inorganic fine particles, the size of the liquid droplets is determined by the size of the fine particles, so that the epoch-making effect that the size of the liquid droplets can be made uniform is achieved. Obtainable. When a nematic liquid crystal or a mixture of a nematic liquid crystal and a cholesteric liquid crystal is included, it is suitable for a display device, and when a cholesteric liquid crystal is included, it is suitable for a temperature sensor. Therefore, it can be provided as a fine particle material which can be applied to various uses depending on the type of the liquid crystal material contained therein. Further, the fact that the size of the liquid droplets can be made uniform is particularly effective when a liquid crystal display device is constructed, and the display device can be designed very easily and highly accurately. Further, since the liquid crystal and the inorganic substance come into contact with each other, a reaction between the liquid crystal and the fine particles does not occur, and a wider range of liquid crystal materials can be used. In particular, a wide range of materials can be used as a coloring solvent for cholesteric liquid crystals.

Further, in the display device, since the liquid crystal and the base material made of the polymer substance are separated by the inorganic substance forming the fine particles, there is no reaction between the liquid crystal and the polymer substance. The degree of freedom in selecting materials for liquid crystals and polymer materials is higher than in the past.

Further, by dissolving a dichroic dye in the liquid crystal contained therein, the same color display as in the conventional case can be realized, but since the liquid crystal comes into contact with the inorganic substance as described above, in selecting the dye. Would only need to consider the compatibility with the liquid crystal.

As described above, the liquid crystal-encapsulating inorganic hollow fine particles of the present invention have many excellent features as means for obtaining droplets having a uniform diameter, and are extremely extensively used in liquid crystal display devices, liquid crystal temperature sensors, and the like. It has a range.

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing an embodiment of the present invention,
(A) is a cross-sectional explanatory view of the inorganic porous spherical fine particles enclosing the liquid crystal, and (B) is a cross-sectional explanatory view of a unit pixel portion of the liquid crystal display device using the inorganic porous spherical fine particles enclosing the liquid crystal shown in (A).

FIG. 2 is an explanatory cross-sectional view of a unit pixel portion of a liquid crystal display device according to the related art.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fine particles 2 Wall surface 3 Hollow part 4 Liquid crystal material 5 Small hole 6,7 Electrode 8,9 7059 Glass 10 Polymer substance 20 Electrode 21 Supporting substrate 22 Droplet 23 Substrate

Claims (10)

[Claims] 1. A liquid crystal-encapsulating inorganic hollow fine particle, characterized in that a hollow internal fine particle made of an inorganic material has a liquid crystal encapsulated in the hollow portion. 2. The liquid crystal-encapsulating inorganic hollow fine particles according to claim 1, wherein the liquid crystal is a nematic liquid crystal. 3. The liquid crystal-encapsulated inorganic hollow fine particles according to claim 1, wherein the liquid crystal is a mixture of nematic liquid crystal and cholesteric liquid crystal. 4. The liquid crystal-encapsulating inorganic hollow fine particles according to claim 1, wherein the liquid crystal is a cholesteric liquid crystal. 5. The liquid crystal-encapsulated inorganic hollow fine particles according to claim 1, wherein a dye is dissolved in the liquid crystal. 6. The inorganic hollow particles containing liquid crystal according to claim 5, wherein the dye is a dichroic dye. 7. A polymer substance in which the liquid crystal-encapsulating inorganic hollow particles according to claim 1 are dispersed, and the polymer substance is sandwiched between two supporting substrates provided with electrodes on the surface. Liquid crystal display device. 8. The liquid crystal display device according to claim 7, wherein the polymer substance is a hydrophilic substance. 9. The liquid crystal display device according to claim 7, wherein the polymer substance is a photocurable resin. 10. The liquid crystal display device according to claim 7, wherein the polymer substance is a thermosetting resin.