KR101959749B1 - Coloring resin particles, and production method and uses therefor - Google Patents

Abstract

A resin particle derived from a single or a plurality of polymerizable vinyl monomers and a coating layer containing a polymer as a coloring agent derived from a nitrogen-containing aromatic compound covering the surface of the resin particle, wherein the coating layer has a thickness of 30 to 300 nm By weight.

Description

COLORING RESIN PARTICLES, PRODUCTION METHODS THEREOF, AND USE THEREOF. (COLORING RESIN PARTICLES AND PRODUCTION METHOD AND USES THEREFOR)

TECHNICAL FIELD The present invention relates to colored resin particles, a production method thereof, and uses thereof. More specifically, the present invention can be applied to various display devices such as a liquid crystal display (LCD), a plasma display (PDP), or the like, or on the surface of various screens such as a transmissive screen and a reflective screen, A method for producing the same, and a light-scattering member provided with a coating film of a mixture including the colored resin particles and a binder resin on a transparent base resin.

In a display device such as a liquid crystal display, when the surroundings are bright, external light is reflected on the display surface like a mirror, and information such as an image or a video displayed on the display surface becomes difficult to see.

In order to solve such a problem, there has been adopted a technique of forming a diaphragm film on the display surface side and diffusing the light passing through the display surface, thereby imparting a diaphragm to the surface to reduce non-visualization of external light by surface reflection.

The conventional retardation film has a structure in which the display surface of the display device is imparted with antifogging property by the fine uneven shape formed on the surface thereof.

As a method of forming the fine concavo-convex shape, from the viewpoints of ease of adjustment of the concavo-convex shape and production efficiency, a method of coating the film by applying the resin particle and the binder resin to the film and drying them has become mainstream.

However, with the above method, there is a problem that the antiglare layer (the coating film in which the resin particles are dispersed) is whitened by the light confusion due to the irregularities on the surface thereof and the contrast of display by the display device is lowered, So that the display appears to be flashing. In addition, there has also been a problem that the contrast of display is lowered due to the backward confusion light (light generated when the light generated in the display device is disturbed by resin particles).

As a technique for solving the above problems, a diaphragm member using black particles has been proposed (see Patent Document 1).

According to Patent Document 1, by using black particles instead of conventional resin particles, it is possible to suppress the increase of rear diffuse light, the decrease of display contrast and the glare. Further, it is said that the contrast can be improved by making the dark display part appear darker due to the fact that the particles are black.

International Publication No. WO2008 / 018339

However, in the technique according to Patent Document 1, The light transmittance is very low since the black particles are entirely black until the whole of the particles, that is, the inside of the particle. Therefore, the anti-glare member using the anti-glare member has a problem of darkening the display of the display device.

Accordingly, the present invention provides a colored resin particle for a light-scattering member capable of suppressing low contrast or glare of a display and preventing visible light from appearing on the display surface without significantly lowering the display brightness of the display device .

As described above, according to the present invention, there is provided a resin composition comprising a resin particle derived from a single or a plurality of polymerizable vinyl monomers, and a coating layer containing a polymer as a coloring agent derived from a nitrogen-containing aromatic compound covering the surface of the resin particle, A colored resin particle having a thickness of 30 to 300 nm is provided.

According to the present invention, there is also provided a light-scattering member comprising a transparent base resin, a coating film of the colored resin particles and a binder resin, and having a total light transmittance of 75% or more.

According to the present invention, an emulsion in which resin particles derived from one or more polymerizable vinyl monomers are dispersed and a nitrogen-containing aromatic compound as a monomer are added to the nitrogen-containing aromatic compound in an amount of 0.2 to 1.9 molar equivalents, And the resulting mixture is stirred under a temperature condition of -20 to 40 占 폚 to cover the surface of the resin particle with a covering layer containing a polymer as a coloring agent derived from the nitrogen-containing aromatic compound, There is provided a method for producing colored resin particles comprising a step of obtaining a colored resin particle having a thickness variation of a coating layer composed of a polymer of the nitrogen-containing aromatic compound covering the resin particle of 50% or less.

The colored resin particles according to the present invention are uniformly coated on the entire surface of the colored resin particles by a polymer as a coloring agent derived from a nitrogen-containing aromatic compound so as to ensure uniformity of light transmittance, And has the function of preventing the same light diffusing as that of the particles.

Thus, the light-diffusing member obtained by using the colored resin particles of the present invention can prevent the brightness of display by the display device from being greatly lowered, suppress the deterioration of display contrast and glare, .

In addition, when the coating layer has a thickness suppressed by a deviation of 50% or less, the colored resin particles can be provided which are evenly coated with the polymer of the nitrogen-containing aromatic compound evenly over the entire surface.

In addition, when the polymer of the nitrogen-containing aromatic compound is a polymer of pyrrole or a derivative thereof, the colored resin particle for the retardation member of the present invention can make the above effect more prominent.

When the colored resin particles for the light-diffusing member have an average particle diameter of 1 to 10 mu m, they can be more preferably used as the light-scattering member.

1 is a transmission electron micrograph of the colored resin particles obtained in Example 1. Fig.
Fig. 2 is a transmission electron micrograph of the colored resin particles obtained in Example 2. Fig.
3 is a transmission electron micrograph of the colored resin particle obtained in Example 3. Fig.
4 is a transmission electron micrograph of the colored resin particles obtained in Example 4. Fig.
5 is a transmission electron micrograph of the colored resin particles obtained in Example 5. Fig.
6 is a transmission electron micrograph of the colored resin particle obtained in Comparative Example 3. Fig.

The colored resin particle according to the present invention has a resin particle derived from a polymerizable vinyl monomer and a coating layer composed of a polymer as a coloring agent derived from a nitrogen-containing aromatic compound covering the surface of the resin particle. The coating layer has a thickness of 30 to 300 nm.

