KR20050091078A - Composite particles and method for production thereof and use thereof - Google Patents

Abstract

Composite particles which are composed of larger particles and, carried thereon, smaller particles, wherein said smaller particles are fine particles containing a photocatalyst and having an average particle diameter of 0.005 to 0.5 mum as calculated from a BET specific surface area, and said larger particles have an average particle diameter of 2 to 200 mum as measured by the laser diffraction/scattering particle size measuring method. The smaller particle is preferably a composite particle comprising titanium dioxide and an inorganic compound exhibiting no photocatalytic activity, such as silica, or a particle containing a salt of a bronsted acid, in particular, a titanium dioxide particle having a bronsted acid present on the surface thereof; and an advantageous method for producing the above composite particles which comprises subjecting above larger particles and smaller particles to a dry mixing by means of a ball-mill or to a mixing by the rotation of a blade or by shaking, with an energy coefficient controlled within a specific range. Forming a composition comprising an organic polymer and the above composite particles into a shaped article can provide a shaped article, such as a fiber, film or a plastic, exhibiting ultraviolet ray shielding capability.

Description

Composite particle | grains, its manufacturing method, and its use {COMPOSITE PARTICLES AND METHOD FOR PRODUCTION THEREOF AND USE THEREOF}

TECHNICAL FIELD This invention relates to a composite particle, its manufacturing method, and its use.

The composite particles of the present invention carry fine particles having a photocatalytic ability with large particles, and are thus useful as structures, moldings, films, fibers and the like having a photocatalytic function because they effectively exhibit the photocatalytic ability.

Many are known as inorganic fine particles having a photocatalytic ability. The most representative of the inorganic fine particles is titanium dioxide.

Titanium dioxide absorbs ultraviolet light and generates electrons and holes inside it. The hole reacts with the adsorbed water of titanium dioxide to produce hydroxy radicals and decomposes the organic matter adsorbed on the titanium dioxide particle surface into carbon dioxide gas or water. (Co-authored by Akira Fujishima, Kazuhito Hashimoto, and Watabe Toshiya, SIEM, Inc. (1997). Although this is called a photocatalytic action, as conditions of the strong titanium dioxide of this action, the thing which is easy to generate | occur | produce a hole, and the thing which is easy to reach a hole in the titanium dioxide surface are mentioned. `` All of titanium dioxide photocatalyst '' (Hashimoto Kazuhito, Fujishima Akira, CEM Co., Ltd., (1997)) is a titanium dioxide having a high photocatalytic effect, anatase-type titanium dioxide, titanium dioxide with little lattice defect, Small and large specific surface area titanium dioxide is mentioned.

Since this photocatalytic action can decompose most organic materials, it functions as antibacterial, self-self cleaning, deodorant, antifouling by supporting titanium dioxide on the surface of tiles, building materials, building structural materials, fibers, films and the like. Can be given.

However, since photocatalytic action takes place on the surface of titanium dioxide, it is necessary to arrange titanium dioxide on the surface of the member. As a simple method of responding to this demand, a method of mixing titanium dioxide with a binder and applying it to a member is usually performed. However, when the organic polymer is used as the binder, since the binder is oxidized and decomposed by the photocatalytic action, it is necessary to use a hardly decomposable binder such as a fluororesin or a silicone resin (Japanese Patent No. 2756474, Japan). Patent 3027739).

By the way, when a photocatalytic semiconductor particle is mix | blended and used for these resin binders, there existed a problem that a binder coat | covers the surface of titanium dioxide, hinders the arrival of the light or a to-be-decomposed substance to a photocatalyst particle, and reduces the effect of a photocatalytic effect. Moreover, it was also necessary to harden resin by heating.

Next, a composite particle is demonstrated. Titanium dioxide particles are compounded for various purposes. In most cases, compounding is composed of a combination of large-diameter particles (hereinafter referred to as "parent particles") and small-diameter particles (hereinafter referred to as "subparticles"), so that the mother particles can more effectively draw out the functions of their own particles. It is used for When there is no big difference in particle diameter, the microparticles | fine-particles which have an expected function are called particle | grains, and the particle used for expressing it effectively is called a mother particle.

In the production of composite particles containing titanium dioxide, most of them use titanium dioxide as their own particles. This is because titanium dioxide has various functions such as hiding ability, photocatalytic ability, and ultraviolet shielding ability, and the parent particles are selected to effectively express their functions. For example, in order to maximize the ultraviolet shielding ability of ultra-titanium dioxide particles, a method of using a mother particle defined by a refractive index difference and a band gap (Japanese Patent Laid-Open No. 11-131048, Japanese Patent Laid-Open No. 9) -100112, Japanese Patent Application Laid-Open No. 8-268707), a method of using silica particles as a mother particle to impart transparency for the same purpose (Japanese Patent Application Laid-Open No. 2000-344509), and the concealability of titanium dioxide In order to be appropriately expressed, there is a method of combining with calcium carbonate particles as parent particles (Japanese Patent Laid-Open No. 2002-29739). In addition, in order to effectively express the photocatalytic ability of titanium dioxide, a method of supporting titanium dioxide with an organic binder on the surface of the inorganic powder (Japanese Patent No. 3279755), even when in contact with the resin, exhibits a photocatalytic ability without deteriorating the resin. For this purpose, there is a method of using aluminosilicate particles as the mother particles (Japanese Patent Laid-Open No. 11-76835). In addition, as a method of compounding particles, a high-speed airflow impact method (Japanese Patent Laid-Open Publication No. Hei 3-2009, Japanese Patent Laid-Open Publication No. Hei 6-210152) which mechanically combines a mother particle and a magnetic particle, and a surface fusion method (Japan Patent 2672671).

Since titanium dioxide has a photocatalytic ability, it was practically very restrictive. That is, when organic polymer is used as the binder, the binder is oxidized and decomposed by the photocatalytic action. For example, even if a hardly decomposable binder such as a fluororesin or a silicone resin is used, the surface of the titanium dioxide is coated, which hinders the arrival of light or the substance to be decomposed to the photocatalyst particles, thereby reducing the effect of the photocatalytic action. . Furthermore, it was necessary to harden resin by heating. In addition, in order to sufficiently exhibit the function of titanium dioxide, such a problem could not be avoided even as a composite particle.

