JPH10279625A - Colored microparticle, its production, spacer for liquid crystal display and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide colored microparticles being exactly spherical, being uniform in particle diameter and having excellent hue stability, heat resistance and solvent resistance, a process for producing the same, a spacer for a liquid crystal display and a liquid crystal display element. SOLUTION: This invention provides colored microparticles comprising a copolymer which comprises at least one silyl-containing colorant, at least one silyl-containing vinyl monomer and at least one vinyl monomer copolymerizable with the above vinyl monomer and in which the silyl group derived from the colorant and the silyl group derived from the vinyl monomer are crosslinked with each other, a spacer for a liquid crystal display element comprising the colored microparticles and a liquid crystal display element containing the spacer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored fine particles which are suitably used as a colorant in the fields of paints, inks, toners, synthetic resins, cosmetics and the like, and which are preferably used as spacers for liquid crystal display elements. The present invention relates to a manufacturing method, a spacer for a liquid crystal display element, and a liquid crystal display element.

[0002]

2. Description of the Related Art Spherical polymer fine particles are used as raw materials for powder coatings,
Toners for electronic copying, fillers for paints and cosmetics showing good spreadability, fillers for processing such as adsorption processing and ion exchange processing with high processing efficiency, or the contents of fillers, and opal-like plastic molded articles It is currently in the limelight as being useful as a filler for imparting gloss and as being useful as a spacer for liquid crystal display elements.

Conventionally, such spherical polymer fine particles have been
It is known that a monomer can be dissolved but a copolymer based on the monomer can be obtained by a dispersion polymerization method in which the monomer is polymerized in a solvent in which the monomer is not dissolved. In particular, it is described that a dispersion having a uniform particle size can be obtained by a dispersion polymerization method using a polymer dissolved in the above-mentioned solvent together with a quaternary ammonium salt as a dispersion stabilizer (for example, polymer such as Y. Almog). Journal, 14th
Vol. 131, 1982).

[0004] Further, attempts have been made to obtain spherical polymer fine particles having a uniform particle size by subjecting styrene to dispersion polymerization in various solvents using a nonionic cellulose derivative as a dispersion stabilizer (see, for example, Japanese Patent Application Laid-Open Publication No. H11-163873). CK Oper et al., Journal of Polymer Science, 23rd.
Vol. 103, 1985). As another method for producing spherical polymer fine particles, Japanese Patent Application Laid-Open No. 61-215602 discloses a method in which a polymer is used as a seed and a predetermined monomer is absorbed by the polymer fine particles. A seed polymerization method for polymerizing is disclosed.

[0005] However, the spherical polymer fine particles having a uniform particle size obtained as described above have poor heat resistance and solvent resistance when they do not have a cross-linked three-dimensional structure, and the range of use is extremely limited. . Therefore, when a divinyl compound such as divinylbenzene or diallyl phthalate is copolymerized to impart a crosslinked three-dimensional structure to the polymer fine particles, the sphericity and uniformity of the particle size of the polymer fine particles are reduced. There was a problem.

[0006] As a method for producing colored spherical polymer fine particles, Japanese Patent Application Laid-Open No. 1-138114 discloses silicon alkoxide, titanium oxide, carbon black, and the like.
There is disclosed a method of obtaining colored fine particles by dropping a liquid mixture with an organic or inorganic coloring material such as Red No. 2 into diluted ammonia water. In this method, when the silicon oxide fine particles are formed, coloring of the fine particles is caused by the organic or inorganic coloring material present in the surroundings in a dissolved or dispersed state being taken into the inside of the fine particles. Therefore, the coloring property of the fine particles in the fine particle forming step varies significantly depending on the characteristics of the individual materials such as the affinity between the organic or inorganic coloring material used and the silicon alkoxide.

In such a method, since it is difficult to control the coloring of the fine particles, poor coloring of the fine particles occurs due to a shortage of the coloring material, and when an excessive coloring material that cannot be incorporated into the fine particles occurs, There is a problem that a step of separating them is required. The fine particles obtained by the above method have a particle size of 10 μm or more. If such fine particles having a large particle diameter are used as a coloring material for paints, inks, toners, synthetic resins, cosmetics, and the like, the resulting product may have difficulty in color transparency and sharpness. Furthermore, in the fine particles obtained by the above-described method, the coloring material taken into the fine particles is merely held inside the fine particles by a physical action, and thus the formed fine particles have poor hue stability. In general, the hue stability of colored fine particles decreases significantly as the size of the fine particles formed becomes smaller. Normal,
The preferred size for the colorant is 10 μm or less,
Even if fine particles of such a size are formed by the above-described method, there is a problem that hue stability is poor.