(Resin particle)

(1) Polymerizable vinyl monomers

Examples of the polymerizable vinyl monomers include monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate Methacrylic acid alkyl ester monomers such as methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate, styrene, Aromatic vinyl monomers such as methyl styrene, vinyl toluene and ethyl vinyl benzene, saturated vinyl monomers such as vinyl acetate, vinyl propionate and vinyl versatate, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, Ethylenic carboxylic acid such as methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, and fumaric acid, an ethylenic carboxylic acid anhydride such as maleic anhydride, Monoalkyl esters of ethylenic dicarboxylic acids such as ethyl maleic acid and butyl maleic acid, and ethylenic carboxylic acid salts such as ammonium salts and alkali metal salts thereof, and acidic carboxylic acids such as acrylamide, methacrylamide and diacetone acrylamide. Amides, N-methylol acrylamide, N-methylol methacrylamide, methylol diacetone acrylamide, and their monomers and ethers of alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethyl acrylamide ), Esters of alcohols having an epoxy group and an ethylenic carboxylic acid such as glycidyl acrylate and glycidyl methacrylate, esters of an aliphatic carboxylic acid such as 2-hydroxyethyl Hydroxyalkyl esters of ethylenic carboxylic acids such as methacrylate, 2-hydroxypropyl acrylate and 2-hydroxymethacrylate, Esters of an alcohol having an amino group with an ethylenic carboxylic acid such as aminoethyl methacrylate and diethylaminoethyl methacrylate; monomers having one ethylenic unsaturated bond; and monomers having one ethylenic unsaturated bond such as divinylbenzene, diallyl phthalate, And monomers having two or more non-conjugated unsaturated bonds such as maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, and maleic anhydride.

These may be used singly or in combination of plural species. A hydrophobic monomer having a solubility in water (20 캜) of 1.5% by weight or less in the polymerizable vinyl monomer is preferable because a more uniform coating layer can be obtained. Among them, styrene, butyl acrylate and butyl methacrylate are more preferable, and butyl acrylate and butyl methacrylate are particularly preferable.

(2) Polymerization method (resin particle production method)

The polymerization method is not particularly limited as long as it is a known polymerization method. Examples of the known polymerization method include bulk polymerization, emulsion polymerization, soap-free emulsion polymerization, seed polymerization and suspension polymerization. In the case of bulk polymerization, resin particles having desired particle diameters can be obtained by classifying after pulverization. Emulsion polymerization is a polymerization method in which monomers and an emulsifier (surfactant) which are not soluble in a medium such as water and a medium are mixed and a polymerization initiator soluble in the medium is added thereto. And the deviation of the obtained particle diameters is small. The soap-free emulsion polymerization is an emulsion polymerization without using an emulsifier. It is possible to obtain particles of uniform diameter. The seed polymerization is a polymerization in which seed (seed) particles separately prepared at the start of polymerization are put in. The particle diameter and the particle diameter distribution and the amount (number) of the seed particles are arbitrarily determined and polymerized, and the polymer can be polymerized with a desired particle size and particle size distribution. The suspension polymerization is a polymerization method in which water of a monomer and a solvent is mechanically stirred and suspended. It is characterized in that it is possible to obtain particles having a small particle size and arranged.

The general method of the seed polymerization method is described below, but the production method of the resin particle according to the present invention is not limited to this method.

First, seed particles are added to an emulsion (suspension) composed of a monomer and an aqueous medium. The emulsion can be prepared by a known method. For example, an emulsion can be obtained by adding a monomer to an aqueous medium and dispersing it by a micro emulsifier such as a homogenizer, an ultrasonic processor, or a nanometer. Examples of the aqueous medium include water or a mixture of water and an organic solvent (for example, a lower alcohol). The method for producing the seed particles to be produced separately is not particularly limited, but emulsion polymerization, soap-free emulsion polymerization or suspension polymerization may be used. Emulsion polymerization and soap-free emulsion polymerization are preferable in view of the uniformity of grain size of the seed particles and the simplicity of the production method. The weight average molecular weight of the seed particles may be adjusted by adding or subtracting the amount of the polymerization initiator used, or by adding or subtracting the addition amount of the molecular weight adjuster.

The monomer may contain a polymerization initiator if necessary. The polymerization initiator may be dispersed in an aqueous medium after being preliminarily mixed with the monomers, or both may be dispersed in an aqueous medium. The particle size of the droplets of the monomer present in the obtained emulsion is preferably smaller than that of the seed particle because the monomer is efficiently absorbed to the seed particle.

The seed particles may be directly added to the emulsion or may be added in the form of dispersing the seed particles in an aqueous medium (hereinafter referred to as seed particle dispersion). After the seed particles are added to the emulsion, the monomers are absorbed by the seed particles. This absorption can be usually carried out by stirring the emulsion after seed particle addition at room temperature (about 20 ° C) for 1 to 12 hours. Further, in order to accelerate the absorption of the monomer, the emulsion may be heated to about 30 to 50 占 폚.

The seed particles swell by absorbing the monomers. The mixing ratio of the monomers to the seed particles is preferably in the range of 5 to 300 parts by weight, more preferably 100 to 250 parts by weight, based on 1 part by weight of the seed particles. When the mixing ratio of the monomers is small, the increase of the particle diameter due to polymerization becomes small. When the mixing ratio of the monomers increases, the monomers are not completely absorbed by the seed particles, and suspension polymerization is carried out independently in the aqueous medium to generate abnormal particles. The completion of absorption of the monomer by the seed particles can be judged by confirming enlargement of the particle size by observing with an optical microscope.

Examples of the polymerization initiator to be added as needed include, but are not limited to, benzoyl peroxide, lauroyl peroxide, orthochloro benzoyl peroxide, orthomethoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t Organic peroxides such as butyl peroxy-2-ethylhexanoate and di-t-butyl peroxide; (2,4-dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'- Azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile) Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-carbamoyl azo) iso Azo compounds such as butyronitrile, 4,4'-azobis (4-cyanovaleric acid), and dimethyl-2,2'-azobisisobutylate. The polymerization initiator is preferably used in a range of 0.1 to 1.0 part by weight based on 100 parts by weight of the polymerizable monomer.