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocatalyst particle which effectively elicits a function of an inorganic oxide having titanium dioxide and other photocatalytic ability, and also has few practical restrictions, an organic polymer composition and an application product containing the same. To provide.

As a result of the careful investigation by the present inventors, as a small particle, photocatalyst-containing fine particles having a specific average particle diameter in terms of a BET specific surface area in terms of particle size, in particular, titanium dioxide silica composite fine particles, or fine particles containing Brönstedate, in particular Bronsted By using titanium dioxide microparticles | fine-particles which an acidic acid exists in the surface, and carrying out complex granulation with large particle | grains, the knowledge which the problem of the said prior art can be solved was acquired, and based on this knowledge, the present invention was completed.

That is, according to this invention, the following composite microparticles | fine-particles, the manufacturing method of composite microparticles | fine-particles, the organic polymer composition containing composite microparticles | fine-particles, and application of composite microparticles | fine-particles are provided.

(1) A composite particle in which small particles are supported on large particles, wherein the small particles are photocatalyst-containing fine particles having an average particle diameter of 0.005 µm to 0.5 µm in terms of BET specific surface area, and the large particles are laser diffraction / A composite particle having an average particle diameter of 2 to 200 µm measured by a scattering particle size analysis method.

As typical embodiment of the composite grain | particle of said (1), following (2)-(12) is mentioned.

(2) The composite particle according to the above (1), wherein the small particles contain titanium dioxide as a photocatalyst.

(3) The composite particle according to the above (1), wherein the small particle is a composite particle of titanium dioxide and an inorganic compound that does not express photocatalytic ability.

(4) The composite particle according to the above (3), wherein the inorganic compound that does not exhibit photocatalytic ability is silica, and the proportion of silica contained in the small particles is 0.5% by mass or more and 50% by mass or less.

(5) The composite particle according to any one of (1) to (4), wherein the small particles contain Bronsted Salt.

(6) The composite particle according to the above (5), wherein the small particles are titanium dioxide particles in which Bronsted acid salt is present on the surface.

(7) The composite particle according to the above (6), wherein the brönsted acid salt is a condensed phosphate.

(8) The composite particle according to any one of the above (5) to (7), wherein the small particles contain 0.01% by mass to 50% by mass of Bronsted Salt.

(9) The composite particle according to any one of (2) to (8), wherein titanium dioxide contains a brookite crystal phase.

(10) The composite particle according to any one of (1) to (9), wherein the large particle is a spherical resin particle having a melting point of 150 ° C or higher.

(11) The composite particle according to any one of (1) to (9), wherein the large particle is a hydroxide, oxide, or carbonate containing at least one selected from the group consisting of Al, Mg, Ca, and Si.

(12) The composite particle according to any one of (1) to (11), wherein the ratio of the small particles to the large particles is 0.5% by mass or more and 40% by mass or less.

(13) In the method of dry mixing a material containing large particles and small particles in a ball mill, and manufacturing the composite particles, the energy constant (k) of the dry mixing is defined as wp (g) for the total mass of the particles to be mixed. When the media mass is wm (g), the ball mill vessel diameter is d (m), the rotation speed is n (rpm), and the mixing time is t (minutes),

       k = (wm / wp) × d × n × t (1)

Dry mixing is performed on condition that k represented by the relationship which becomes into 50 or more and 50,000 or less is manufactured, The method of manufacturing the composite particle in any one of said (1)-(12) characterized by the above-mentioned.

(14) Using a powder processing apparatus of a type that mixes, pulverizes and stirs materials containing large particles and small particles by rotating the blades, the blade rotation speed is n (rpm) and the mixing time is t (minutes). When I made it)

                        k2 = n × t (2)

A method for producing the composite particle according to any one of the above (1) to (12), wherein the blades are rotated under the condition that k2 represented by the relation to be 250 or more and 50,000 or less.

(15) Using a powder processing apparatus of a type which mixes, pulverizes and stirs materials containing large particles and small particles by vibrating, n is set for vibration frequency (times / minute) and t is the mixing time. When we did)

                         k3 = n × t

The method for producing a composite particle according to any one of the above (1) to (12), wherein the vibration is performed under the condition that k3 represented by the relation to be 50 or more and 50,000 or less.

(16) An organic polymer composition comprising an organic polymer and the composite particles according to any one of the above (1) to (12), wherein the content of the composite particles is 0.01 to 80 mass% in the total mass of the composition. .

As typical embodiment of the organic polymer composition as described in said (16), following (17)-(19) is mentioned.

The organic polymer composition as described in said (16) whose organic polymer is at least 1 sort (s) of resin chosen from the group which consists of a synthetic thermoplastic resin, a synthetic heat changeable resin, and a natural resin.

(18) The organic polymer composition according to the above (16) or (17), wherein the organic polymer composition is a compound.

(19) The organic polymer composition according to the above (16) or (17), wherein the organic polymer composition is a master batch.

(20) A molded article formed by molding the organic polymer composition according to any one of (16) to (19).

Examples of the application of the composite particles described in the above (1) to (12) include the following (21) to (26).

(21) The coating agent containing the composite grain | particle of any one of said (1)-(12).

(22) A paint containing the composite particles according to any one of (1) to (12).

(23) The structure provided with the composite particle in any one of said (1)-(12) on the surface.

(24) Cosmetics containing the composite particle in any one of said (1)-(12).

(25) Fibers containing the composite particle in any one of said (1)-(12).

(26) The film containing the composite grain | particle of any one of said (1)-(12).

In the composite particles according to the present invention, the small particles supported on the large particles are photocatalyst-containing fine particles having an average particle diameter of 0.005 µm to 0.5 µm in terms of BET specific surface area, and the large particles are laser diffraction / scattering particle size analysis methods. It is characterized by having an average particle diameter of 2-200 micrometers measured by.

As the photocatalyst-containing particles, particles which are excited by ultraviolet light or visible light to generate conduction electrons and holes are used. Specific examples thereof include titanium dioxide, tin oxide, zinc oxide, ferric oxide, tungsten trioxide, bismuth trioxide, and titanium. And particles of strontium oxide. Among them, chemically stable titanium dioxide is preferable.

