JP5535118B2 - Hollow carbon particles and method for producing the same - Google Patents

Description

  The present invention relates to a hollow carbon particle having a hollow structure in which a hollow portion is formed inside a carbon layer, and a method for producing the same.

  As a method for producing the hollow carbon particles, for example, a microcapsule is produced from a thermodegradable polymer such as polymethyl methacrylate and a carbon precursor polymer such as polyacrylonitrile resin, and the microcapsule is produced by firing. A method (see Patent Document 1 below) is known.

  Further, as a method for producing hollow carbon particles, spherical particles composed of a liquid phase carbonizable material such as polyacrylonitrile or a copolymer thereof and an easily decomposable polymer such as polymethyl methacrylate are maintained, and the shape of the spherical particles is maintained. The spherical particles coated with silica gel are heated in a nitrogen atmosphere so that the spherical particles are carbonized, and then the silica gel is dissolved and removed with an aqueous sodium hydroxide solution (see Patent Document 2 below) ) Is also known.

JP 2003-48705 A JP 2006-151797 A

  However, the method described in Patent Document 1 uses a polyacrylonitrile resin or the like as the carbon precursor polymer. Since polyacrylonitrile-based resin has a cyano group on the hydrocarbon chain, there is a concern about toxicity.

  Further, the method described in Patent Document 2 requires a step of coating with silica gel and a step of dissolving and removing silica gel with an aqueous sodium hydroxide solution after carbonization of spherical particles, and the manufacturing process is complicated and time-consuming. There was a problem of being.

  The present invention has been made in view of the above-mentioned problems, and the hollow carbon particles can be easily produced without using a resin having a concern about toxicity and without requiring a complicated manufacturing process. It aims at providing the manufacturing method of the hollow carbon particle which can be performed, and the hollow carbon particle manufactured using this method.

  In order to achieve the above object, the method (1) for producing hollow carbon particles according to the present invention derives the surface of resin particles obtained by polymerizing a polymerizable vinyl monomer from a nitrogen-containing aromatic compound. It is characterized by firing in an inert gas atmosphere after coating with a polymer.

  According to the manufacturing method (1) of the hollow carbon particles, the polymer derived from the nitrogen-containing aromatic compound is carbonized by firing the resin particles coated with the polymer derived from the nitrogen-containing aromatic compound. While the carbon layer is formed, the resin particles disappear and a hollow portion is formed inside the carbon layer, so that carbon particles having a hollow structure are generated. In the above method, since resin particles obtained by polymerizing a polymerizable vinyl-based monomer are used, it is not necessary to use a resin such as a polyacrylonitrile-based resin having a concern about toxicity. Moreover, in the said method, since the surface of the resin particle should just be coat | covered with the polymer derived from a nitrogen-containing aromatic compound, and it only sinters in the atmosphere of inert gas, a complicated manufacturing process is not required. Therefore, the hollow carbon particles can be easily produced without requiring the use of a resin having a concern of toxicity and without requiring a complicated manufacturing process.

  Moreover, the manufacturing method (2) of the hollow carbon particle which concerns on one form of this invention is a manufacturing method (1) or (2) of the said hollow carbon particle, The said nitrogen-containing aromatic compound is a pyrrole or a pyrrole derivative. It is characterized by that.

  According to the production method (2) of the hollow carbon particles, the coating layer of the polymer derived from the nitrogen-containing aromatic compound can be stably formed, and therefore the carbon layer of the hollow carbon particles can be stably formed. it can.

  Moreover, the method (3) for producing hollow carbon particles according to one aspect of the present invention is the method for producing hollow carbon particles (1) or (2), wherein the shape of the resin particles communicates in the diameter direction. It is characterized by a concave cross section having a notch.

  According to the method (3) for producing hollow carbon particles, hollow carbon particles having a concave outer shape can be produced.

  Moreover, the method (4) for producing hollow carbon particles according to one aspect of the present invention is characterized in that, in the method for producing hollow carbon particles (1) or (2), the resin particles have a mushroom shape. It is said.

  According to the method (4) for producing hollow carbon particles, hollow carbon particles having an outer shape having a mushroom shape can be produced.

  The method (5) for producing hollow carbon particles according to one aspect of the present invention is characterized in that, in the method for producing hollow carbon particles (1) or (2), the resin particles have a hemispherical shape. It is said.

  According to the method (5) for producing hollow carbon particles, hollow carbon particles having a hemispherical outer shape can be produced.

  Moreover, the manufacturing method (6) of the hollow carbon particle which concerns on one form of this invention is that the shape of the said resin particle is a double-sided convex lens shape in the manufacturing method (1) or (2) of the said hollow carbon particle. It is a feature.

  According to the method (6) for producing hollow carbon particles, hollow carbon particles having an outer shape that is a double-sided convex lens shape can be produced.

  Moreover, the manufacturing method (7) of the hollow carbon particle which concerns on one form of this invention is 0 with respect to a nitrogen-containing aromatic compound in any one of the manufacturing methods (1)-(6) of the said hollow carbon particle. By dispersing the resin particles in an aqueous medium containing an alkali metal salt of an inorganic peracid in an amount of 5 to 2.0 molar equivalents, adding a nitrogen-containing aromatic compound to the dispersion, and stirring. The surface of the resin particles is covered with a polymer derived from a nitrogen-containing aromatic compound.

  According to the production method (7) of the hollow carbon particles, the entire surface of the resin particles can be uniformly coated with the polymer derived from the nitrogen-containing aromatic compound, so that the hollow having a carbon layer with a uniform thickness Carbon particles can be produced.

  Moreover, the hollow carbon particle (8) according to the present invention is obtained by any one of the above production methods (1) to (7).

  According to the hollow carbon particles (8), hollow carbon particles having various shapes suitable for various applications can be provided.

It is a schematic explanatory drawing which shows four irregular shaped resin particles which concern on the manufacture example of this invention. It is an electron micrograph which shows the true spherical hollow carbon particle obtained by Example 1 of this invention. It is a transmission electron micrograph which shows the true spherical hollow carbon particle obtained by Example 1 of this invention. It is a scanning electron micrograph which shows the true spherical hollow carbon particle obtained by Example 2 of this invention. It is a scanning electron micrograph which shows the hemispherical hollow carbon particle obtained by Example 3 of this invention. It is a scanning electron micrograph which shows the hollow carbon particle of the double-sided convex lens shape obtained by Example 4 of this invention. It is a scanning electron micrograph which shows the hollow carbon particle of a cross-sectional concave shape obtained by Example 5 of this invention.

  In the method for producing hollow carbon particles according to the present invention, the surface of a resin particle obtained by polymerizing a polymerizable vinyl monomer is coated with a polymer derived from a nitrogen-containing aromatic compound, and then a nitrogen-containing aromatic. In this method, resin particles coated with a polymer derived from a compound (hereinafter referred to as coated resin particles) are fired in an inert gas atmosphere.