Then, the resin particles can be obtained by polymerizing the monomer absorbed in the seed particles. The polymerization temperature may be appropriately selected depending on the type of monomer or polymerization initiator. Concretely, the temperature is preferably 25 to 110 占 폚, more preferably 50 to 100 占 폚. The polymerization time may be 1 to 12 hours. The polymerization may be carried out under an inert gas atmosphere inert to polymerization such as a nitrogen atmosphere. It is preferable that the polymerization reaction is carried out by raising the temperature of the seed particles after the monomer and optionally used polymerization initiator are completely absorbed.

In the polymerization step, a polymer dispersion stabilizer may be added to improve the dispersion stability of the resin particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, cellulose (such as hydroxyethylcellulose, carboxymethylcellulose), and polyvinylpyrrolidone. In addition, an inorganic water-soluble polymeric compound such as sodium tripolyphosphate may be used in combination. Of these polymer dispersion stabilizers, polyvinyl alcohol and polyvinyl pyrrolidone are preferable. The addition amount of the polymer dispersion stabilizer is preferably 1 to 10 parts by weight based on 100 parts by weight of the monomer.

Further, in order to suppress the generation of emulsified particles in the aqueous system in the above-mentioned polymerization step, water-soluble polymerization inhibitors such as nitrates, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin B, citric acid and polyphenols do.

(Method for producing colored resin particles)

The colored resin particles are not particularly limited. For example, resin particles obtained by the seed polymerization method and the like introduced above may be dispersed in an aqueous medium containing alkali metal salts of inorganic acids and acids, by adding a nitrogen-containing aromatic compound as a monomer in an optional amount Followed by oxidative polymerization. The nitrogen-containing aromatic compound is a compound which becomes a polymer colored by oxidation polymerization.

(1) A nitrogen-containing aromatic compound

Examples of the nitrogen-containing aromatic compound as the monomer include nitrogen-containing heterocyclic aromatic compounds such as pyrrole, indole, imidazole, pyridine, pyrimidine and pyrazine, primary amino group substituted aromatic compounds such as aniline, (E.g., alkyl group substituents having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl and the like), halogen substituents (for example, halogen substituents such as fluoro, chloro and bromo) and nitrile substituents. These monomers may be used singly or in combination of two or more. Polymers of pyrrole and pyrrole derivatives are preferable because a more uniform coating layer tends to be formed.

The amount of the nitrogen-containing aromatic compound can be set in accordance with the desired degree of coloration in the range of 1 to 30 parts by weight based on 100 parts by weight of the resin particles. Preferably 3 to 20 parts by weight. If the amount is less than 1 part by weight, the entire surface of the resin particles may not be uniformly coated with the polymer of the nitrogen aromatic compound, and desired coloring degree may not be obtained in some cases. On the other hand, when the amount is more than 30 parts by weight, the added nitrogen-containing aromatic compound may be polymerized singly, and other than the desired colored resin particle may be produced.

(2) Alkali metal salts of inorganic and organic acids (oxidizing agents)

Alkali metal salts of inorganic and organic acids are compounds which act as oxidizing agents for nitrogenous aromatic compounds. Specific examples thereof include potassium persulfate and sodium persulfate.

The alkali metal salt of the inorganic acid and the acid is used in an amount of 0.2 to 1.9 molar equivalents based on the total amount of the nitrogen-containing aromatic compound. When the amount is less than 0.2 molar equivalents, the entire surface of the resin particles is not uniformly covered with the coating layer containing the polymer of the nitrogen aromatic compound, and desired coloring degree may not be obtained in some cases. On the other hand, when the amount exceeds 1.9 molar equivalents, the added nitrogen-containing aromatic compound may be polymerized singly to produce the desired colored resin particle. Preferably 0.5 to 1.5 molar equivalents.

(3) aqueous medium

The alkali metal salts of the inorganic and the acid are added to the aqueous medium and used as an aqueous medium at a predetermined pH. The aqueous medium is not particularly limited as long as it dissolves the nitrogen-containing aromatic compound, but water or a mixture of water and an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Ether, ether, butyl ether, methyl cellosolve, tetrahydrofuran and the like, and ketones such as acetone, methyl ethyl ketone and diethyl ketone.

The aqueous medium to which the alkali metal salt of the inorganic acid and the acid is added preferably has a pH of 3 or more. If the pH is less than 3, the entire surface of the resin particles becomes uniform. The coating layer containing the polymer of the nitrogen aromatic compound is not covered, and the desired blackness may not be obtained in some cases. It is more preferable to have a pH of 3 to 10 because it is stably coated.

(4) Surfactants

A surfactant may be added to the aqueous medium. As the surfactant, an anionic surfactant, a cationic surfactant, a cationic surfactant, and a nonionic surfactant can all be used.

Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil potassium, alkylsulfuric acid ester salts such as sodium laurylsulfate and ammonium laurylsulfate, alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, Salts of alkylnaphthalenesulfonic acid, salts of alkylnaphthalenesulfonic acid, salts of alkanesulfonic acid, succinosulfonic acid salts, dialkylsulfosuccinic acid salts, alkylphosphoric acid ester salts, condensates of naphthalenesulfonic acid formalin, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene alkylsulfuric ester salts etc. .

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester , Oxyethylene-oxypropylene block polymer, and the like.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of the amphoteric surfactant include lauryldimethylamine oxide, a phosphate ester-based surfactant or a phosphorous ester-based surfactant.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant to be added may be 0.0001 to 1 part by weight based on 100 parts by weight of the aqueous medium.

In addition to the surfactant, a polymer dispersion stabilizer may be added to the aqueous medium. Examples of the polymer dispersion stabilizer include polyacrylic acid, a copolymer thereof and a neutralized product thereof, and polymethacrylic acid, a copolymer thereof and a neutralized product thereof, polyvinylpyrrolidone, hydroxypropylcellulose (HPC), etc. . The polymer dispersion stabilizer may be used in combination with the above-described surfactant.

(5) Oxidation polymerization

The colored resin particles in which the resin particle surface is covered with a coating layer containing a polymer of a nitrogen-containing aromatic compound can be obtained, for example, by the following method. That is, the emulsion (suspension) and the nitrogen-containing aromatic compound in which the resin particles obtained by the seed polymerization method or the like are dispersed are added to an aqueous medium containing an alkali metal salt of inorganic and acid to obtain a mixture. Subsequently, the mixture is stirred at a temperature of preferably -20 to 40 캜 for 0.5 to 10 hours to obtain colored resin particles.