In particular, the magnetic particles are preferably composite particles of titanium dioxide, which is a photocatalyst, and an inorganic compound that does not express photocatalytic ability. As an inorganic compound which does not express photocatalytic ability, the inorganic compound containing Mg, Si, Ca, Fe, Zr etc. is used, and silica is especially preferable.

As the self-particles, composite particles of titanium dioxide, which is a photocatalyst, and an inorganic compound that does not exhibit photocatalytic ability, particularly titanium dioxide-silica composite particles, are preferable because the titanium dioxide component in the self-particles has a photocatalytic ability and a photocatalyst. Mg, Al, Si, Ca, Fe, Zr, etc., in the inorganic compound particles that do not express their ability, have a strong connection between organic particles such as parent particles and magnetic particles, or magnetic particles and resin via oxygen atoms. This is because the function as a binder is expressed. Moreover, since the magnetic particle component which does not express a photocatalytic ability does not decompose binders, such as an organic polymer in contact, it becomes excellent also in weather resistance. In addition, selecting a combination in which the magnetic particles and the mother particles firmly bond is particularly excellent as the composite particles. Thus, by using a composite particle of titanium dioxide and an inorganic compound which does not express photocatalytic ability as a magnetic particle, as a magnetic particle, even if a normal organic polymer binder is used, a photocatalyst is used. It became possible to manufacture the structure which exhibits a capability and also excellent in durability.

Moreover, the small particle containing Bronsted salt can also be used preferably. As small particles containing Bronsted acid salts, self-particles having Bronsted acid salts present on the photocatalytic particle surface, particularly titanium dioxide particle surface, are preferable. This is because the Brönstedate present on the surface of the titanium dioxide particles expresses its function as a firm binder for connecting the parent particles and the child particles. In the case where particles of Brönstedate are present on the surface of the magnetic particles are used, the photocatalytic ability can be exhibited even by weak light having an ultraviolet intensity of about 6 mW / cm 2 such as a fluorescent lamp.

Thus, by using titanium dioxide silica composite fine particles and / or titanium dioxide fine particles containing Bronsted acid salt as the self-particles, a structure having excellent photocatalytic ability and excellent durability even using a conventional organic polymer binder can be easily Can be manufactured.

Although the form of Bronsted salt on the surface of a small particle | grain is not specifically limited, It is preferable to partially cover a particle surface, and it may exist in what kind of states, such as island shape and a muskmelon shape.

In addition, when the composite particles of the present invention are incorporated into a resin or the like to form a film or fibrous when the titanium dioxide silica composite fine particles or the titanium dioxide fine particles containing Bronsted acid salt as composite particles are complexed with the parent particles having an appropriate size When applied to the surface of the substrate together with the binder, or introduced into the structure member, a part of the parent particles can be exposed on the surface of the film, fiber, coating film or structure, and furthermore, The titanium dioxide component may be exposed. In addition, even when an organic polymer is used as the binder, since the surface of the parent particles having no photocatalytic ability is in contact with the binder, even if a part of the organic binder in contact with titanium dioxide is oxidized and decomposed by the photocatalytic action of titanium dioxide. Since the bond between the organic binder and the composite particles is maintained, the titanium dioxide-silica composite fine particles or the titanium dioxide fine particles containing the bronsted acid salt on the surface of the mother particles do not fall off from the mother particles. Therefore, when the composite particle of this invention is used, it can be set as the structure which can exhibit a photocatalytic ability for a long time. Therefore, there is no need to use an expensive decomposable binder such as an expensive fluororesin or a silicone resin.

In the composite particles of the present invention, the ratio of the small particles to the large particles is preferably 0.5% by mass or more and 40% by mass or less. If the amount of the small particles is too small, sufficient photocatalytic ability cannot be obtained. On the contrary, if the amount of the small particles is excessive, the above exfoliation effect of exposing a part of the parent particles on the surface of the structure is insufficient, and further, the dioxide present on the surface of the mother particles is insufficient. Exposure of the titanium component is also likely to be insufficient.

The titanium dioxide-silica composite fine particles which can be preferably used in the present invention are preferably a composite metal oxide (mixed particles) in which titanium dioxide and silicon oxide exhibit a mixed state in the primary particles. The method for producing ultrafine grained mixed oxides in which titanium dioxide and silicon oxide exhibit a mixed state in the primary particles may be either a liquid phase method or a vapor phase method, and there is no particular limitation, for example, in a method as shown in WO01 / 56930. It can manufacture. For example, a mixed gas and an oxidizing gas each containing at least one compound selected from chlorides, sulphides, and oxides of titanium, and at least one compound selected from chlorides, sucrose, and oxides of silicon are preheated to 500 ° C or higher, respectively. It is produced by the gas phase reaction.

When the composite particles used in the present invention are expected to have functions other than the photocatalytic ability of titanium dioxide, the composite particles may have a core (nucleus) / shell (shell) structure with a dissimilar metal oxide crystal structure, for example, in primary particles. In the titanium dioxide-silica composite fine particles containing a mixed state in which a titanium-oxygen-silicon bond is present, it is possible to have a structure in which the TiO ₂ phase is rich in the core and the SiO ₂ phase is rich in the shell. As a form in which a silicon oxide phase exists in a shell, it may exist as a dense layer, and may be an island shape, an island shape, and a muskmelon shape.

Regardless of the application, however, the magnetic particles of the present invention are preferably not a simple mixture of titanium dioxide powder and silica powder. As the titanium dioxide contained in the composite metal oxide in which titanium dioxide and silicon oxide exhibit a mixed state in the primary particles, any of the crystal phases of anatase type, rutile type, and brookite type can be preferably used. In view of the height of the photocatalytic activity, it is preferable to contain anatase type or brookite type titanium dioxide. From the standpoint of UV shielding, rutile type or anatase type is preferable.

As for the magnetic particle used by this invention, primary particle diameter (it shows as particle diameter converted from BET specific surface area in this invention) is 0.005-0.5 micrometer (5-500 nm), Preferably it is 0.02-0.2 micrometer, More preferably, Is 0.05-0.15 micrometer. Here, the BET specific surface area converted particle diameter (D1) can be calculated | required from the following formula after converting a particle into spherical form.