  The resin particles obtained by polymerizing the polymerizable vinyl monomer used in the production method of the present invention are not particularly limited as long as they are thermally decomposed and disappeared upon firing.

  The resin particles may be spherical resin particles (hereinafter referred to as spherical resin particles) or irregularly shaped resin particles (hereinafter referred to as irregular resin particles) having a shape different from the spherical shape. Below, a manufacturing method is demonstrated separately in the case of a spherical resin particle, and the case of a deformed resin particle.

(I) Production of spherical resin particles (Polymerization method)
First, a method for producing spherical resin particles according to the embodiment will be described.

  The method for producing the spherical resin particles is not particularly limited, and examples thereof include known polymerization methods such as bulk polymerization, emulsion polymerization, soap-free emulsion polymerization, seed polymerization, and suspension polymerization. In the case of bulk polymerization, resin particles having a desired particle diameter can be obtained by classification after pulverization. Emulsion polymerization refers to a polymerization method in which an aqueous medium such as water, a monomer that is difficult to dissolve in the medium, and an emulsifier (surfactant) are mixed and a polymerization initiator that is soluble in the aqueous medium is added thereto. Emulsion polymerization is characterized by little variation in the particle size obtained. Soap-free emulsion polymerization refers to emulsion polymerization that does not use an emulsifier, and is characterized in that particles having a uniform diameter can be obtained. Seed polymerization refers to emulsion polymerization performed by absorbing a polymerizable vinyl-based monomer into seed (seed) particles separately prepared at the start of polymerization. The seed polymerization is performed by adjusting the particle size, particle size distribution, and amount (number) of the seed particles and the amount of the polymerizable vinyl monomer to be absorbed by the seed particles. It has the characteristic that it can be made to polymerize aiming at the resin particle. Suspension polymerization refers to a polymerization method in which a monomer and an aqueous medium (dispersion medium) such as water are mechanically stirred and suspended. Suspension polymerization is characterized in that particles having a small particle size and a well-shaped shape can be obtained.

  Hereinafter, although seed polymerization is described as an example, the method for producing resin particles according to the present invention is not limited to this polymerization method.

  First, seed particles are added to an emulsion (suspension) composed of a polymerizable vinyl monomer and an aqueous medium. The emulsion can be prepared using a known method. For example, an emulsion can be obtained by adding a polymerizable vinyl monomer to an aqueous medium and dispersing it using a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer. Examples of the aqueous medium include water, a mixture of water and a lower alcohol (alcohol having 5 or less carbon atoms), and the like. The method for producing seed particles is not particularly limited, and methods such as emulsion polymerization, soap-free emulsion polymerization, and suspension polymerization can be used. In consideration of the uniformity of the particle diameter of the seed particles and the simplicity of the production method, emulsion polymerization and soap-free emulsion polymerization are preferable as the production method of the seed particles. The weight average molecular weight of the seed particles can be adjusted by adjusting the amount of the polymerization initiator used or adjusting the amount of the molecular weight modifier added.

(Polymerizable vinyl monomer)
Examples of the polymerizable vinyl monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, Acrylic acid alkyl ester monomers such as stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, alkyl methacrylate monomers, styrene, Aromatic vinyl monomers such as α-methylstyrene, vinyl toluene and ethyl vinyl benzene, saturated fatty acid vinyl monomers such as vinyl acetate, vinyl propionate and vinyl versatic acid, cyanides such as acrylonitrile and methacrylonitrile Single vinyl chloride , Acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid and other ethylene carboxylic acids, maleic anhydride and other ethylene carboxylic acid anhydrides, monobutylmaleic acid and other ethylene dicarboxylic acids Monoalkyl esters, ethylene carboxylates such as ammonium salts or alkali metal salts thereof, acid amides of ethylene carboxylic acids such as acrylamide, methacrylamide, and diacetone acrylamide, N-methylol acrylamide, N-methylol methacryl Methylolated products of ethylene-based carboxylic acid amides such as amides, methylolated diacetone acrylamide, and etherified products of these monomers with alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethylacrylamide) Derivatives thereof, esters of ethylene carboxylic acids such as glycidyl acrylate and glycidyl methacrylate with alcohols having an epoxy group, hydroxyalkyl of ethylene carboxylic acids such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxy methacrylate Monomers having one ethylenically unsaturated bond, divinylbenzene, diallyl phthalate, triaryl, such as esters, esters of ethylene carboxylic acids such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate with alcohols having amino groups And monomers having two or more non-conjugated unsaturated bonds such as lucyanurate and diethylene glycol dimethacrylate.

  These can be used alone or in combination of two or more. Among these polymerizable vinyl monomers, a hydrophobic polymerizable vinyl monomer having a water (20 ° C.) solubility of 1.5% by weight or less is preferable because a more uniform coating film can be obtained. Among hydrophobic polymerizable vinyl monomers having a water (20 ° C.) solubility of 1.5 wt% or less, styrene, butyl acrylate, and butyl methacrylate are more preferable, and butyl acrylate and butyl methacrylate are particularly preferable. preferable. Of these polymerizable vinyl monomers, acrylic acid alkyl ester monomers and methacrylic acid alkyl ester monomers are preferred.

  The polymerizable vinyl monomer may contain a polymerization initiator as necessary. The polymerization initiator may be preliminarily mixed with the polymerizable vinyl monomer and then dispersed in an aqueous medium, or a mixture of both separately dispersed in an aqueous medium may be mixed. The particle diameter of the polymerizable vinyl monomer droplets present in the emulsion is preferably smaller than the seed particles because the polymerizable vinyl monomer is efficiently absorbed by the seed particles.

  The seed particles may be added directly to the emulsion, or may be added in a form in which the seed particles are dispersed in an aqueous medium. After the seed particles are added to the emulsion, the monomer is absorbed by the seed particles. This absorption can be usually performed by stirring the emulsion after addition of seed particles at room temperature (about 20 ° C.) for 1 to 12 hours. Moreover, in order to accelerate | stimulate absorption of a monomer, you may heat an emulsion to about 30-50 degreeC.

  The seed particles swell by absorbing the polymerizable vinyl monomer. The mixing ratio of the polymerizable vinyl monomer and the seed particles is preferably in the range of 5 to 300 parts by weight of the polymerizable vinyl monomer with respect to 1 part by weight of the seed particles, and 100 to 250 parts by weight. More preferably, it is the range. When the mixing ratio of the polymerizable vinyl monomer is small, the increase in the particle diameter due to polymerization is small, and when the mixing ratio of the polymerizable vinyl monomer is large, the polymerizable vinyl monomer is completely seed particles. In some cases, abnormal particles are generated by suspension polymerization in an aqueous medium. The end of absorption of the polymerizable vinyl monomer by the seed particles can be determined by confirming the expansion of the particle diameter by observation with an optical microscope.