[0008]

DISCLOSURE OF THE INVENTION In view of the above, the present invention provides colored fine particles having a perfect spherical shape, a uniform particle size, excellent hue stability, and excellent heat resistance and solvent resistance, and a process for producing the same. It is another object of the present invention to provide a liquid crystal display element spacer and a liquid crystal display element.

[0009]

According to the present invention, at least one kind of a dye having a silyl group, at least one kind of a vinyl monomer having a silyl group, and a copolymer with the above-mentioned vinyl monomer are provided. A copolymer comprising at least one of other possible vinyl monomers, wherein the copolymer is obtained by crosslinking a silyl group derived from the dye and a silyl group derived from the vinyl monomer. Colored fine particles. Hereinafter, the present invention will be described in detail.

The dye having a hydrolyzable silyl group used in the present invention has a structure represented by the following formula.

[0011]

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In the formula, R represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and X represents an alkoxyl group having 1 to 5 carbon atoms or Represents a halogen atom. n represents an integer of 1 to 3.

The structure of the coloring portion of the dye having a hydrolyzable silyl group used in the present invention has an ionic functional group capable of affecting the hydrolysis-condensation reaction with the vinyl monomer having a silyl group. For example, a sulfonyl group, etc.)
Is not particularly limited as long as the dye is soluble in an organic solvent, but from the viewpoints of abundance of hue and color stability, it is preferable to use an azo type or anthraquinone type.

Of these, at least one of a dye having an anthraquinone nucleus and having a hydrolyzable silyl group and a dye having an azo group and having a hydrolyzable silyl group is particularly preferable.

Specific examples of the dye having a hydrolyzable silyl group used in the present invention include the following formulas:

[0016]

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An azo dye represented by the following formula:

[0018]

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An azo dye represented by the following formula:

[0020]

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An anthraquinone dye represented by the following formula:

[0022]

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Anthraquinone dye represented by the following formula:

[0024]

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A dye represented by the following formula:

[0026]

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And the like. In the present invention, fine particles of various colors can be easily obtained by using two or more kinds of dyes having a hydrolyzable silyl group having different hues.

The amount of the dye having a hydrolyzable silyl group is 0.4 to 1 mol of all vinyl monomers.
It is preferably at most mol. If it exceeds 0.4 mol, it may be difficult to obtain a copolymer. More preferably, it is 0.2 mol or less. The lower limit of the addition amount is not particularly limited, and is appropriately selected depending on the coloring power of the pigment and the desired density of the fine particles.

The vinyl monomer having a hydrolyzable silyl group used in the present invention includes, for example, γ
-Methacryloxypropyltrimethoxysilane, N-β
-(N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.hydrochloride, vinyltriacetoxysilane, vinyltrimethoxysilane and the like.

The amount of the vinyl monomer having a hydrolyzable silyl group is 0.01 to 0.01% of all vinyl monomers.
~ 30 mol%, more preferably,
0.2 to 20 mol%.

The other vinyl monomer copolymerizable with the above-mentioned vinyl monomer used in the present invention is not particularly restricted but includes, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, -Ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-
Ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, Examples include vinyl monomers such as vinyl fluoride, vinylidene fluoride, ethylene, propylene, isoprene, chloroprene, and butadiene.

Further, vinyl monomers having a functional group such as a carboxyl group, a hydroxyl group, a methylol group, an amino group, an acid amide group and a glycidyl group can also be used. Among the vinyl monomers having such a functional group, those having a carboxyl group include, for example, acrylic acid,
Methacrylic acid, itaconic acid and the like, and those having a hydroxyl group include, for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β
-Hydroxypropyl acrylate, β-hydroxypropyl methacrylate, allyl alcohol and the like, and those having a methylol group include, for example, N
-Methylol acrylamide, N-methylol methacrylamide and the like, examples of those having an amino group include, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and those having an acid amide group include, for example, acrylamide ,
Examples of methacrylamide include those having a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether.