                    D1 = 6 / ρS

                    (ρ: density of particles, S: specific surface area of particles)

The smaller the particle diameter, the larger the specific surface area, the higher the photocatalytic activity of the photocatalyst, so that the primary particle diameter is 0.5 µm or less. When the primary particle diameter of the magnetic particles is larger than 0.5 mu m (500 nm), the photocatalytic function is generally low. However, when the primary particle diameter of the magnetic particles is smaller than 5 nm, the powder containing the magnetic particles is high in volume, making handling difficult or extremely deteriorating in productivity.

The silica concentration in this magnetic particle is 0.5-50 mass%, Preferably it is 1-30 mass%, More preferably, it is 1.5-25 mass%. When the composition of silica is lower than 0.5 mass%, yellowing and the fall of intensity | strength by the light irradiation of the organic structure containing it are confirmed. This may be because the contact probability between titanium dioxide and organic components increases. In the case of the self-particles having more than 50% by mass of silica, a defect occurs that makes it difficult to express the function of the photocatalyst of titanium dioxide. This is because the proportion of titanium dioxide in the magnetic particles becomes small.

Next, the small particle containing Bronsted salt will be described.

Although it does not specifically limit as Bronsted salt, A phosphate, a condensation phosphate, a borate, a sulfate, a condensation sulfate, a carboxylate, etc. are mentioned. Especially, the salt which can produce | generate the metal which comprises a mother particle and a poorly water-soluble compound is preferable. Especially, polybasic acid salts, such as a condensation phosphate, a borate, a condensation sulfate, and a polyvalent carboxylate, are preferable, More preferably, they are condensation phosphate.

Examples of condensed phosphates include pyrroline salts, tripolyphosphates, tetrapolyphosphates, metaphosphates and ultraphosphates. Especially, pyrroline salt and a tripolyphosphate salt are preferable.

The braunstain salts may be present alone, or may be present as a plurality of combinations.

It is preferable that content of Bronsted salt in a small particle is 0.01 mass%-50 mass%. When the content of Bronsted acid salt is too small, it becomes difficult to exert a photocatalytic ability in response to weak light, and the durability of the photocatalyst structure tends to be lowered. Conversely, when the content of bronsted acid salt is excessive, the area of a substance having a photocatalytic ability, such as titanium dioxide, exposed to the particle surface may be reduced, and the photocatalytic ability may be lowered.

It is preferable that the BET specific surface area of a small particle is 5-300 m <2> / g, and the average particle diameter converted from the BET specific surface area in this case is 0.005-0.3 micrometer. The BET specific surface area of the small particles is more preferably 30 to 250 m 2 / g, still more preferably 50 to 20 m 2 / g. If the BET specific surface area of the small particles is less than 10 m 2 / g, the photocatalytic capacity is small. If it is larger than 30Om2 / g, productivity is bad and it is not practical.

The crystal form of titanium dioxide does not mind any of anatase type, rutile type, and brookite type. Preferably, it is anatase type or brookite type, More preferably, it is brookite type. Moreover, even if it contains 2 or more types of crystal forms of an anatase type, a rutile type, and a brookite type, it does not mind. If it contains 2 or more types of crystal forms, the activity may improve compared with the case of each single crystal form.

As the production process of titanium dioxide, is not particularly limited, for example, a vapor phase method and, TiCl ₄ aqueous solution of sulfuric acid or an aqueous solution of titanyl the TiCl ₄ as raw materials has a liquid phase method in which a raw material. As an example of a liquid phase method, the method described in Unexamined-Japanese-Patent No. 11-43327, ie, titanium tetrachloride is added to the hot water of 75-100 degreeC, and it hydrolyzes in the temperature range of 75 degreeC-the boiling point of a solution, and the brookite type dioxide The method of manufacturing the water dispersion sol of a titanium particle is mentioned.

In order to efficiently support titanium dioxide on the surface of the mother particle, it is preferable to use such liquid-synthesized titanium dioxide as a raw material. In addition, it is preferable to use liquid-synthesized titanium dioxide, without the process of obtaining the powder of titanium dioxide, in other words, maintaining the slurry state at the time of the synthesis | combination. This is because if the step of obtaining powder after liquid phase synthesis is adopted, aggregation of titanium dioxide occurs. In addition, there is a method of cracking the agglomeration by using an airflow grinder such as a jet mill or a micronizer, a roller mill, a pulperizer, or the like, but this is not preferable because the process becomes long.

It is preferable that the density | concentration of titanium dioxide in the aqueous slurry containing titanium dioxide is 0.1-10 mass%. More preferably, it is 0.5-5 mass%. If the slurry concentration of titanium dioxide is larger than 10% by mass, it is not preferable because titanium dioxide aggregates in the mixing step described later. Moreover, when it is less than 0.1 mass%, productivity is bad and it is unpreferable.

Moreover, as for pH of titanium dioxide in the aqueous slurry containing titanium dioxide, 3-5 are preferable. If the pH is lower than 3, it is not preferable in the following reaction step because of the aggregation of titanium dioxide by local neutralization and heat generation during mixing. It is not preferable because the aggregation of titanium dioxide proceeds when the pH is higher than 5 Can not do it. After adjustment of the aqueous slurry of vapor phase titanium dioxide or liquid phase titanium dioxide, the pH can be adjusted using methods such as electrodialysis or treatment with an ion exchange resin, if necessary.

The means for complexing the bromide salt with titanium dioxide is not particularly limited, but it is preferable to prepare an aqueous solution containing bromide salt. The method of adding and dissolving it as a powder as a bruxed acid salt to a titanium dioxide slurry may be undesirable because the absorption rate of visible light of titanium dioxide may decrease.

In addition, when Bronsted acid salt is poorly water-soluble, it is preferable to prepare the aqueous solution of the some raw material which can produce a poorly water-soluble compound. For example, in order to complex | combine calcium pyrrolate with titanium dioxide, it is preferable to prepare the sodium pyrolate aqueous solution and the calcium chloride aqueous solution.

40 mass% or less is preferable, and, as for the density | concentration of the compound in the aqueous solution containing Bronsted salt, More preferably, it is 20 mass% or less. When the concentration exceeds 40% by mass, local agglomeration of titanium dioxide occurs in the next mixing step, which is not preferable.