In addition, the emulsion in which the colored resin particles are dispersed is centrifuged if necessary to remove the aqueous medium, washed with water and solvent, and then dried and isolated.

(Colored resin particles)

The colored resin particles obtained by the oxidation polymerization are covered with a coating layer containing a polymer of a nitrogen aromatic compound having a uniform surface as a whole.

Here, the term " uniform " means that the thickness of the coating layer containing the polymer of the nitrogen-containing aromatic compound covering the resin particles is small. The deviation is preferably 50% or less, more preferably 40% or less.

The thickness of the coating layer is 30 to 300 nm. Preferably 50 to 200 nm. When the thickness of the coating layer is less than 30 nm, the degree of coloring is low and desired antifogging properties may not be obtained. On the other hand, if it exceeds 300 nm, the light transmittance is lowered, and the display of the display device provided with the anti-glare member may be dimmed.

The method of measuring the thickness of the coating layer and the method of calculating the thickness deviation will be described in the section of the embodiment.

The average particle diameter of the colored resin particles is not particularly limited, but is preferably 1 to 10 占 퐉 from the viewpoint of its use as a repellent member. More preferably 3 to 7 mu m. When the average particle diameter of the colored resin particles is less than 1 占 퐉, fine irregularities are not formed in the light-diffusing member and desired antireflection property may not be obtained. On the other hand, when it exceeds 10 탆, it is difficult to adjust fine irregularities and desired antireflection property may not be obtained.

Since the colored resin particles of the present invention are coated with a coating layer containing a polymer of a nitrogen aromatic compound in which the entire surface is homogeneous, it has a desired degree of coloration derived from this polymer. In addition, since only the surface portion of the particles is colored, the amount of light passing through the particles is not significantly lowered compared with known black particles which are black to the inside of the particles. Therefore, by dispersing the colored resin particles in a film or a sheet, a retardation member having a desired total light transmittance can be stably produced.

(An example of a method of producing a flameproof member)

Hereinafter, an example of a method for producing a light-scattering member using the colored resin particles of the present invention is shown, but the present invention is not limited thereto.

The repellent member can be obtained by applying a mixture containing the colored resin particles and a binder resin to the transparent base resin.

(1) Transparent base resin

Examples of the transparent base resin include polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate; cellulose-based polymers such as diacetylcellulose and triacetylcellulose (TAC); polycarbonate-based polymers; And acryl-based polymers such as acrylate and acrylate. Examples of the polymer include styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer, olefin-based polymers such as polyethylene, polypropylene, polyolefins having a cyclic to norbornene structure, ethylene-propylene copolymers, vinyl chloride-based polymers, And amide-based polymers such as aromatic polyamides. Further, it is also possible to use an imide polymer, a sulfon polymer, a polyether sulfone polymer, a polyether ether ketone polymer, a polyphenyl sulfide polymer, a vinyl alcohol polymer, a vinylidene chloride polymer, a vinyl butyral polymer, A film made of a polymer such as a polyoxymethylene polymer, an epoxy polymer, or a mixture of the above polymers. Particularly, those having a small birefringence are preferably used. Further, a film in which an easy adhesive layer such as an acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, and an acrylic graft polyester resin is formed on these films may be used have.

The thickness of the transparent base resin can be suitably determined, but generally it is about 10 to 500 占 퐉 in terms of workability such as strength and handling, and thin layer properties. Preferably from 20 to 300 mu m, more preferably from 30 to 200 mu m.

Additives may be added to the substrate. Examples of the additive include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and an enhancer.

(2) resin mixture

(2-1) Binder resin

The binder resin is not particularly limited as long as it is used in the field according to required properties such as transparency, resin particle dispersibility, light resistance, moisture resistance and heat resistance. As the binder resin, for example, a (meth) acrylic resin; (Meth) acrylic urethane-based resin; Urethane resin; Polyvinyl chloride resins; Polyvinylidene chloride resins; Melamine resin; Styrene type resin; Alkyd resins; Phenolic resin; Epoxy resin; Polyester-based resin; Modified silicone resins such as (meth) acrylic silicone resin, alkylpolysiloxane resin, silicone resin, silicone alkyd resin, silicone urethane resin, silicone polyester resin and silicone acrylic resin; Fluorinated resins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymer, and the like. These binder resins may be thermoplastic or may be a curable resin such as a thermosetting resin, a heat curable resin, an ultraviolet curable resin, or an electron beam curable resin.

In addition to the above, organic binder resins such as synthetic rubbers and natural rubbers, and inorganic binders may also be used. Examples of the organic binder resin include an ethylene-propylene copolymer rubber, a polybutadiene rubber, a styrene-butadiene rubber, and an acrylonitrile-butadiene rubber. Examples of the binder resin of the inorganic binder include silica sol, alkali silicate, silicon alkoxide, condensates thereof (hydrolysis), and phosphates. These may be used alone or in combination of two or more.

Such a binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the resin composition. The binder resin can be cured under various curing conditions. Depending on the curing type, an inorganic or organic-inorganic hybrid matrix obtained by hydrolysis and dehydration condensation of an ionizing radiation curable resin such as an ultraviolet ray curable resin or an electron beam curable resin, a thermosetting resin, a thermoplastic resin or a metal alkoxide may be used.

Examples of the thermosetting resin include a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin.

Examples of the ionizing radiation curable resin include multifunctional acrylate resins such as acrylic acid or methacrylic acid esters of polyhydric alcohols, polyfunctional urethane acrylates synthesized with diisocyanates, polyhydric alcohols, and hydroxy esters of acrylic acid or methacrylic acid Resins and the like. In addition, polyether resins, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins and the like having an acrylate functional group can also be used.

When an ultraviolet ray curable resin is used in the ionizing radiation curable resin, a photopolymerization initiator is added to the binder resin. Any photopolymerization initiator may be used, but it is preferable to use a photopolymerization initiator.