In the present invention, as the other vinyl monomer, a vinyl monomer having a hydrolyzable silyl group, for example, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltriacet Methoxysilane and the like can also be used.

The amount of the other vinyl monomer is preferably 0.01 to 15 mol%, more preferably 0.1 to 10 mol%, based on all vinyl monomers. .

In the production of the colored fine particles of the present invention, it is preferable to use a precipitation polymerization method or a seed polymerization method. Hereinafter, these polymerization methods will be described. (A) Precipitation polymerization method In the precipitation polymerization method, at least one of the above-mentioned dyes having a hydrolyzable silyl group and at least one of the above-mentioned vinyl monomers having a hydrolyzable silyl group are used.
Species, and at least one of the other vinyl monomers copolymerizable with the vinyl monomer, dissolves these constituents, but does not dissolve the copolymer based on these constituents Polymerize in a solvent. By such polymerization, the copolymer is precipitated in the solvent as fine spherical polymer particles having a uniform particle size.

The solvent is not particularly restricted but includes, for example, methanol, ethanol, isopropanol, n-
Lower alcohols such as butanol; mixed solvents of the above lower alcohols and water; and inorganic solvents such as n-hexane and n-heptane.

As the dispersion stabilizer used in the above precipitation polymerization method, a polymer soluble in the above-mentioned solvent is preferable, and examples thereof include polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl alkyl ether and the like.

If desired, a surfactant may be used in addition to the above polymer. The surfactant is not particularly limited and includes, for example, higher alcohol sulfate and its Na salt or amine salt, alkyl allyl sulfonate and its Na salt, alkyl naphthalene sulfonate,
Anionic ones such as alkyl phosphate, dialkyl sulfone succinate, rosin soap; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, sorbitan alkyl ester And nonionic ones such as polyoxyethylene sorbitan alkyl ester; and cationic ones such as trimethylaminoethylalkylamide halogenide, alkylpyridinium sulfate, and alkyltrimethylammonium halogenide.

The above-mentioned polymer is usually used in the above-mentioned solvent in an amount of 0.5 to 0.5.
About 5% by weight is dissolved, and the surfactant is usually dissolved in the above solvent in about 0.1 to 1% by weight. The polymer and the surfactant may be used alone, respectively, or 2
More than one type may be used in combination.

Examples of the polymerization initiator used in the above precipitation polymerization method include oil-soluble initiators such as lauroyl peroxide, benzoyl peroxide, cumene hydroxy peroxide and azobisisobutyronitrile. The polymerization initiator is usually added in an amount of about 0.1 to 2% by weight based on the total amount of the vinyl monomers.

In the above precipitation polymerization method, the above components are usually mixed in an amount of about 10 to 30% by weight based on the above solvent. The above components are dissolved in the above solvent, the above polymerization initiator is added, and the mixture is heated and stirred usually at about 50 to 80 ° C. in a reactor equipped with a stirrer, a condenser, a thermometer and the like to carry out polymerization. At this time, it is preferable to replace most of the air in the reactor with an inert gas such as a room gas or an argon gas in order to smoothly carry out the polymerization.

As the polymerization of the vinyl monomer progresses, the vinyl monomer becomes a polymer and precipitates in the solvent as fine spherical polymer particles. After the completion of the polymerization, the obtained spherical polymer fine particles are separated from the solvent by filtration, centrifugation or the like, and if desired, further washed, and then dried at room temperature or by heating. Although the particle diameter of the thus obtained spherical polymer fine particles is affected by the types of the above-mentioned components and the solvent, the particle diameter is in the range of about 1 to 10 μm and uniform.

(B) Seed Polymerization Method In the seed polymerization method, a seed polymer fine particle and a swelling agent of the seed polymer fine particle are dispersed in water to prepare a swelling aqueous dispersion of the seed polymer fine particle. At least one of the dyes having a hydrolyzable silyl group, at least one of the vinyl monomers having a hydrolyzable silyl group, and a copolymerizable with the vinyl monomer. A component mixture is prepared by mixing at least one of the other vinyl monomers, and the component mixture is added to the aqueous dispersion, and is absorbed by the swelling of the seed polymer fine particles and polymerized. I do. By such polymerization, the copolymer is collected as spherical polymer fine particles having a uniform particle size, similarly to the precipitation polymerization method.