The total amount of Bronsted acid salt to be prepared may be obtained by obtaining a small particle containing 0.01 mass% to 50 mass% of Bronsted acid salt, and is usually 0.01 mass% to 10.0 mass% with respect to the titanium dioxide mass, preferably Is in the range of 0.1% by mass to 50% by mass. If the total amount of Bronsted acid salt is less than 0.01% by mass, the reactivity with titanium dioxide deteriorates. On the other hand, when the total amount of Bronsted acid salt is more than 50 mass%, it will become economically disadvantageous and the aggregation of titanium dioxide may advance.

Next, the aqueous slurry containing titanium dioxide and the aqueous solution containing Bronsted acid salt are mixed and reacted.

As pH to mix, 4-10 are preferable. Also preferably, they are 5-9. If the pH is lower than 4, the reactivity of the titanium dioxide and the bransted acid salt is low and undesirable. In addition, when the pH is higher than 10, aggregation of titanium dioxide occurs during mixing, which is not preferable.

In order to adjust the pH at the time of mixing, pH may be adjusted when mixing with the slurry containing titanium dioxide and the aqueous solution containing Brönstedate, and it may be adjusted in advance so that pH at the time of reaction mixing may enter into a setting range. The pH of the aqueous solution containing tedate may be adjusted. As a method of pH adjustment, the mineral acid like hydrochloric acid and a sulfuric acid, the aqueous solution of sodium hydroxide, ammonia, etc. can be used. However, in order to avoid local aggregation of titanium dioxide and the produced composite grain | particle of a raw material in the mixing part of a pH adjuster, it is preferable to suppress the use amount of a pole force, or to use it at a lean density | concentration.

As a method of mixing the aqueous slurry containing titanium dioxide and the aqueous solution containing Bronsted acid salt, the method of continuously adding the aqueous solution containing Bronsted acid salt to the aqueous slurry containing titanium dioxide may be sufficient, and both The method of adding to a reaction tank simultaneously is mentioned.

It is preferable that the density | concentration of titanium dioxide after mixing the aqueous slurry containing titanium dioxide and the aqueous solution containing Brönstedate is 5 mass% or less. Preferably, it is 3 mass% or less. When compounding is carried out so that the concentration after mixing exceeds 5% by mass, local aggregation of titanium dioxide occurs at the time of mixing, which is not preferable.

It is preferable that the reaction temperature of the aqueous slurry containing titanium dioxide and the aqueous slurry containing Brönstedate is 50 degrees C or less. More preferably, it is 30 degrees C or less. When it exceeds 50 degreeC, aggregation of the microparticles | fine-particles in a reaction tank may advance.

The aqueous slurry after the reaction can also be desalted. Removing excess salt is effective because it increases the dispersibility of the particles. Examples of the desalting method include a method of using an ion exchange resin, a method of using electrodialysis, a method of using an ultrafiltration membrane, a method of using a rotary filter press (for example, manufactured by Kotobuki Institute of Technology), and the like. have.

Normally, photocatalytic activity decreases when a compound that is inert as a photocatalyst is present on the surface of titanium dioxide, but surprisingly, when surface treatment is performed by the above method, an inert compound as a photocatalyst is present on the surface of titanium dioxide, compared to an untreated product. It found that the photocatalytic activity improved. Moreover, such an effect is reliably exhibited by suppressing aggregation of raw material titanium dioxide and the produced | generated composite particle as much as possible throughout the process like this invention. In particular, when partially surface-treated with a polybasic acid, it becomes remarkable and evident. The reason for this is not clear, but a plurality of electron-absorbing carboxyl groups or sulfonyl groups preferentially interact with specific Ti atoms on the surface of titanium dioxide, so that electrons generated in the titanium dioxide particles by light absorption are absorbed on the surface. It is thought that one reason may be that charge is separated and the photocatalytic activity is improved as a result.

In addition, it is considered that the energy level of the complex oxide containing specific Ti is newly formed on the surface of titanium dioxide, and depending on the kind of the complex oxide, it may have a band gap capable of responding to visible light. In general, it is thought that the surface treatment of an inert material as a photocatalyst inhibits the photocatalytic activity of titanium dioxide, but not necessarily. On the other hand, the surface treatment unit is at least the terminal atomic end portion thereof is photocatalytically inert, and in three dimensions also suppresses contact between the organic material and titanium dioxide, and when the particles are applied to the organic material, the durability is improved. There is also an advantage. Generally, the substance to be degraded is a gas or a liquid, and the positional relationship between them and the photocatalyst particles is fluid (that is, the substance to be hydrolyzed), whereas the organic substrate is solid, and the three-dimensional positional relationship between the photocatalyst particles and the organic substrate is It can be understood that the above phenomenon can be realized from a fixed relationship.

That is, by the surface treatment process in which the dispersibility of titanium dioxide particles is maintained, an efficient interaction of polybasic acid and a specific surface Ti atom is realized for the first time, whereby both of the photocatalytic activity exceeding the raw material and weather resistance can be reliably shown simultaneously. Can be.

Small particles in which Brönstedate is present on the surface of titanium dioxide can be dried and taken out as a powder. In that case, it is accompanied by aggregation, and it is good to crack using an airflow grinder, a roller mill, a pulverizer, etc., such as a jet mill and a micronizer.

As the parent particles, particles having an average particle diameter of 2 to 200 µm, preferably 3 to 100 µm, and more preferably 3 to 80 µm, measured by laser diffraction / scattering particle size analysis are used. It is suitable to arrange | position to a member surface that particle diameters are this range, and when it is smaller than this, it is difficult to arrange | position to a member surface, and when it is large, the smoothness of an external appearance will be lost.

In addition, in this invention, the dimension of a parent particle (large particle) and a magnetic particle (small particle) of a composite particle is a dimension after compounding. Therefore, when large particles and small particles are mixed and pulverized and complexed, the size of the large particles before the treatment may be larger than the average particle diameter of 200 µm measured by laser diffraction / scattering particle size analysis. The same applies to the small particles, but in general, the small particles are often not substantially miniaturized by the complexing treatment.

As the mother particles, it is also possible to use spherical resin particles. When spherical particles are used, it is possible to easily avoid overcharging of the coating compounding process, that is, sticking of the processing object and the processing medium (ball, etc.) when performing the compounding treatment (ball mill treatment, etc.). have.

It is preferable that a mother particle is 150 degreeC or more of melting | fusing point. When the composite particles are kneaded and molded with other resins, they are heated. If the melting point is 150 ° C or higher, the shape of the parent particles can be maintained and the function of the magnetic particles can be sufficiently expressed.