Examples of the photopolymerization initiator (radical polymerization initiator) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal, and alkyl ethers thereof. The amount of the photopolymerization initiator to be used is 0.5 to 20% by weight based on the binder resin. Preferably 1 to 5% by weight.

Examples of the thermoplastic resin include vinyl resins such as acetyl cellulose, nitrocellulose, cellulose derivatives such as acetyl butyl cellulose, ethyl cellulose and methyl cellulose, vinyl acetate and its copolymers, vinyl chloride and its copolymers, vinylidene chloride and copolymers thereof Acrylic resins such as acrylic resins and their copolymers, methacrylic resins and their copolymers, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, polyvinyl chloride resins, And the like.

As the inorganic or organic-inorganic composite matrix, a material using a silicon oxide-based matrix containing a silicon alkoxide-based material as a raw material can be used. Specific examples thereof include tetraethoxysilane and the like.

(2-2) Organic solvents

The resin mixture may contain an organic solvent. The organic solvent is not particularly limited so long as it can be easily coated on the base resin. For example, aromatic solvents such as toluene and xylene; Alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and propylene glycol methyl ether; Glycol ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate and propylene glycol methyl ether acetate; Chlorinated solvents such as chloroform, dichloromethane, trichloromethane and methylene chloride; Ether-based solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,3-dioxolane; N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide, and the like, or a mixture of two or more of them may be used.

(3) Formation of the resin mixture on the base resin

As a method of forming the resin mixture on the base resin, the curable composition may be applied to a base resin such as a bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, microgravure coating, There is a method of crosslinking and curing the curable composition by coating the base resin with a known coating method such as a dipping method, drying the solvent if necessary, and further irradiating an active energy ray. Examples of the active energy ray include ultraviolet rays generated from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp or a tungsten lamp or a Cockcroft Walton type or a Bandegraph type Electron beams, alpha rays, beta rays, gamma rays, and the like extracted from electron beam accelerators such as resonance type, resonance type, insulating core transformer type, linear type, dynamictron type and high frequency type can be used. The thickness of the layer (the antiglare layer) in which the colored resin particles thus formed is dispersed is not particularly limited and is appropriately determined depending on the particle diameter of the colored resin particles, but is preferably 1 to 10 mu m. More preferably 3 to 7 mu m.

(Non-flammable member)

The deflecting member obtained by the method or the like suppresses the increase of the backward confusion light from the display device (which is a light source) without significantly lowering the amount of light transmitted through the deflecting member, while suppressing the decrease in display contrast and glare, It is possible to prevent the external light from impinging on the display surface (on which the repellent member is provided).

It is preferable that the transmissive amount of the antireflective member is 75% or more. More preferably, it is 80% or more. If the total light transmittance is less than 75%, the user of the display device may feel that the display surface of the display device or the like becomes considerably darker than a state in which the display member is not provided.

The anti-glare member is preferably 35 or less in 45-degree reflected light intensity, which is an evaluation criterion for prevention of external light. More preferably 30 or less. If the 45 ° reflection light intensity exceeds 35, there is a case where the non-reflection of the external light (on the display surface provided with the anti-static member) becomes worrisome. Here, the 45 ° reflection light intensity is a regular reflection angle at an angle of reflection of 45 ° when the incident angle is -45 ° measured by a three-dimensional photometer. The method of measuring the 45 占 reflected light intensity will be described in the section of the embodiment.

The colored resin particles of the present invention are covered with a coating layer composed of a polymer of a nitrogen aromatic compound having a uniform surface as a whole. Therefore, it has a desired degree of coloration derived from the polymer. Therefore, by dispersing the colored resin particles in a film or a sheet, a film or sheet having a desired total light transmittance can be stably produced. Therefore, it can be preferably used for an antiglare member such as an antiglare film or the like.

Example

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited thereto.

First, measurement methods and calculation methods in the examples and comparative examples will be described.

(Average particle diameter of seed particles)

The average particle diameter of the seed particles is measured by LS230 manufactured by Beckman Coulter, Inc. Specifically, 0.1 g of the seed particles and 10 ml of the 0.1% nonionic surfactant solution were added and mixed for 2 seconds on a touch mixer TOUCHMIXER MT-31 manufactured by Yamato Scientific Co., Ltd. Thereafter, the test tube is dispersed for 10 minutes using ULTRASONIC CLEARNER VS-150 manufactured by Belvo Clear Co., Ltd., which is a commercially available ultrasonic cleaner. The dispersion was measured while irradiating ultrasonic waves with LS230 manufactured by Beckman Coulter. The optical model at that time is measured according to the refractive index of the produced particles.

(Average particle diameter and coefficient of variation of resin particles)

The measurement of the average particle diameter of the resin particles is performed by a method of performing calibration using a 280 mu m aperture in accordance with Reference MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited. For the measurement, a precision particle size distribution measuring apparatus (Coulter Multisizer II manufactured by Beckman Coulter Inc.) is used. Specifically, 0.1 g of the resin particles was preliminarily dispersed in 10 ml of a 0.1% nonionic surfactant solution using a touch mixer and an ultrasonic wave, and the dispersion was filled with ISOTON II (manufactured by Beckman Coulter, Inc., measurement electrolyte solution) While stirring slowly in a beaker, drop with a syringe and adjust the concentration meter to about 10%. Then, manual measurement is performed by inputting an aperture size of 280 μm, a current of 800, a gain of 4, and a polarity of + to the multisizer II body. During the measurement, the inside of the beaker is slowly stirred so that no air bubbles enter, and the measurement is terminated when 100,000 resin particles are measured.

The volume average particle diameter (arithmetic average particle diameter in volume% mode: volume median diameter) is calculated as the average particle diameter (x) of the resin particles.

The coefficient of variation (CV value) is a value calculated from the standard deviation (?) And the average particle diameter (x) by the following equation.