  A polymerization initiator is added as needed. The polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and t-butyl. Organic peroxides such as peroxy-2-ethylhexanoate and di-t-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) ), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethylbutyro) Nitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, (2-carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisiso Examples thereof include azo compounds such as butyrate, etc. The polymerization initiator is preferably used in the range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  Next, the polymerizable vinyl monomer absorbed in the seed particles is polymerized to obtain resin particles. The polymerization temperature can be appropriately selected according to the type of the polymerizable vinyl monomer or the polymerization initiator. Specifically, the polymerization temperature is preferably in the temperature range of 25 to 110 ° C, and more preferably in the temperature range of 50 to 100 ° C. The polymerization time is desirably 1 to 20 hours. The polymerization is desirably performed in an inert gas atmosphere inert to the polymerization such as a nitrogen atmosphere. The polymerization reaction is preferably performed by raising the temperature after the polymerizable vinyl monomer and the polymerization initiator are completely absorbed by the seed particles.

  In the polymerization step, a polymer dispersion stabilizer may be added in order to improve the dispersion stability of the resin particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinyl pyrrolidone. An inorganic water-soluble polymer compound such as sodium tripolyphosphate may be used in combination. Of these polymer dispersion stabilizers, polyvinyl alcohol and polyvinyl pyrrolidone are preferred. The addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  In order to suppress the generation of emulsified particles in the aqueous system in the polymerization step, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, polyphenols, etc. May be used.

(II) Production of irregularly shaped resin particles Next, a method for producing irregularly shaped resin particles according to the embodiment will be described.

  The irregular shaped resin particles can be produced by adopting a so-called seed polymerization method in which the seed particles absorb the polymerizable vinyl monomer in the aqueous emulsion and polymerize the absorbed polymerizable vinyl monomer. .

(Shape of irregular shaped resin particles)
The irregular shaped resin particles used in the present invention can be made into various shapes. For example, the irregular resin particles include resin particles having a cross-sectional concave shape (hereinafter referred to as a cross-section horseshoe shape), a mushroom shape, a hemispherical shape, or a double-sided convex lens shape having one notch communicating in the diameter direction. It is done.

  The said shape is demonstrated using Fig.1 (a)-(d).

  FIG. 1 (a) is a projected view showing deformed resin particles having a cross-section of a horseshoe, with the upper drawing showing the maximum projected area and the lower drawing showing the minimum. The outer shape of the particle in the figure with the maximum projected area is circular. Moreover, the external shape of the particle | grain of the figure where a projection area becomes the minimum becomes a shape which the recessed part and sector corresponding to the projection figure of a notch part combined. Here, the deformed resin particles having a horseshoe cross-section have a recess B having a depth B that is 0.1 to 0.9 times the particle diameter A of the resin particles, and 0.1 to the particle diameter A of the resin particles. The width C of the opening is 0.95 times.

  FIG.1 (b) has shown the figure in case the projection area which shows a mushroom-like deformed resin particle becomes the minimum. The odd-shaped resin particles having a mushroom shape or a similar shape as shown in this figure can be considered to be composed of an umbrella portion and a shaft portion. The mushroom-shaped deformed resin particles have a shaft portion having a bottom width D1 of 0.1 to 0.8 times the particle diameter A of the resin particles, and an intermediate portion width D2 of the resin particles. It is 0.2 to 0.9 times A, and the height E in the axial length direction is 0.2 to 1.5 times the particle diameter A of the resin particles.

  FIG.1 (c) is a projection figure which shows hemispherical irregular shaped resin particles, an upper figure is a figure which shows the case where a projection area becomes the maximum, and a lower figure is a figure which shows the case where it becomes the minimum. Here, in the hemispherical irregular shaped resin particles, the height F of the irregular shaped resin particles is 0.2 to 0.8 times the particle diameter A of the resin particles in the semicircular figure having the smallest projected area. Is.

  FIG. 1 (d) is a projected view showing irregularly shaped resin particles having a double-sided convex lens shape (meteorite shape), the upper figure is a figure showing a circular shape with the maximum projected area, and the lower figure shows a case where it is the smallest. FIG. Here, the double-sided convex lens-shaped deformed resin particles are those in which the thicknesses H and I of the convex lenses are 0.2 to 0.8 times the particle diameter A of the resin particles in the lower figure where the projected area is minimized. .

  1A to 1D, the particle diameter A can be set in the range of 0.5 to 30 μm. Moreover, the spherical equivalent volume average particle diameter of the irregular shaped resin particles can be set in the range of 0.5 to 30 μm.

  1 (a) to 1 (d) are diagrams showing shapes for explaining the shapes of deformed resin particles in an easy-to-understand manner. Actually, deformed resin particles having some bulges and dents are also present. Can be used for invention. In addition to the above, irregularly shaped irregular shaped resin particles can also be used in the present invention.

  The shape of the irregular shaped resin particles can be made by appropriately adjusting the ratio of raw materials used, polymerization conditions, and the like. For example, the shape is adjusted by adjusting the composition of the seed particles, the weight average molecular weight of the seed particles, the amount of the polymerizable vinyl monomer used for the seed particles, and the amount of the (meth) acrylic acid ester having an alkylene oxide group. Can be made separately. For example, when the amount of the polymerizable vinyl monomer used for the seed particles is increased, odd-shaped resin particles having a cross-section horseshoe shape are easily obtained. Moreover, when the (meth) acrylic acid ester having an alkylene oxide group is not used, irregularly shaped resin particles having a double-sided convex lens shape are easily obtained. When a small amount of (meth) acrylic acid ester having an alkylene oxide group is used, hemispherical irregular shaped resin particles are easily obtained, and when the amount of (meth) acrylic acid ester having an alkylene oxide group is increased, It is easy to obtain irregular shaped resin particles. Furthermore, when the molecular weight of the seed particles is low, deformed resin particles having a horseshoe cross section are easily obtained. When the molecular weight of the seed particles is increased, hemispherical shaped resin particles are easily obtained, and when the molecular weight of the seed particles is further increased, mushroom-shaped shaped resin particles are easily obtained. In addition, (meth) acryl means methacryl or acryl.

(Raw material for producing irregular shaped resin particles and production method)
Hereinafter, the raw material for manufacturing irregular shaped resin particles and the manufacturing method will be described.

(1) Seed particles Seed particles are (meth) acrylic acid esters (condensation of alkyl alcohols having 3 to 6 carbon atoms and (meth) acrylic acid) containing an alkyl group having 3 to 6 carbon atoms in the ester portion. It is preferable that the resin particle is derived from a polymerizable vinyl monomer containing). The polymerizable vinyl monomer more preferably contains 50% by weight or more of (meth) acrylic acid ester containing an alkyl group having 3 to 6 carbon atoms in the ester portion. Resin particles derived from such a polymerizable vinyl monomer are likely to be non-spherical (deformed) particles. Examples of the alkyl group having 3 to 6 carbon atoms include linear alkyl groups such as n-propyl group, n-butyl group and n-pentyl group, and branched alkyl groups such as isopropyl group, isobutyl group and t-butyl group. Can be mentioned. Specific examples of the (meth) acrylate ester containing an alkyl group having 3 or more and less than 6 carbon atoms in the ester portion include n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Monomers such as butyl, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. These monomers may be used alone or in combination of two or more. Among these, (meth) acrylic acid ester having a branched alkyl group (for example, isopropyl group, isobutyl group, t-butyl group) is preferable because the obtained resin particles are likely to be non-spherical (unshaped) resin particles. .