In the above seed polymerization method, the seed polymer fine particles are preferably swellable in an organic solvent which is a swelling agent, for example, polystyrene, polymethacrylate,
Polyacrylate, polyvinyl chloride, polyvinyl acetate,
Examples thereof include polyacrylonitrile and styrene-butadiene copolymer. The particle size of the seed polymer fine particles is usually 1 μm or less, preferably 0.2 to 0.9 μm
It is about.

Examples of the swelling agent for the seed polymer fine particles include methanol, ethanol, n-butanol, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, toluene, xylene, n-hexane and n-hexane.
Heptane, n-octane, methylene chloride, 1,2
-Dichloroethane, 1,2,3-trichloroethylene,
Organic solvents such as 1-chlorododecane, dimethylformamide, tetrahydrofuran and the like can be mentioned. Among them, an organic solvent having a solubility in water of 0.02% by weight or less is preferable. These may be used alone or in combination of two or more.

In the polymerization, usually, the seed polymer fine particles are dispersed in water first, and then the swelling agent is dispersed in water, or the swelling agent is dispersed in water first, and then the seed is dispersed in water. Disperse the polymer particles,
An aqueous dispersion of the swelled seed polymer particles is prepared. In this case, a part of the swelling agent may be mixed with the seed polymer fine particles. In order to stably disperse the seed polymer fine particles and the swelling agent in water, usually, the same surfactant as described in the precipitation polymerization method,
And / or water-soluble polymers such as polyvinyl alcohol, carboxymethyl cellulose, sodium alginate, and sodium polyacrylate are added.

Separately, at least one kind of the dye having a hydrolyzable silyl group, at least one kind of the vinyl monomer having a hydrolyzable silyl group, and A component mixture is prepared by mixing at least one of other copolymerizable vinyl monomers, and then the component mixture is dispersed in the aqueous dispersion, and the component is dispersed in the swelled body. Is absorbed and polymerization is carried out. As the polymerization initiator used in the above polymerization, those similar to those described in the precipitation polymerization method and the like can be mentioned. The polymerization initiator is usually used as the swelling agent and / or
Alternatively, it is dissolved in the above component mixture. The polymerization is usually carried out at a temperature of about 60 to 80 ° C., preferably in an inert gas atmosphere.

The polymer fine particles thus obtained are collected by filtration, centrifugation, etc., and, if desired, further washed with water and dried to obtain spherical polymer fine particles having a uniform particle size. The particle diameter of the spherical polymer fine particles is influenced by the particle diameter of the seed polymer fine particles and the like.
It is uniform at 10 μm.

The colored fine particles of the present invention can be obtained by hydrolyzing the hydrolyzable silyl groups contained in the spherical fine polymer particles comprising the copolymer obtained by the above-mentioned polymerization method to form crosslinks. . The hydrolyzable silyl group becomes a silanol group by hydrolysis with an acid or alkali, and the silanol groups react with each other to form a silane crosslink. The acid is not particularly limited as long as it is an inorganic acid such as hydrochloric acid, sulfuric acid, and nitric acid; formic acid,
Organic acids such as oxalic acid and acetic acid are exemplified. The alkali is not particularly limited, for example, potassium hydroxide,
Examples include sodium hydroxide, ammonia, and amine.

To carry out the above-mentioned hydrolysis, the obtained spherical polymer fine particles are immersed in an aqueous solution of the above-mentioned acid or alkali. The concentration of the acid or alkali aqueous solution used at this time depends on the strength of the selected acid or alkali, but is usually 5%.
A low concentration of less than or equal to% by weight is sufficient. The hydrolysis is performed at room temperature, but may be heated to about 80 ° C. if desired. The time required for the hydrolysis is affected by the strength and concentration of the acid or alkali and the hydrolysis temperature, but is usually about 2 to 3 hours.

In the present invention, at least one of the above-mentioned dyes having a hydrolyzable silyl group, at least one of the above-mentioned vinyl monomers having a hydrolyzable silyl group, and By copolymerizing at least one of the other vinyl monomers copolymerizable with the monomer, the hydrolyzable silyl group is incorporated into the copolymer. Thereafter, the hydrolyzable silyl group becomes a silanol group by hydrolysis, and the silanol groups react with each other to form a silane crosslink. In the precipitation polymerization method, the hydrolyzable silyl group has a favorable effect on the sphericity and uniformity of the particle diameter of the colored fine particles. Also in the above seed polymerization method, the hydrolyzable silyl group has a favorable effect on the sphericity of the colored particles and the uniformity of the particle diameter.