CV value (%) = (? / X) 占 100

(Method for Measuring Thickness and Deviation of Coating Layer Containing Polymer of Containing Nitrogen Aromatic Compound)

The colored resin particles are encapsulated with an epoxy resin and divided into two parts by a plane passing through the center of the particle. The divided surfaces are dyed with ruthenium tetroxide (RuO ₄ ), and then observed with a transmission electron microscope (SEM). Since ruthenium tetraoxide stains the coating layer containing the polymer of the nitrogen-containing aromatic compound more stably than the resin particles derived from the polymerizable vinyl-based monomer, the coating state is easy to grasp. The division plane is divided into eight lines passing through the center of the plane, and divided into 16 equal numbers. For each arc, measure the maximum and minimum thicknesses. The average thickness (x) and the standard deviation (?) Are obtained from the values of the 32 points measured by the above, and the thickness variation width (%) is obtained by the following equation.

Deviation width of thickness (%) = (? / X) 占 100

(Evaluation of surface state of the repellent member)

The obtained film is attached to a black ABS plate, and the reflected light intensity at a reflection angle of 45 DEG at an incident angle of -45 DEG is measured by a three-dimensional photometer (Gonio Photometer GP-200 manufactured by Murakami Color Research Laboratory).

The reflectance of the film made of only the binder resin containing no particles was set to 100 and the reflectance of the film made of the particles and the binder resin was measured and evaluated. The lower the reflected light intensity, the more diffuse or absorbed the light, the less the glare, and the more excellent the scattering property. Specifically, the reflectance is preferably 35 or less, more preferably 30 or less.

(Method for Measuring Total Light Transmittance of Diffusible Member)

The total light transmittance of the antifogging member is measured by a haze meter (NDH-2000 manufactured by Nippon Telegraph and Telephone Corporation). Measurement conditions are in accordance with JIS K 7105.

(Seed particle synthesis example 1)

A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 1,300 g of ion-exchanged water and 320 g of methyl methacrylate (MMA) in which 3 g of 1-octanethiol had been dissolved as a molecular weight adjusting agent, Lt; / RTI > 1.6 g of ammonium persulfate as a polymerization initiator was dissolved in 300 g of ion-exchanged water, and the mixture was stirred at 70 캜 for 12 hours to carry out a polymerization reaction. By this polymerization reaction, a dispersion liquid containing polymethyl methacrylate particles having an average particle diameter of 0.5 mu m was obtained.

A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 1,300 g of ion-exchanged water and 320 g of methyl methacrylate dissolved in 3 g of 1-octanethiol as a molecular weight regulator. Further, 160 g of the dispersion obtained above was added, and the mixture was heated to 70 DEG C in a stream of nitrogen while stirring. 1.6 g of ammonium persulfate as a polymerization initiator was dissolved in 300 g of ion-exchanged water, and the mixture was stirred at 70 캜 for 12 hours to carry out a polymerization reaction. By this polymerization reaction, a dispersion liquid containing polymethyl methacrylate particles having an average particle diameter of 1.1 탆 (hereinafter referred to as seed particles 1) was obtained.

(Resin Particle Production Example 1)

100 g of methyl methacrylate (MMA) as a polymerizable vinyl monomer, 600 g of styrene, 300 g of ethylene glycol dimethacrylate (EGDMA) as a polymerizable vinyl monomer, 20 g of 2,2'-azobis (2-methylbutyronitrile) were added and mixed. 1,000 g of ion-exchanged water containing 10 g of sodium succinate sulfonate as a surfactant was mixed with the obtained mixture and treated at 8000 rpm for 10 minutes with a TK homomixer (manufactured by Primix) to obtain a water-based emulsion. To the aqueous emulsion was added 360 g of a dispersion containing the seed particles 1 while stirring.

After stirring for 3 hours, the dispersion was observed with an optical microscope. As a result, it was confirmed that the polymerizable vinyl monomer in the aqueous emulsion was absorbed into the seed particle 1 (swelling magnification of about 120 times). Thereafter, 2000 g of an aqueous solution in which 40 g of polyvinyl alcohol (PVA-224E manufactured by Kuraray Co., Ltd.) was dissolved as a dispersion stabilizer was further added to the reactor and polymerization was carried out with stirring at 60 DEG C for 6 hours. The volume average particle diameter of the obtained resin particles (hereinafter referred to as Resin Particle 1) was 5.2 탆.

(Resin Particle Production Example 2)

Resin particles were obtained in the same manner as in Resin Particle Production Example 1 except that 350 g of butyl acrylate, 350 g of butyl methacrylate, and 300 g of ethylene glycol dimethacrylate were used as the polymerizable vinyl monomer. The spherical reduced volume average particle diameter of the obtained resin particles (hereinafter referred to as resin particles 2) was 5.2 탆.

(Resin Particle Production Example 3)

700 g of methyl methacrylate (MMA) as a polymerizable vinyl monomer, 300 g of ethylene glycol dimethacrylate (EGDMA), and 5 g of 2,2'-azobis (2-azobisisobutyronitrile) as a polymerization initiator were charged in a 5 L reactor equipped with a stirrer, Methylbutyronitrile) were added and mixed. 1 liter of ion-exchanged water containing 10 g of sodium succin sulfonate as a surfactant was mixed with the obtained mixture and treated at 8000 rpm for 10 minutes by T. K homomixer (manufactured by Primix) to obtain a water-based emulsion. To the aqueous emulsion was added 360 g of a dispersion containing the seed particles 1 while stirring.

After stirring for 3 hours, the dispersion was observed with an optical microscope. As a result, it was confirmed that the polymerizable vinyl monomer in the aqueous emulsion was absorbed into the seed particle 1 (swelling magnification of about 120 times). Thereafter, 2000 g of an aqueous solution in which 40 g of polyvinyl alcohol (PVA-224E manufactured by Kuraray Co., Ltd.) was dissolved as a dispersion stabilizer was further added to the reactor and polymerization was carried out with stirring at 60 DEG C for 6 hours. The volume average particle diameter of the obtained resin particles (hereinafter referred to as resin particles 3) was 5.2 탆.

(Resin Particle Production Example 4)

Resin particles were obtained in the same manner as in Resin Particle Production Example 1 except that 400 g of butyl methacrylate, 300 g of styrene and 300 g of ethylene glycol dimethacrylate were used as the polymerizable vinyl monomer. The volume conversion average volume diameter of the obtained resin particles (hereinafter referred to as resin particles 4) was 5.1 탆.