  The weight average molecular weight of the seed particles is preferably in the range of 150,000 to 1,000,000, and more preferably in the range of 200,000 to 800,000, as measured by GPC (gel permeation chromatography). When the weight average molecular weight of the seed particles is greater than 1,000,000, it is difficult to obtain deformed resin particles, and spherical resin particles may be mixed. That is, when the weight average molecular weight is greater than 1,000,000, the monomer particle absorption capacity of the seed particles may be reduced. As a result, since the polymerizable vinyl monomer is independently polymerized without being absorbed, spherical resin particles different from the target irregular resin particles may be generated. On the other hand, when the weight average molecular weight of the seed particles is less than 150,000, phase separation between the seed particles and the polymerizable vinyl monomer hardly occurs, and it becomes difficult to obtain the desired deformed resin particles.

  The size and shape of the seed particles are not particularly limited. As the seed particles, spherical particles having a particle diameter of 0.1 to 5 μm are usually used.

(2) Method for producing seed particles The method for producing seed particles is not particularly limited, but known methods such as emulsion polymerization, soap-free emulsion polymerization, seed polymerization, suspension polymerization, and the like can be used. The seed particle production method is preferably emulsion polymerization, soap-free emulsion polymerization, or seed polymerization in consideration of the uniformity of the particle diameter of the seed particles and the simplicity of the production method.

  The polymerization for producing seed particles may be performed in the presence of a molecular weight modifier. Examples of molecular weight regulators include α-methylstyrene dimer; mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan; terpenes such as t-terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride. Such chain transfer agents can be used. The molecular weight modifier is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer for producing seed particles.

(3) Polymerizable vinyl monomer The polymerizable vinyl monomer that is absorbed and polymerized by the seed particles preferably contains a crosslinkable monomer. The crosslinking monomer is not particularly limited, and any known crosslinking monomer can be used. As the crosslinkable monomer, for example, a polyfunctional monomer having two or more polymerizable vinyl groups in one molecule, such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and divinylbenzene is used. The amount of the crosslinkable monomer used is preferably in the range of 5 to 50% by weight based on the total amount of the polymerizable vinyl monomer. When the ratio of the crosslinkable monomer is less than 5% by weight or more than 50% by weight, particles having small deformation and almost spherical shape may be obtained. A more preferable amount of the crosslinking monomer used is in the range of 10 to 40% by weight based on the total amount of the polymerizable vinyl monomer.

  If necessary, the polymerizable vinyl monomer preferably contains a monomer other than the crosslinkable monomer. Other monomers include (meth) acrylic acid ester having an alkylene oxide group, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid t-butyl, (meth) acrylamide, 2-hydroxylethyl (meth) acrylate, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate; vinyl acetate; acrylonitrile, etc. It is done.

  Among these, (meth) acrylic acid ester having an alkylene oxide group is preferable as another monomer because non-spherical (abnormal) particles are easily obtained. Examples of the (meth) acrylic acid ester having such an alkylene oxide group include compounds represented by the following general formula.

In the above general formula, R ₁ represents H or CH ₃ , and R ₂ and R ₃ are different and represent an alkylene group selected from C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , and C ₅ H _10. M is 0 to 50, n is 0 to 50 (provided that m and n are not 0 at the same time), and R ₄ represents H or CH ₃ .

  In addition, in the monomer of Formula 1, when m is larger than 50 and when n is larger than 50, the polymerization stability may be lowered and coalescence particles may be generated. The preferable range of m and n is 0-30, and the more preferable range of m and n is 0-15.

A commercially available product can be used as the (meth) acrylic acid ester having an alkylene oxide group. Examples of commercially available products include NOF's Blemmer (registered trademark) series. Furthermore, in the Blemmer (registered trademark) series, Blemmer (registered trademark) 50 PEP-300 (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , R ₃ is C ₃ H ₆ , m and n are averaged. A mixture of m = 3.5 and n = 2.5, R ₄ is H), BREMMER® 70PEP-350B (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , R ₃ Is C ₃ H ₆ , m and n are on average a mixture of m = 3.5 and n = 2.5, R ₄ is H), Blemmer® PP-1000 (R ₁ is CH ₃ R ₃ is C ₃ H ₆ , m is 0, n is a mixture of 4 to 6 on average, R ₄ is H), Blemmer® PME-400 (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , m is a mixture of 9 on average, n is 0, and R ₄ is CH ₃ ).

  The amount of the (meth) acrylic acid ester having an alkylene oxide group is preferably in the range of 0 to 40% by weight, more preferably in the range of 1 to 40% by weight, based on the total amount of the polymerizable vinyl monomer. The range of 5 to 30% by weight is more preferable, and the range of 10 to 20% by weight is particularly preferable. If the amount of the (meth) acrylic acid ester having an alkylene oxide group exceeds 40% by weight of the total amount of the polymerizable vinyl monomer, the polymerization stability may be lowered and the number of coalesced particles may be increased.

(4) Manufacture of irregularly shaped resin particles Manufacture of irregularly shaped resin particles is carried out by allowing the seed particles to absorb the polymerizable vinyl monomer in the aqueous emulsion and polymerize the absorbed polymerizable vinyl monomer. Performed using seed polymerization. Hereinafter, a general method of the seed polymerization method will be described, but the method for producing the irregular shaped resin particles is not limited to this method.

  First, seed particles are added to an aqueous emulsion composed of a polymerizable vinyl monomer and an aqueous medium.

  Examples of the aqueous medium include water, a mixed medium of water and a water-soluble solvent (for example, a lower alcohol having 5 or less carbon atoms), and the like.

  The aqueous medium includes a surfactant. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.

  Examples of anionic surfactants include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfone. Acid salts, alkane sulfonates, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkenyl succinates (dipotassium salts), alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkylphenyl ether sulfates Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfate salts.

  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 zwitterionic surfactants include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants.

  You may use the said surfactant individually or in combination of 2 or more types. Among the surfactants, anionic surfactants are preferable from the viewpoint of dispersion stability during polymerization.

  The aqueous emulsion can be prepared by a known method. For example, an aqueous emulsion can be obtained by adding a polymerizable vinyl monomer to an aqueous medium and dispersing it using a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer. The polymerizable vinyl monomer may contain a polymerization initiator as necessary. The polymerization initiator may be mixed with the polymerizable vinyl monomer in advance and then dispersed in an aqueous medium, or a mixture obtained by separately dispersing both in an aqueous medium. The droplet diameter of the polymerizable vinyl monomer in the obtained aqueous emulsion is preferably smaller than the seed particle because the polymerizable vinyl monomer is efficiently absorbed by the seed particle.