In the colored fine particles of the present invention, the above-mentioned dye having a hydrolyzable silyl group is incorporated into polymer fine particles by polymerization, and then the silyl group is hydrolyzed to form cross-links. Since the dye is bonded and fixed to the dye, the hue stability is excellent.

The colored fine particles of the present invention have a perfect spherical shape, a uniform particle size, and are excellent in heat resistance, solvent resistance, etc. by being cross-linked, and are used as fillers for paints and cosmetics. It can be suitably used for applications such as fillers for plastics and fillers for plastics. Further, the colored fine particles of the present invention can be suitably used as a spacer for a liquid crystal display device, and such a spacer for a liquid crystal display device and a liquid crystal display device using the same are also included in the present invention.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 0.98 parts by weight of 1,8-bis (β-hydroxyethylamino) anthraquinone, γ-isocyanatopropyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.)
The reaction was carried out by heating and refluxing a mixture consisting of 1.85 parts by weight, 0.05 parts by weight of triethylamine and 50 parts by weight of methyl ethyl ketone for 6 hours. Then, the solvent and low-boiling substances were removed under reduced pressure to obtain a dye having a trimethoxysilyl group.

A reactor equipped with a stirrer, a cooler, a thermometer, and a gas inlet was charged with a solution prepared by dissolving 5 parts by weight of polyvinylpyrrolidone in 200 parts by weight of ethanol, and the trimethoxysilyl group obtained above was further added. Dye having 1.2
5 parts by weight, 6.25 parts by weight of γ-methacryloxypropyltrimethoxysilane and 37.5 parts by weight of styrene were mixed, and a solution in which 0.63 parts by weight of azobisisobutyronitrile was dissolved was added. While stirring at several 430 rpm, the mixture was heated to 75 ° C. and reacted for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, 11.2 parts by weight of 28% aqueous ammonia was added, and the mixture was stirred at room temperature for 3 hours to carry out hydrolysis and cross-linking reactions. The resulting colored fine particles were collected by centrifugation and washed with water. After that, it was dried by heating at 60 ° C. for 6 hours.

The obtained colored fine particles were arbitrarily selected from 100 fine particles by a scanning electron micrograph and the particle diameter was measured. The colored fine particles were spherical, and the average particle diameter was 3.64 μm. The variation coefficient of the particle size (a value obtained by dividing the standard deviation of the particle size by the average particle size) was 2.7%.

Example 2 A solution prepared by dissolving 0.4 part by weight of sodium lauryl sulfate in 130 parts by weight of water was charged into a beaker, and 15 parts by weight of 1,2-dichloroethane and 22 parts by weight of 1-chlorododecane were mixed and swollen. A solution in which 3 parts by weight of benzoyl peroxide was dissolved was added to the agent, and the mixture was stirred with a homogenizer and dispersed so that the average particle diameter of the droplets of the swelling aid was 0.5 μm or less. The same reactor as in Example 1 was charged with 125 parts by weight of an aqueous polystyrene dispersion having an average particle size of 0.59 μm at a solid content of 10% by weight, and 25 parts by weight of acetone was added. The aqueous dispersion of the auxiliary agent was poured, and the mixture was gently stirred at 38 ° C. for 20 hours to swell the polystyrene particles with the swelling auxiliary agent. Then, 10 parts by weight of the dye having a trimethoxysilyl group obtained in Example 1, 80 parts by weight of vinyltrimethoxysilane, 250 parts by weight of methyl methacrylate and styrene 5
50 parts by weight, and the mixture was poured into a reactor together with a solution of 0.9 part by weight of sodium lauryl sulfate in 5000 parts by weight of water.
By stirring at a rotational speed of m, the above-mentioned constituents were absorbed into the swollen body of the polystyrene particles.