(Example 1)

A suspension of 50 g of Resin Particle 1 dispersed in 50 g of isopropanol was added to a solution of 20 g of potassium persulfate dissolved in 300 g of water, followed by stirring. The suspension was cooled to 5 DEG C, and a solution composed of 5 g of pyrrole and 50 g of isopropanol was further added, followed by polymerization for 3 hours with stirring. Thereafter, solid content was obtained by filtration. The solid component was taken out, washed with water and isopropanol, and dried at 60 DEG C for 12 hours by a vacuum drier to obtain black colored resin particles (hereinafter referred to as colored resin particles 1).

The colored resin particle 1 was observed by a transmission electron microscope. As a result, it was found that the thickness of the coating layer containing the polymer derived from pyrrole (nitrogen-containing aromatic compound) was 94 nm, and the entire surface of the particles was covered uniformly. The deviation of the coating layer thickness was 24.6%. A photograph using a transmission electron microscope is shown in Fig.

(Example 2)

Black colored resin particles (hereinafter referred to as colored resin particles 2) were obtained in the same manner as in Example 1, except that the amount of pyrrole was changed to 2.5 g.

The colored resin particles 2 were observed with a transmission electron microscope. As a result, it was found that the thickness of the coating layer was 37 nm, and the entire surface of the particles was covered uniformly. The deviation of the coating layer thickness was 22.9%. A photograph by a transmission electron microscope is shown in Fig.

(Example 3)

Colored resin particles (hereinafter referred to as colored resin particles 3) were obtained in the same manner as in Example 1, except that 50 g of Resin Particle 2 was used instead of Resin Particle 1.

The colored resin particles 3 were observed with a transmission electron microscope. As a result, the thickness of the coating layer was 120 nm and the variation width of the thickness was 11.9%. It was found that the entire surface of the particles was uniformly coated. A photograph using a transmission electron microscope is shown in Fig.

(Example 4)

A suspension of 50 g of Resin Particle 3 dispersed in 50 g of isopropanol was added to a solution of 20 g of potassium persulfate dissolved in 300 g of water, followed by stirring. The suspension was cooled to 5 DEG C, and a solution composed of 10 g of pyrrole and 50 g of isopropanol was further added, followed by polymerization for 3 hours with stirring to obtain a black dispersion. Thereafter, solid content was obtained by filtration. The solid component was taken out, washed with water and isopropanol, and dried at 60 DEG C for 12 hours by a vacuum drier to obtain black colored resin particles (0.5 molar equivalent of the alkali metal salt of inorganic and acidic acid added to the heterocyclic aromatic amine monomer) .

The obtained colored resin particles were observed by a transmission electron microscope. As a result, it was found that the average thickness of the coating layer was 149 nm and the variation width of the thickness was 35.7%, and the entire surface of the particles was uniformly coated. A photograph using a transmission electron microscope is shown in Fig.

(Example 5)

Colored resin particles were obtained in the same manner as in Example 1 except that 50 g of Resin Particle 2 was used instead of Resin Particle 1.

The obtained colored resin particles were observed with a transmission electron microscope. As a result, the thickness of the coating layer was 120 nm and the variation width of the thickness was 11.9%. It was found that the entire surface of the particles was uniformly coated. FIG. 5 shows a photograph by a transmission electron microscope.

(Example 6)

Colored resin particles were obtained in the same manner as in Example 1 except that 50 g of Resin Particle 4 was used instead of Resin Particle 1.

The obtained colored resin particles were observed by a transmission electron microscope. As a result, the thickness of the coating layer was 91 nm and the variation width of the thickness was 14.7%. It was found that the entire surface of the particles was uniformly coated.

(Comparative Example 1)

(Hereinafter referred to as colored resin particle 4) was obtained in the same manner as in Example 1, except that the amount of pyrrole was changed to 1.0 g.

As a result of observing the colored resin particles 4 with a transmission electron microscope, it was impossible to confirm the coating layer in the transmission electron microscope.

(Comparative Example 2)

100 g of carbon black was added to 900 g of methyl methacrylate (MMA) and 100 g of ethylene glycol dimethacrylate (EGDMA), and the mixture was uniformly mixed with a ball mill. Then, 3000 g of water and 100 g of tribasic calcium phosphate as a dispersion stabilizer were added to the mixture to obtain a mixed solution. This mixed solution was stirred with a T. K homomixer (manufactured by Primemix) at 7000 rpm for 10 minutes to prepare a solution having a droplet diameter of 5 탆. Subsequently, the mixed solution was heated to 65 캜 and subjected to suspension polymerization for 10 hours while stirring. After completion of the polymerization, the mixture was cooled to room temperature, and the colored resin particles in the mixture were filtered, washed and dried. The resulting colored resin particles (hereinafter referred to as colored resin particles 5) were black resin particles having an average particle diameter of 5.1 탆.

(Comparative Example 3)

A suspension of 50 g of Resin Particle 2 dispersed in 50 g of isopropanol was added to a solution of 300 g of water and 10 g of ammonium persulfate dissolved therein, followed by stirring. The suspension was cooled to 5 占 폚, and a solution comprising 5 g of pyrrole and 50 g of isopropanol was further added, followed by polymerization for 3 hours with stirring to obtain a black dispersion. Thereafter, solid content was obtained by filtration. The solids were taken out, washed with water and isopropanol, and dried at 60 ° C for 12 hours in a vacuum drier to obtain colored resin particles (amount of addition of ammonium salt of inorganic and acidic acid to heterocyclic aromatic amine monomer: 0.59 molar equivalent).

The obtained colored resin particles were observed with a transmission electron microscope. As a result, the average thickness of the coating layer was 178 nm and the variation width of the thickness was 54.6%. Many of the surfaces of the particles not covered with the polymer can be seen, and it can not be said that they are uniformly coated. FIG. 6 shows a photograph using a transmission electron microscope.