As a mother particle, the hydroxide, oxide, or carbonate containing at least 1 sort (s) chosen from the group which consists of Al, Mg, Ca, and Si can be used. Preferably, hydroxide particles or oxide particles of Al, Mg, Ca, carbonate particles of Ca, or silica particles can be used. Specific examples of preferred mother particles include particles such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, aluminum oxide, magnesium oxide, calcium oxide, calcium carbonate and silica. The parent particles do not mind their complex.

If a mother particle has said average particle diameter, a shape does not matter. The particles obtained by any method are not concerned.

When the mother particles composed of these substances are subjected to a treatment in which the energy constant k (defined by the late (1) formula) in dry mixing by a rolling method such as a ball mill is 50 or more and 50,000 or less, In the powder processing apparatus of the type which mixes, pulverizes, and stirs by rotating the blades, when the energy constant k2 (defined by late equation (2)) is 250 or more and 50,000 or less, the mixture is also mixed by vibration. In the powder processing apparatus of the type which grinds and stirs, when the energy constant k3 (defined by late formula (3)) is 50 or more and 50,000 or less, it strongly bonds with silica or Brønstedate in the magnetic particles. It is possible.

The complexing of the magnetic particles (small particles) and the mother particles (large particles) can be carried out by providing the small particles and the large particles or the spare particles of the large particles in a mixing operation at a predetermined energy constant. In the mixing operation, the powder surface is compounded by activating the powder surface by energy such as impact, friction, shear, etc., which are pulverized, mixed, and stirred by the powder.

As a mixing method capable of compounding the particles, for example, a variety of mixed grinding and mechanical fusing apparatuses such as an electric ball mill, a high speed mill, a medium stirring mill, a high speed air impact method, and a surface fusion method can be used. As the operation factor, for example, adjustment of rotation speed, residence time, etc. in a high speed rotary mill, adjustment of stirring speed, media mass, stirring time, etc. in a medium stirring type mill, etc. are mentioned. In the pulverizer, the pressure of the carrier gas, the residence time, etc. are adjusted, and appropriate energy is given to the to-be-processed object.

The ball mill is the most common mixing and pulverizing device, but may be a complexing device by selecting conditions, and is suitable because it can quantify the energy received by the coated alloy. The energy consumed for this compounding can use energy constant k as an index. Energy constant (k) has been proposed as an indicator for uniformly evaluating the mixing and grinding effects of electric ball mills (LDHart and LK Hadson, The American Ceramic Society Bulletin, 43, No. 1, (1964)). Is represented.

                     k = (wm / wp) × d × n × t (1)

Where k is the energy constant, wp is the total mass of the powder to be mixed (g), wm is the media mass (g), d is the ball mill vessel diameter (m), n is the rotational speed (rpm), and t is the mixing time ( Min).

Moreover, in the powder processing apparatus of the type which mixes, grinds, and stirs by rotation of a blade, when the rotation speed of a blade is n (rpm) and processing time is t (minute),

                      k2 = n × t (2)

K2 represented by the relationship of is called an energy constant.

In the powder processing apparatus of the type which mixes, grinds and stirs by vibration, when the number of vibrations (times / minute) is n and the mixing time is t (minutes),

                      k3 = n × t (3)

K3 represented by the relationship of is called an energy constant.

As both energy constants increase, the collision, friction, and shear energy that the powder receives increases, and the bond between the parent particles and the magnetic particles is likely to occur.

In the method for producing a composite particle according to the present invention, in an apparatus for energizing powder by rolling a pulverizing / mixing medium such as a ball mill, the energy constant (k) of the mixing operation of the large particles and the magnetic particles is 50 or more, 50,000. It is set as follows. Preferably it is 750 or more, 20,000 or less, More preferably, it is 1,000 or more and 15,000 or less.

In the device which energizes powder by rotating a blade, the energy constant (k2) should just be 250 or more and 50,000 or less. Preferably it is 500 or more and 20,000 or less, More preferably, it is 700 or more and 15,000 or less.

In the apparatus for energizing the powder by vibration of the pulverizing / mixing medium, the energy constant k3 may be 50 or more and 50,000 or less, preferably 250 or more, 20,000 or less, more preferably 700 or 15,000 or less.

If the energy constant is below the lower limit, the surface activity of the powder is insufficient, and the bonding between the particles is unlikely to occur. If the energy constant is higher than the above upper limit, the pulverization proceeds excessively, not only the particles become fine grains, but also the active surface is relatively increased, which causes problems such as compacting and hardening to form coarse particles. It is also undesirable because it also binds to a pulverized medium, a container, or the like, and causes adhesion of the coated alloy and the medium, adhesion to the container, and the like.

As the apparatus used for compounding, besides the general-purpose ball mill, the rotary blade type can be exemplified by Kawata Super Mixer, and the vibration type paint shaker of Asada Iron Works Co., Ltd., and the hybridization system manufactured by Nara Machinery Co., Ltd. Registered trademarks), Mekanofusion (registered trademark) of Hosokawa Micron Co., Ltd., a medium flow dryer, an airflow impact method, a surface fusion method, and the like are exemplified, but are not particularly limited to these apparatuses.

Also in a complexation method other than those exemplified above, it is important to appropriately adjust the energy required for the complexation. In a case other than the electric, rotary blade, or vibration type, the power applied to the processed material per unit mass may be set to be equal to the power range prescribed by the energy constant of the ball mill.

In addition, when small particles with Bronsted acid salt on the surface of titanium dioxide are in a slurry state, a large particle may be added to the slurry, and a method of compounding by a medium flow drying apparatus may be employed. It is because a slurry is dripped in the ceramic medium of a fluid state, and large particle | grains and small particle | grains firmly couple | bond by the shear force energy of each medium, and the cohesion force by drying.

In the compounding treatment, generally, the ratio of the magnetic particles to the mother particles is measured to be 0.5% by mass or more and 40% by mass or less and charged into the compounding device.

The composite particles of the present invention can be used for almost the same applications as conventional titanium dioxide, such as resin products, rubber products, paper, cosmetics, paints, printing inks, ceramic products, dye-sensitized solar cells, and photocatalysts. .