  The seed particles may be added directly to the aqueous emulsion, or may be added in a form in which the seed particles are dispersed in an aqueous dispersion medium.

  After the seed particles are added to the aqueous emulsion, the polymerizable vinyl monomer is absorbed into the seed particles. This absorption can usually be performed by stirring the aqueous emulsion after addition of seed particles at room temperature (about 20 ° C.) for 1 to 12 hours. Moreover, you may accelerate | stimulate absorption by heating an aqueous emulsion to about 30-50 degreeC.

  The seed particles are swollen by absorption of the polymerizable vinyl monomer. The mixing ratio of the polymerizable vinyl monomer and the seed particles is preferably in the range of 5 to 150 parts by weight of the polymerizable vinyl monomer with respect to 1 part by weight of the seed particles. More preferably, it is in the range of parts by weight. When the mixing ratio of the polymerizable vinyl monomer is smaller than the above range, the increase in the particle diameter due to the polymerization is reduced, so that the productivity is lowered. When the mixing ratio of the polymerizable vinyl monomer is larger than the above range, the polymerizable vinyl monomer is not completely absorbed by the seed particles, and is uniquely suspended and polymerized in an aqueous medium to generate abnormal particles. Sometimes. The end of absorption can be determined by confirming the enlargement of the particle diameter by observation with an optical microscope.

  A polymerization initiator is added to the aqueous emulsion as necessary. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexano Organic peroxides such as ate and di-t-butyl peroxide; 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4- And azo compounds such as dimethylvaleronitrile). The polymerization initiator is preferably used in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  Next, the deformed resin particles are obtained by polymerizing the polymerizable vinyl monomer absorbed in the seed particles.

  The polymerization temperature is appropriately selected according to the type of the polymerizable vinyl monomer and the polymerization initiator. The polymerization temperature is preferably in the range of 25 to 110 ° C, more preferably in the range of 50 to 100 ° C. The polymerization reaction is preferably performed by raising the temperature after the monomer and the polymerization initiator are completely absorbed by the seed particles. After completion of the polymerization, if necessary, the shaped resin particles are centrifuged to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.

  In the polymerization step, a polymer dispersion stabilizer may be added in order to improve the dispersion stability of the irregular shaped resin particles.

  Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinyl pyrrolidone. An inorganic water-soluble polymer compound such as sodium tripolyphosphate can also be used in combination. Of these, polyvinyl alcohol and polyvinyl pyrrolidone are preferable. The addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  In order to suppress the generation of emulsified particles in an aqueous system, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols may be used. Good.

(III) Production of coated resin particles The coated resin particles used in the present invention are obtained by dispersing resin particles (spherical resin particles or irregularly shaped resin particles) obtained by polymerization of a polymerizable vinyl monomer by the seed polymerization method described above. It can be produced by polymerizing the nitrogen-containing aromatic compound in the medium thus formed to form a polymer layer derived from the nitrogen-containing aromatic compound on the surface of the resin particles.

(Nitrogen-containing aromatic compounds)
Examples of the nitrogen-containing aromatic compound include pyrrole, aniline, indole, imidazole, pyridine, pyrimidine, pyrazine, and alkyl substituents thereof (for example, a C1-C4 such as a methyl group, an ethyl group, a propyl group, and a butyl group). Derivatives of alkyl groups), halogen substituents (for example, substituents of halogen groups such as fluoro, chloro and bromo groups), and nitrile derivatives. These monomers can be used alone to form a homopolymer, or two or more types can be used in combination to form a copolymer. Since a coating film is easily formed stably, pyrrole and pyrrole derivatives are preferred as nitrogen-containing aromatic compounds.

  The addition amount of the nitrogen-containing aromatic compound may be set in accordance with the desired thickness of the coating layer, but is preferably in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the resin particles. More preferably, it is in the range of parts by weight. When the amount of the nitrogen-containing aromatic compound added is less than 1 part by weight based on 100 parts by weight of the resin particles, the entire surface of the resin particles is not uniformly coated with the polymer derived from the nitrogen-containing aromatic compound, and the desired coating The layer thickness may not be obtained. On the other hand, when the addition amount of the nitrogen-containing aromatic compound is more than 30 parts by weight with respect to 100 parts by weight of the resin particles, the added nitrogen-containing aromatic compound is polymerized alone, and other than the intended coated resin particles can be produced. May end up.

(Polymerization of nitrogen-containing aromatic compounds)
Although it does not specifically limit as superposition | polymerization of a nitrogen-containing aromatic compound, The method of oxidatively polymerizing a nitrogen-containing aromatic compound in the aqueous medium containing an oxidizing agent is preferable.

  Therefore, as a method for producing the coated resin particles used in the present invention, the resin particles are dispersed in an aqueous medium containing an oxidizing agent to form a dispersion, and a nitrogen-containing aromatic compound is added to the dispersion and stirred. A method of coating the surfaces of the resin particles with a polymer derived from a nitrogen-containing aromatic compound is preferable. The nitrogen-containing aromatic compound is preferably added to the dispersion in the state of being dissolved in a solvent to form a solution. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol; ethers such as diethyl ether, isopropyl ether, butyl ether, methyl cellosolve, and tetrahydrofuran; acetone, methyl ethyl ketone, and diethyl ketone. Etc. can be used. The nitrogen-containing aromatic compound becomes a black colored polymer by oxidative polymerization.

(Oxidant)
The oxidizing agent used for the oxidative polymerization is not particularly limited, but includes inorganic acids such as hydrochloric acid, sulfuric acid, and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, ferric chloride, Examples thereof include metal halides such as aluminum chloride, halogen acids such as potassium perchlorate, potassium persulfate, ammonium persulfate, sodium persulfate, and peroxides such as hydrogen peroxide. These may be used alone or in combination. Preferable oxidizing agents include alkali metal salts of inorganic peracids. Specific examples of the alkali metal salt of inorganic peracid include potassium persulfate and sodium persulfate.

It is preferable to use the alkali metal salt of an inorganic peracid so that it may become 0.5-2.0 molar equivalent with respect to the nitrogen-containing aromatic compound whole quantity. Thereby, the obtained coated resin particles are uniformly coated with a polymer derived from the nitrogen-containing aromatic compound over the entire surface. Here, “uniform” means that the fluctuation of the thickness of the polymer layer derived from the nitrogen-containing aromatic compound covering the resin particles is 50% or less.
If the amount of the alkali metal salt of the inorganic peracid used is less than 0.5 molar equivalents relative to the total amount of the nitrogen-containing aromatic compound, the entire surface of the resin particles is uniformly coated with the polymer derived from the nitrogen-containing aromatic compound. In other words, hollow carbon particles having a carbon layer with a uniform thickness may not be obtained. On the other hand, when the amount of the alkali metal salt of the inorganic peracid exceeds 2.0 molar equivalents with respect to the total amount of the nitrogen-containing aromatic compound, the added nitrogen-containing aromatic compound is polymerized alone, and the target coated resin particles There may be cases where something other than this is made. Preferably, it is 1-1.5 molar equivalent.