(Comparative Example 4)

A suspension of 50 g of Resin Particle 2 dispersed in 50 g of isopropanol was added to a solution of 5 g of potassium persulfate dissolved in 300 g of water, followed by stirring. The suspension was cooled to 5 占 폚, and a solution comprising 5 g of pyrrole and 50 g of isopropanol was further added, followed by polymerization for 3 hours with stirring to obtain a pale brown dispersion. Thereafter, solid content was obtained by filtration. The solid component was taken out, washed with water and isopropanol, and dried at 60 DEG C for 12 hours in a vacuum dryer. As a result, resin particles were obtained, but the particles were pale brown and a coating layer could not be confirmed by a transmission electron microscope The addition amount of the metal salt to the heterocyclic aromatic amine monomer is 0.24 molar equivalent).

The results of Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1.

(Production example of a repellent member)

10 parts by weight of colored resin particles 1 were compounded in a binder solution prepared by dissolving 100 parts by weight of an acrylic resin (BR106, manufactured by Mitsubishi Rayon Co., Ltd.) as a binder resin in 400 parts by weight of toluene as a solvent and uniformly dispersed to prepare a coating composition. The composition for coating was applied to a PET film as a base resin having a thickness of 100 mu m using a 50 mu m applicator to form a coating film. And the coating film on the PET film was dried by drying in a thermostatic chamber at 70 DEG C for 2 hours to obtain an antifogging member (hereinafter referred to as antifogging member 1).

In the same manufacturing process, the colored resin particles 2 were mixed in place of the colored resin particles 1 to form the coloring resin particles 3, and the coloring resin particles 4 were compounded to form the coloring resin particles 4, Resin Particles 5 were blended to obtain the antifogging member 5.

Table 2 summarizes the total light transmittance and surface state (45 ° reflected light intensity) of the light-shielding members 1 to 5.

It was found that all of the colored resin particles of Examples 1 to 6 were uniformly coated with the entire surface of the resin particles by the coating layer.

The evaluation of the antifogging members 1 to 5 shows that the antifogging member obtained by using the colored resin particles of the present invention according to Examples 1 to 3 has the effect of preventing the external light from being reflected without significantly reducing the transmitted light .

Claims (15)

Resin particles derived from a single or plural kinds of polymerizable vinyl monomers,
And a coating layer containing a polymer as a coloring agent derived from a nitrogen-containing heterocyclic aromatic compound covering the surface of the resin particle,
Wherein the coating layer has a thickness of 30 to 300 nm,
The coating layer has a thickness suppressed by a deviation of 50% or less,
Wherein the polymerizable vinyl monomer is a combination of a monomer selected from a methacrylic acid alkyl ester monomer, an acrylic acid alkyl ester monomer and an aromatic vinyl monomer, and a monomer having at least two non-conjugated unsaturated bonds,
Wherein the amount of the nitrogen-containing heterocyclic aromatic compound is 3 to 30 parts by weight based on 100 parts by weight of the resin particles. The method according to claim 1,
Wherein the colored resin particles for the light-diffusing member are used as particles constituting a coating film as an antiglare layer in the light-shielding member. delete 3. The method according to claim 1 or 2,
Wherein the polymer of the nitrogen-containing heterocyclic aromatic compound is a polymer of pyrrole or a derivative thereof. 3. The method according to claim 1 or 2,
Wherein the colored resin particles for the light-diffusing member have an average particle diameter of 1 to 10 占 퐉. A retardation member comprising a transparent base resin and a coating film of the colored resin particles and the binder resin for the retardation member of claim 1 or 2 and having a total light transmittance of 75% or more. The method according to claim 6,
Wherein the light-diffusing member has a 45-degree reflection intensity of 35 or less. The method according to claim 6,
Wherein the coating film has a thickness of 1 to 10 mu m. An emulsion in which resin particles derived from one or more polymerizable vinyl monomers are dispersed and a nitrogen-containing heterocyclic aromatic compound as a monomer are reacted with an alkali metal salt of an inorganic acid and an acid in an amount of 0.2 to 1.9 molar equivalents relative to the nitrogen-containing heterocyclic aromatic compound , And the mixture is stirred under a temperature condition of -20 to 40 캜 to cover the surface of the resin particle with a coating layer containing a polymer as a coloring agent derived from the nitrogen-containing heterocyclic aromatic compound, And obtaining a colored resin particle having a thickness variation of a coating layer composed of a polymer of the nitrogen-containing heterocyclic aromatic compound covering the resin particle of 50% or less, the method comprising:
Wherein the polymerizable vinyl monomer is a combination of a monomer selected from a methacrylic acid alkyl ester monomer, an acrylic acid alkyl ester monomer and an aromatic vinyl monomer, and a monomer having two or more non-conjugated unsaturated bonds,
Wherein the nitrogen-containing heterocyclic aromatic compound is used in an amount of 3 to 30 parts by weight based on 100 parts by weight of the resin particles. delete delete Resin particles derived from a single or plural kinds of polymerizable vinyl monomers,
And a coating layer containing a polymer as a coloring agent derived from a nitrogen-containing heterocyclic aromatic compound covering the surface of the resin particle,
Wherein the coating layer is a colored resin particle having a thickness of 30 to 300 nm,
The coating layer has a thickness suppressed by a deviation of 50% or less,
Wherein the polymerizable vinyl monomer is a combination of a monomer selected from a methacrylic acid alkyl ester monomer, an acrylic acid alkyl ester monomer and an aromatic vinyl monomer, and a monomer having at least two non-conjugated unsaturated bonds,
The amount of the nitrogen-containing heterocyclic aromatic compound is 3 to 30 parts by weight based on 100 parts by weight of the resin particles,
The coating layer is prepared by adding an emulsion in which the resin particles are dispersed and the nitrogen-containing heterocyclic aromatic compound to an aqueous medium containing 0.2 to 1.9 molar equivalents of an alkali metal salt of an inorganic and an acid with respect to the nitrogen-containing heterocyclic aromatic compound By stirring under a temperature condition of -20 to 40 占 폚,
Wherein the colored resin particles are used as particles constituting a coating film as an antiglare layer in a light-shielding member. delete 13. The method of claim 12,
Wherein the polymer of the nitrogen-containing heterocyclic aromatic compound is a polymer of pyrrole or a derivative thereof. 13. The method of claim 12,
Wherein the colored resin particles have an average particle size of 1 to 10 mu m.

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