Thereafter, the temperature was raised to 70 ° C., and the reaction was carried out for 7 hours. After cooling to room temperature, the colored polymer fine particles obtained were collected by filtration, washed with water, and then subjected to a 0.5% by weight hydroxylation. After immersion in a sodium aqueous solution and left at room temperature for 5 hours to carry out hydrolysis and crosslinking reaction, the obtained colored fine particles were separated by filtration, washed with water and dried at 80 ° C. for 3 hours. The obtained colored fine particles were truly spherical. The average particle diameter determined in the same manner as in Example 1 was 2.96 μm, and the coefficient of variation of the particle diameter was 2.4%.

Evaluation of Performance of Colored Fine Particles The performance of the colored fine particles obtained in Examples 1 and 2 was evaluated as follows. (1) Colored State When the color density of the colored fine particles was visually observed, all of them were dark and uniformly colored. When the surface and the cut surface were observed with a scanning electron microscope, it was confirmed that the dye was uniformly dispersed inside the colored fine particles.

(2) Solvent resistance 1 g of the colored fine particles was added to 50 mL of ethanol and acetone, left at 20 ° C. for 7 days, filtered, and the filtrate was measured for the maximum absorption transmittance in the visible light region. The results are shown in Table 1. From this result, it was found that there was almost no extraction (decolorization) of the dye by the organic solvent, and the solvent resistance was excellent.

(3) Fabrication of Liquid Crystal Display Element As shown in FIG. 1, a transparent electrode (ITO thin film) 2 was deposited on one of the transparent glass substrates 1 at a peripheral portion thereof with a diameter of 3.80 μm.
sealant 5 made of an epoxy-based photocurable adhesive in which m glass fiber (peripheral spacer) is dispersed.
Was screen-printed in a frame shape except for the liquid crystal injection hole 6.
Further, the entire surface of the other transparent glass substrate 1 on which the transparent electrode (ITO thin film) 2 is deposited is provided with a spacer A for a liquid crystal display element.
The aqueous dispersions of the colored fine particles obtained in Examples 1 and ² were sprayed to a spray density of about 120 particles / mm ² and dried. Then, the one transparent glass substrate 1
Is superimposed on the other transparent glass substrate 1 and opposed to each other with a certain gap therebetween via the sealing material 5 and the spacer A for the liquid crystal display element. Then, the liquid crystal injection hole 6 was sealed to produce a liquid crystal display element 9.

(4) Evaluation of Display Quality of Liquid Crystal Display Element Ten liquid crystal display elements were manufactured under the same conditions as above, and the gap between substrates of each liquid crystal display element was measured. The results are shown in Table 1. Further, when a negative type display indicating a dark level was performed in a state where no voltage was applied, both the liquid crystal display device using the colored fine particles of Example 1 and the liquid crystal display device using the colored fine particles of Example 2 showed that the liquid crystal layer was dark in the liquid crystal layer. Were not visually recognized as white spots, and the contrast of the liquid crystal display device was good.

[0064]

[Table 1]

[0065]

As described above, the colored fine particles of the present invention are spherical, uniform in particle diameter, excellent in hue stability, and excellent in heat resistance and solvent resistance. And cosmetic fillers, processing fillers, plastic fillers and the like. When the colored fine particles are used as a spacer for a liquid crystal display device, a liquid crystal display device having good display quality can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing one embodiment of a liquid crystal display device of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent glass substrate 2 Transparent electrode 3 Alignment film 4 Polarizer 5 Sealing material 6 Liquid crystal injection hole 7 Liquid crystal injection hole sealant 8 Liquid crystal 9 Liquid crystal display element A Liquid crystal display element spacer

Claims (4)

[Claims] At least one kind of a dye having a silyl group, at least one kind of a vinyl monomer having a silyl group, and another vinyl monomer copolymerizable with the vinyl monomer. Colored fine particles, comprising a copolymer comprising at least one of a copolymer and a crosslinked silyl group derived from the dye and a silyl group derived from the vinyl monomer. . 2. A copolymer having at least one kind of a dye having a hydrolyzable silyl group, at least one kind of a vinyl monomer having a hydrolyzable silyl group, and the vinyl monomer. Polymer particles are produced by polymerizing at least one of other possible vinyl monomers, and a hydrolyzable silyl group contained in the polymer particles is
A method for producing colored fine particles, comprising hydrolyzing with an acid or an alkali to form crosslinks. 3. A spacer for a liquid crystal display element, comprising the colored fine particles according to claim 1. 4. A liquid crystal display device comprising the liquid crystal display device spacer according to claim 3.