(Aqueous medium)
The oxidizing agent used for oxidative polymerization is added to an aqueous medium. The aqueous medium is not particularly limited, but water or water and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol; diethyl ether, isopropyl ether, butyl ether, Examples thereof include mixed media with ethers such as methyl cellosolve and tetrahydrofuran; and ketones such as acetone, methyl ethyl ketone and diethyl ketone.

  The aqueous medium to which the oxidizing agent is added preferably has a pH of 3 or more. When the pH is less than 3, the entire surface of the resin particles is not uniformly coated with the polymer derived from the nitrogen-containing aromatic compound, and hollow carbon particles having a carbon layer with a desired thickness may not be obtained. In order to realize a stable coating, it is preferable to adjust the pH to a range of 3 to 10.

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

  Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylsulfonic acids. Salt, alkyl naphthalene sulfonate, alkane sulfonate, succi sulfonate, dialkyl sulfo succinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl phenyl ether sulfate salt, polyoxyethylene alkyl Examples thereof include sulfate ester salts.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxy Examples include ethylene-oxypropylene block polymers.

  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 zwitterionic surfactant include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants.

  You may use the said surfactant individually or in combination of 2 or more types. The addition amount of the surfactant is preferably in the range of 0.0001 to 1 part by weight with respect to 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, copolymers thereof and neutralized products thereof, and polymethacrylic acid, copolymers thereof and neutralized products thereof, polyvinylpyrrolidone, hydroxypropylcellulose (HPC) and the like. Is mentioned. The polymer dispersion stabilizer may be used in combination with the above-described surfactant.

(Oxidative polymerization method)
For example, the above-described oxidation polymerization is performed by using a dispersion (emulsion or suspension) in which resin particles obtained by the seed polymerization method described above and the like and a nitrogen-containing aromatic compound are mixed with an alkali metal salt of an inorganic peracid. It can be carried out by a method in which a mixture is obtained by adding to an aqueous medium, and the mixture is stirred and subjected to oxidative polymerization. The temperature of oxidative polymerization is preferably in the range of -20 to 40 ° C. The time for oxidative polymerization is preferably in the range of 0.5 to 10 hours. If necessary, the dispersion liquid in which the coating resin particles are dispersed is subjected to centrifugal separation or the like to remove the aqueous medium, washed with water or a solvent, and then dried to obtain the coating resin particles.

(IV) Coated resin particles The coated resin particles preferably have a thickness fluctuation of the polymer layer derived from the nitrogen-containing aromatic compound covering the resin particles of 50% or less, preferably 40% or less. preferable.

(V) Production of hollow carbon particles The hollow carbon particles are obtained by firing the coated resin particles in an atmosphere of an inert gas such as nitrogen or argon. By firing in an inert gas atmosphere, the resin particles are thermally decomposed and disappear, while the polymer derived from the nitrogen-containing aromatic compound is carbonized to form a carbon layer, and hollow carbon particles are generated. In order to promote the thermal decomposition of the resin particles and the carbonization of the polymer derived from the nitrogen-containing aromatic compound, the firing temperature is preferably in the range of 500 to 1000 ° C., and the firing time is also the firing temperature. However, it is preferably in the range of 30 minutes to 2 hours.

  The hollow carbon particles obtained by the production method according to the present invention can have a uniform thickness, and can have various irregular shapes. Suitable for Typical applications of the hollow carbon particles obtained by the production method according to the present invention include pigments, ink for inkjet printers, field emission displays, lithium batteries, adsorbents of specific substances and gases, and fuel cells. Catalyst carriers, various polymer conductivity-imparting materials, coating solutions for forming an antistatic layer, conductive fillers in transparent conductive films, in vivo diagnostic reagents, monitor reagent indicating materials, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.

  First, measurement methods and calculation methods in Examples and Comparative Examples will be described.

(Average particle size of seed particles)
The average particle size of the seed particles was measured with an LS230 type manufactured by Beckman Coulter Inc. Specifically, 0.1 g of seed particles and 10 m of a 0.1% nonionic surfactant solution are added and mixed for 2 seconds with a touch mixer TOUCHMIXER MT-31 manufactured by Yamato Scientific Co., Ltd. Thereafter, the test tube is dispersed for 10 minutes using a commercially available ultrasonic cleaner, ULTRASONIC CLEARNER VS-150, manufactured by VervoCrea. The dispersed material is measured while irradiating ultrasonic waves with an LS230 type manufactured by Beckman Coulter, Inc. The optical model at that time is measured according to the refractive index of the prepared seed particles.

(Measurement method of sphere equivalent volume average particle diameter of resin particles)
The electrolyte solution is filled in pores having a pore diameter of 50 to 280 μm, the volume is obtained from the change in conductivity of the electrolyte solution when the particles pass through the electrolyte solution, and the volume-average particle diameter in terms of sphere is calculated. Specifically, the measured average particle diameter is a volume average particle diameter measured by Coulter Multisizer II manufactured by Beckman Coulter, Inc. The measurement is performed according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited. Calibrate and measure using an aperture suitable for the particle size.

  Specifically, 0.1 g of particles and 10 ml of a 0.1% nonionic surfactant solution are put into a commercially available glass test tube. After the input material was mixed for 2 seconds with a touch mixer TOUCHMIXER MT-31 manufactured by Yamato Scientific Co., Ltd., the test tube was preliminarily prepared for 10 seconds using ULTRASONIC CLEANER VS-150 manufactured by VervoCrea Co., Ltd., which is a commercially available ultrasonic cleaner. Disperse. In a beaker filled with ISOTON II (manufactured by Beckman Coulter, Inc .: electrolyte for measurement) equipped with the dispersion, drop it with a dropper while gently stirring, and the concentration meter reading on the body screen is 10%. Fit back and forth. Next, the aperture size, Current, Gain, and Polarity are input to the Multisizer II body according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited, and measured manually. During the measurement, the beaker is stirred gently to the extent that bubbles do not enter, and the measurement is terminated when 100,000 particles are measured.

(Measurement method of weight average molecular weight)
The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC). A weight average molecular weight means a polystyrene (PS) conversion weight average molecular weight. Specifically, the weight average molecular weight is measured as follows.

  A 50 mg sample is dissolved in 10 ml of tetrahydrofuran (THF), filtered through a non-aqueous 0.45 μm chromatographic disk, and then measured using a gel permeation chromatograph. The conditions of the gel permeation chromatograph are as follows.