The composite particles of the present invention can be used, for example, as a composition in addition to an organic polymer. As an organic polymer, a synthetic thermoplastic resin, a synthetic heat-change resin, a natural resin, etc. are mentioned, for example.

Specific examples of such organic polymers include polyolefins such as polyethylene, polypropylene and polystyrene, polyamides such as nylon 6, nylon 66 and aramid, polyesters such as polyethylene terephthalate and unsaturated polyester, polyvinyl chloride and poly Vinylidene chloride, polyethylene oxide, polyethylene glycol, silicone resin, polyvinyl alcohol, vinyl acetal resin, polyacetate, ABS resin, epoxy resin, vinyl acetate resin, cellulose and rayon and other cellulose derivatives, polyurethane, polycarbonate, urea Resin, fluororesin, polyvinylidene fluoride, phenol resin, celluloid, kitchen, starch sheet, acrylic resin, melamine resin, alkyd resin and the like. An organic polymer may be used individually by 1 type, or may be used in combination of 2 or more type.

These organic polymer compositions containing the composite particles of the present invention are, for example, a masterbatch used for paints (coating compositions), compounds (for example, powder-containing resin compositions), molded articles containing the composite particles at high concentration, and the like. It can be used in the form of. You may add additives, such as antioxidant, an antistatic agent, a metal fatty acid salt, to an organic polymer composition.

As for the density | concentration of the composite particle of this invention in an organic polymer composition, 0.01-80 mass% is preferable with respect to the total mass of an organic polymer composition, Especially preferably, it is 0.01-60 mass%, More preferably, it is 1-50 mass% Most preferably, it is 1-40 mass%.

By molding such a polymer composition, a molded article having ultraviolet shielding ability can be obtained. As such a molded object, the molded object, such as a fiber, a film, plastic, etc. are mentioned, for example.

Examples of the fibers include polyolefin fibers, polyamide fibers, polyester fibers, acrylic fibers, rayon, and the like. These fibers can be made into various photocatalyst fiber products. Specific examples thereof include cloth products such as towels, cloths, towels, eyeglasses wipes and handkerchiefs; Bedding and nursing cloth products such as pajamas, diapers, sheets, toilet seat covers, blankets and blankets; Underwear such as underwear and socks; Hospital textile products such as masks, white coats, nursing caps, curtains and sheets; Sports textile products such as supporters, trainers and sportswear; Automotive textile products such as automobile seats, seat covers, automobile ceiling materials and automobile flooring materials; House textile products such as carpets, curtains, rolls, decorative paws, fabrics of chairs and sofas; Medical textile products, such as a sweater, are mentioned. Moreover, photocatalyst fiber can be used for paper products, such as a wallpaper and sliding door.

As a film, cosmetic films, such as a garbage bag, a food packaging wrap, a film for wraps, the shrink film for PET bottles, and a makeup board, etc. are mentioned.

Examples of the molded article include a sink unit, a bus unit, a resin part of a dishwasher unit, a resin part of a railing, a television, a personal computer, an air conditioner indoor unit, a copy machine, a washing machine, a dehumidifier, a telephone, an electric pot, a resin such as a vacuum cleaner, and a resin for lighting equipment. And a cover, a resin hanger, a resin clothes case, a resin trash box, and a dashboard for an automobile.

In general, the composite particles of the present invention can obtain the effect that large particles of the composite particles are derived by blending and molding the organic polymer composition. However, when the organic polymer composition is molded into fibers or films, the fiber diameter or film thickness is limited. However, two times or more and 200 times or less of the parent particle diameter are preferable, and five times or more and 100 times or less are more preferable.

In addition, the composite particles of the present invention can be dispersed in water or an organic solvent, and optionally a binder can be added to form a coating agent. There is no restriction | limiting in particular about a binder material, An organic type binder or an inorganic type binder may be sufficient.

As such a binder, For example, polyester, such as polyvinyl alcohol, melamine resin, urethane resin, celluloid, kitchen, starch sheet, polyacrylamide, acrylamide, unsaturated polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene Oxide, polyethylene glycol, silicone resin, vinyl acetal resin, epoxy resin, vinyl acetate resin, polyurethane, urea resin, fluororesin, polyvinylidene fluoride, phenol resin and the like. As the inorganic binder, for example, a zirconium compound such as zirconium oxychloride, hydroxy zirconium chloride, zirconium acetate, zirconium sulfate, zirconium acetate, zirconium carbonate ammonium, zirconium carbonate, zirconium propionate, alkoxysilane, silicate, or aluminum And metal alkoxides of titanium.

0.01 mass%-20 mass% are preferable, and, as for the addition amount of the binder in a coating agent, the range of 1 mass%-10 mass% is especially preferable. If content of a binder is less than 0.01 mass%, sufficient adhesiveness cannot be obtained after application | coating, On the contrary, when it exceeds 20 mass%, problems, such as a thickening, arise and become economically disadvantageous.

In addition, the composite particles of the present invention may be provided on the surface of the structure. Such a structure is not specifically limited, For example, it may be comprised from inorganic materials, such as metal, concrete, glass, and a pottery, may be comprised from organic materials, such as paper, plastics, wood, and leather, or It may be a combination of them. Examples of these include building materials, machinery, vehicles, glass products, home appliances, agricultural materials, electronic devices, tools, tableware, bath products, toiletries, furniture, clothing, fabrics, textiles, leather products, papermaking Articles, sporting goods, duvets, containers, glasses, signs, plumbing, wiring, metal fittings, sanitary materials, automobile articles, outdoor articles such as tents, stockings, socks, gloves, masks, and the like. The present invention can also be applied to environmental clean-up devices and devices effective for the prevention of seek house, decomposition of organic chlorine compounds such as PCBs and dioxins in water, air and soil, and decomposition of residual pesticides and environmental hormones in water and soil.

In addition, as the light source capable of effectively expressing the photocatalytic property or the hydrophilicity of the article, the sun, fluorescent lamps, incandescent lamps, mercury lamps, xenon lamps, halogen lamps, mercury xenon lamps, halogenated metal lamps, light emitting diodes, lasers, organic materials Combustion salt etc. can be illustrated. Examples of the fluorescent lamps include white fluorescent lamps, day white fluorescent lamps, daylight fluorescent lamps, warm white fluorescent lamps, electric bulb color fluorescent lamps, and black lights.