Gel permeation chromatograph: manufactured by Tosoh Corporation, trade name “Gel permeation chromatograph HLC-8020”
Column: Tosoh Corporation, trade name “TSKgel GMH-XL-L” φ7.8 mm × 30 cm × 2 Column temperature: 40 ° C.
Carrier gas: Tetrahydrofuran (THF)
Carrier gas flow rate: 1 ml / min Injection / pump temperature: 35 ° C
Detection: RI
Injection amount: 100 microliters Standard polystyrene for calibration curve: manufactured by Showa Denko KK, trade name “shodex” weight average molecular weight: 1030000, manufactured by Tosoh Corporation, weight average molecular weight: 5480000, 3840000, 355000, 102000, 37900, 9100 , 2630, 870
(Measuring method of length A to I of irregular shaped resin particles)
The lengths A to I of the irregular shaped resin particles are measured as follows.

  Using a scanning electron microscope JSM-6360LV (manufactured by JEOL Ltd.), observe any 30 deformed resin particles at 5,000 to 10,000 times, measure the dimensions of each part, and calculate the average value. The length was A to I.

(Seed Particle Synthesis Example 1)
A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 600 g of water, 100 g of methyl methacrylate (MMA), and 1.0 g of 1-octanethiol as a molecular weight regulator, and the contents in the separable flask were stirred. The air was replaced with nitrogen and the temperature was raised to 70 ° C. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When the solid content was isolated from the obtained emulsion, the solid content was true spherical fine particles having an average particle diameter of 0.4 μm and a weight average molecular weight of 30,000.

(Seed Particle Synthesis Example 2)
A separable flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 600 g of water, 100 g of methyl methacrylate, and 0.5 g of n-dodecyl mercaptan as a molecular weight regulator, and the air in the separable flask was nitrogenated while stirring. And the temperature was raised to 70 ° C. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When the solid content was isolated from the obtained emulsion, the solid content was spherical fine particles having an average particle diameter of 0.4 μm and a weight average molecular weight of 600,000.

(Seed Particle Synthesis Example 3)
A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 600 g of water and 100 g of methyl methacrylate, the air in the separable flask was replaced with nitrogen while stirring, and the temperature was raised to 70 ° C. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When the solid content was isolated from the obtained emulsion, the solid content was true spherical fine particles having an average particle diameter of 0.43 μm and a weight average molecular weight of 820,000.

(Seed Particle Synthesis Example 4)
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 550 g of water, 70 g of an emulsion containing 14% by weight of spherical particles obtained in Seed Particle Synthesis Example 1, 100 g of methyl methacrylate (MMA), and 1 -The octanethiol 1.0g was prepared, the air in a separable flask was substituted with nitrogen, stirring, and it heated up at 70 degreeC. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When the solid content was isolated from the obtained emulsion, the solid content was spherical fine particles having an average particle diameter of 1.1 μm and a weight average molecular weight of 30,000.

(Seed Particle Synthesis Example 5)
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 550 g of water, 70 g of an emulsion containing 14% by weight of spherical particles obtained in Seed Particle Synthesis Example 2, 100 g of isobutyl methacrylate, and n-dodecyl mercaptan 0.3 g was charged, the air in the separable flask was replaced with nitrogen while stirring, and the temperature was raised to 70 ° C. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When solid content was isolated from the obtained emulsion, the solid content was true spherical fine particles having an average particle diameter of 1.1 μm and a weight average molecular weight of 610,000.

(Seed Particle Synthesis Example 6)
A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 550 g of water, 70 g of an emulsion containing 14% by weight of spherical particles obtained in Seed Particle Synthesis Example 3, and 100 g of isobutyl methacrylate, and stirred. While the air in the separable flask was replaced with nitrogen, the temperature was raised to 70 ° C. While maintaining the internal temperature of the separable flask at 70 ° C., 0.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and stirred for 8 hours to carry out the polymerization reaction. By this polymerization reaction, an emulsion containing 14% by weight of solid content was obtained. When the solid content was isolated from the obtained emulsion, the solid content was true spherical fine particles having an average particle diameter of 1.1 μm and a weight average molecular weight of 830,000.

(Resin Particle Production Example 1)
In a 5 L reactor equipped with a stirrer and a thermometer, 700 g of methyl methacrylate (MMA) as a polymerizable vinyl monomer, 300 g of ethylene glycol dimethacrylate (EGDMA), and 2,2′-azobis ( 6 g of 2-methylbutyronitrile) was added and mixed. The obtained mixture was mixed with 1000 g of ion-exchanged water containing 10 g of sodium succinate as a surfactant, and treated with TK homomixer (manufactured by PRIMIX Corporation) at 8000 rpm for 10 minutes to obtain an aqueous emulsion. To this aqueous emulsion, 360 g of an emulsion containing 14% by weight of true spherical fine particles obtained in Seed Particle Synthesis Example 4 was added with stirring.

  When the aqueous emulsion was observed with an optical microscope after stirring for 3 hours, it was confirmed that the polymerizable vinyl monomer in the aqueous emulsion was absorbed by the seed particles. Thereafter, 2000 g of an aqueous solution in which 40 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA-224E) was dissolved as a dispersion stabilizer was further added to the reactor and polymerized while stirring at 60 ° C. for 6 hours. Resin particles were isolated from the aqueous emulsion after polymerization. The obtained resin particles (hereinafter referred to as “resin particles 1”) had a sphere-converted volume average particle size of 5.2 μm.

(Resin Particle Production Example 2)
In a 5 L reactor equipped with a stirrer and a thermometer, 700 g of methyl methacrylate (MMA) as a polymerizable vinyl monomer, 300 g of ethylene glycol dimethacrylate (EGDMA), and 6 g of benzoyl peroxide as a polymerization initiator were placed. Mixed. The obtained mixture was mixed with 300 g of ion-exchanged water containing 10 g of sodium succinate as a surfactant, and treated with TK homomixer (manufactured by Primics Co., Ltd.) at 8000 rpm for 10 minutes to obtain an aqueous emulsion. To this aqueous emulsion, 360 g of an emulsion containing 14% by weight of true spherical fine particles obtained in Seed Particle Synthesis Example 1 was added with stirring.

  When the aqueous emulsion was observed with an optical microscope after stirring for 3 hours, it was confirmed that the polymerizable vinyl monomer in the aqueous emulsion was absorbed by the seed particles. Then, it superposed | polymerized, stirring at 75 degreeC for 6 hours. The obtained resin particles (hereinafter referred to as “resin particles 2”) had a sphere equivalent volume average particle size of 1.0 μm.

(Resin Particle Production Example 3)
In a 5 L reactor equipped with a stirrer and thermometer, 600 g of methyl methacrylate (MMA), 300 g of ethylene glycol dimethacrylate (EGDMA), poly (ethylene glycol-propylene glycol) monomethacrylate (product) Name: Blemmer (registered trademark) 50PEP-30 / manufactured by NOF Corporation) and 6 g of azobisbutyronitrile as a polymerization initiator were added and mixed. The obtained mixture was mixed with 1000 g of ion-exchanged water containing 10 g of sodium succinate as a surfactant, and treated with TK homomixer (manufactured by PRIMIX Corporation) at 8000 rpm for 10 minutes to obtain an aqueous emulsion. To this aqueous emulsion, 360 g of an emulsion containing 14% by weight of true spherical fine particles having an average particle diameter of 1.1 μm obtained in Seed Particle Synthesis Example 5 was added with stirring.

  After stirring for 3 hours, when the aqueous emulsion was observed with an optical microscope, it was confirmed that the polymerizable vinyl monomer in the aqueous emulsion was absorbed by the seed particles (swelling ratio was about 20 times). Thereafter, as a dispersion stabilizer, 2000 g of an aqueous solution in which 40 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA-224E) was dissolved was further added to the reactor and polymerized while stirring at 60 ° C. for 6 hours. The obtained resin particles (hereinafter referred to as resin particles 3) were hemispherical irregularly shaped resin particles (A = 2.92 μm, F = 1.71 μm) as observed with a scanning electron microscope. The deformed resin particles had a sphere equivalent volume average particle size of 2.60 μm.

(Resin Particle Production Example 4)
Similar to Resin Particle Production Example 3 except that 600 g of methyl methacrylate (MMA) and 300 g of ethylene glycol dimethacrylate (EGDMA) are used as the polymerizable vinyl monomer, and poly (ethylene glycol-propylene glycol) monomethacrylate is not used. Thus, resin particles were obtained.

  The obtained resin particles (hereinafter referred to as resin particles 4) were observed with a scanning electron microscope. As a result, irregularly shaped resin particles having a double-sided convex lens shape (A = 2.88 μm, H = 1.27 μm, I = 0.64 μm). Met. The deformed resin particles had a sphere equivalent volume average particle size of 2.61 μm.

(Resin Particle Production Example 5)
Resin particles were obtained in the same manner as in Resin Particle Production Example 3 except that the swelling ratio was about 40 times.

  The obtained resin particles (hereinafter referred to as “resin particles 5”) were observed with a scanning electron microscope. As a result, the deformed resin particles (A = 3.45 μm) having a concave cross section having one cutout portion communicating in the diameter direction. B = 1.15 μm, C = 1.74 μm). Moreover, the spherical equivalent volume average particle diameter of the irregular shaped resin particles was 3.10 μm.

(Resin Particle Production Example 6)
Resin particles were obtained in the same manner as in Resin Particle Production Example 3 except that the emulsion containing 14% by weight of true spherical fine particles produced in Seed Particle Synthesis Example 6 was used.

  The obtained resin particles (hereinafter referred to as resin particles 6) were observed with a scanning electron microscope. As a result, mushroom-shaped irregular resin particles (A = 3.26 μm, D1 = 1.43 μm, D2 = 1.87 μm, E = 1.80 μm). Moreover, the spherical equivalent volume average particle diameter of the irregularly shaped resin particles was 2.71 μm.

Example 1
To a solution obtained by dissolving 20 g of potassium persulfate in 300 g of water, a suspension (dispersion) in which 50 g of resin particles 1 were dispersed in 50 g of isopropanol was added and stirred. The suspension was cooled to 5 ° C., a solution composed of 10 g of pyrrole and 50 g of isopropanol was further added, and the mixture was stirred for 3 hours for polymerization. Then, solid content was obtained by filtration. The solid content was taken out, washed with water and isopropanol, and dried at 60 ° C. for 12 hours with a vacuum dryer. As a result, black resin particles (coated resin particles) in which the resin particles were coated with a pyrrole polymer were obtained.

  The resulting black resin particles were baked at 500 ° C. for 1 hour in a nitrogen stream to obtain black particles as hollow carbon particles. A scanning electron micrograph of the black particles is shown in FIG. Moreover, the transmission electron micrograph of this black particle is shown in FIG. From these photographs, it can be seen that the black particles obtained in Example 1 are true spherical particles having a hollow structure.

(Example 2)
Black particles were obtained as hollow carbon particles in the same manner as in Example 1 except that the resin particles 2 were used in place of the resin particles 1.

  A scanning electron micrograph of the black particles is shown in FIG. From this photograph, it can be seen that the black particles obtained in Example 2 are true spherical particles.

(Example 3)
Black particles were obtained as hollow carbon particles in the same manner as in Example 1 except that the resin particles 3 were used in place of the resin particles 1.

  A scanning electron micrograph of the black particles is shown in FIG. From this photograph, it can be seen that the black particles obtained in Example 3 are hemispherical irregularly shaped particles.

Example 4
Black particles were obtained as hollow carbon particles in the same manner as in Example 1 except that the resin particles 4 were used in place of the resin particles 1.

  A scanning electron micrograph of the black particles is shown in FIG. From this photograph, it can be seen that the black particles obtained in Example 4 are irregularly shaped particles having a double-sided convex lens shape.

(Example 5)
Black particles were obtained as hollow carbon particles in the same manner as in Example 1 except that the resin particles 5 were used in place of the resin particles 1.

  A scanning electron micrograph of the black particles is shown in FIG. From this photograph, it can be seen that the black particles obtained in Example 5 are irregular shaped particles having a concave cross section.

(Example 6)
Mushroom-like black particles as hollow carbon particles were obtained in the same manner as in Example 1 except that the resin particles 6 were used instead of the resin particles 1.

Claims (8)

  Hollow carbon, characterized in that the surface of resin particles obtained by polymerizing a polymerizable vinyl monomer is coated with a polymer derived from a nitrogen-containing aromatic compound and then fired in an inert gas atmosphere Particle manufacturing method.   The method for producing hollow carbon particles according to claim 1, wherein the nitrogen-containing aromatic compound is pyrrole or a pyrrole derivative.   3. The method for producing hollow carbon particles according to claim 1, wherein the shape of the resin particles is a concave cross section having one notch communicating in the diameter direction.   The method for producing hollow carbon particles according to claim 1, wherein the resin particles have a mushroom shape.   The method for producing hollow carbon particles according to claim 1 or 2, wherein the resin particles have a hemispherical shape.   The method for producing hollow carbon particles according to claim 1 or 2, wherein the resin particles have a double-sided convex lens shape.   The resin particles are dispersed in an aqueous medium containing an alkali metal salt of an inorganic peracid in an amount of 0.5 to 2.0 molar equivalents relative to the nitrogen-containing aromatic compound, and the nitrogen-containing aromatic is added to the dispersion. The hollow carbon particles according to any one of claims 1 to 6, wherein the surface of the resin particles is coated with a polymer derived from a nitrogen-containing aromatic compound by adding and stirring the compound. Production method.   The hollow carbon particle obtained by the manufacturing method of any one of Claims 1-7.