It does not specifically limit as a method of equipping the surface of these structures, For example, you may apply | coat the above-mentioned organic polymer composition and coating agent directly to a structure, or may apply on the structure which already has a coating film on the surface. . When the film is formed by applying the coating agent, the effect that the composite particles are derived by the film is obtained. Although it does not limit as a film thickness, 2 times or more and 200 times or less of a parent particle diameter are preferable, and 5 times or more and 100 times or less are more preferable. Moreover, you may form another coating film on these. In that case, a membrane which does not cover the derived portion of the composite particles or which easily permeates the substance related to the photocatalytic reaction is preferable.

It is also possible to use the composite particles of the present invention in cosmetics and the like. More preferably, when titanium dioxide silica composite fine particles are used for the small particles, smoothness when applied to the skin is superior to cosmetics using only self particles, that is, titanium dioxide silica composite fine particles. This effect is especially remarkable when a mother particle is spherical nylon particle. The composite particles carrying titanium dioxide silica fine particles on the spherical nylon particles not only have excellent smoothness and feel when applied to the skin, but also have ultraviolet shielding ability. The cosmetics generally include oils, whitening agents, moisturizers, anti-aging agents, emollients, concentrates, anti-inflammatory agents, antioxidants, surfactants, chelating agents, antibacterial agents, preservatives, amino acids, sugars, organic acids, and alcohols that are commonly used in cosmetics. Various additives such as oils, esters, fats and oils, hydrocarbons, sunscreens and inorganic powders can be added.

Specifically, polyhydric alcohols such as solvents such as ethanol, isopropanol, butyl alcohol and benzyl alcohol, glycerin, propylene glycol, sorbitan, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol and 1,2-pentanediol , Saccharides such as sorbitol, disaccharides such as trehalose, moisturizing agents such as hyaluronic acid and water-soluble collagen, vegetable oils such as hydrogenated squalene and olive oil, jojoba oil, emollients such as ceramides, magnesium ascorbic acid phosphate and ascorbic acid Whitening agents, such as stable ascorbic acid, arbutin, kojic acid, ellagic acid, rucinol, and chamomile extracts, such as glucoside, butyric acid, and salt-containing agents, such as arantoin, glytitylic acid or its salts, glycerin monostearate, POE sorbitan fatty acid ester , Non-ionic interfaces such as sorbitan fatty acid esters, POE alkyl ethers, POE / POP block polymers and POE-cured castor oil esters Active agents, anionic surfactants such as fatty acid soaps, sodium alkyl sulfates, hydrocarbons such as squalene, liquid paraffin, paraffin, isoparaffin, petrolatum, α-olefin oligomers, almond oil, cacao oil, macadamia nut oil, avocado oil, castor oil, Sunflower oil, evening primrose oil, safflower seed oil, rapeseed oil, horse oil, tallow, oils such as synthetic triglycerides, lead waxes such as yellow beeswax, lanolin, jojoba oil, lauryl acid, atreanic acid, oleic acid, isostearic acid, Fatty acids such as myristylic acid, palmitic acid, behenic acid, glycolic acid, tartaric acid, higher alcohols such as cetanol, stearyl alcohol, behenyl alcohol, octyldodecyl alcohol, glycerin triester, pentaerythritol tetraester, etc. Synthetic esters, silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, chel such as EDTA, glyconic acid, phytic acid, sodium polyphosphate Ytt agent, paraben, sorbic acid, isopropylmethylphenyl, cresol, benzoic acid, ethyl, preservatives such as stearyl dimethylbenzyl ammonium chloride, hinokthiol, furfural, sodium pyrithione, fungicide, vitamin E, dibutylhydroxytoluene, subclass Antioxidants such as sodium hydrogen oxide and butyl hydroxyanisole, buffers such as citric acid, sodium citrate, lactic acid, sodium lactate, amino acids such as glycine and alanine, esters such as butyl mystinate, ethyl oleate and ethyl stearate, Perfumes, pigments, animal and plant extracts, vitamins such as vitamins A, B, and C and derivatives thereof, paraamino benzoic acid, octyl paradimethelaminobenzoate, ethyl paraamino benzoate, phenyl salicylate, benzyl cinnamic acid, octylmethoxycinnamate, synox UV absorbers such as citrate, ethyl urocanate, hydroxymethoxybenzophenone, dihydroxybenzophenone, mica, talc, kaolin, calcium carbonate Inorganic powders such as silicic anhydride, aluminum oxide, magnesium carbonate, barium sulfate, cerium oxide, bengal, chromium oxide, ultramarine black iron oxide, iron sulfate, resin powder such as nylon powder, polymethyl methacrylate powder, etc. can be used. Can be.

In the cosmetics referred to in the present invention, parts other than the present invention can be produced using a technique generally used for production.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although the Example of this invention is described concretely, this invention is not limited to these Examples at all.

In the following Examples and Comparative Examples, the following evaluation was performed.

(1) Photocatalytic property of film

20 parts by mass of the composite particles of the present invention, 2 parts by mass of zinc stearate (manufactured by Nippon Oil Co., Ltd., zinc stearate S), and 78 parts by mass of low density polyethylene (manufactured by Nippon Polyolefin Co., Ltd., J-Rex JH607C) (KZW15-30MG, manufactured by Technobel Co., Ltd.) was melt kneaded at 140 ° C. (staying time about 3 minutes) and pelletized. A compound of low density polyethylene having a composite particle content of 20% is obtained on a diameter of 2 to 3 mm, a length of 3 to 5 mm, a mass of 0.01 to 0.02 g, and a columnar shape.

4 kg of this low density polyethylene compound and 16 kg of low density polyethylene (manufactured by Nippon Polyolefin Co., Ltd., J-Rex JH607C) were mixed for 10 minutes in a V-type blender (manufactured by Ikemoto Rika Co., Ltd., RKI-40) to prepare a mixed pellet. .

Subsequently, the obtained mixed pellets were produced at a die temperature of 250 ° C. with a twin screw kneading extruder (KZW15-30MG, manufactured by Technobel Co., Ltd.) having a T die of 200 mm to produce a film of 80 μm.

On the film thus obtained, the test ink was struck so as to have a circular shape of about 2 cm in diameter, and an ink discoloration test sample was obtained. As test ink, what melt | dissolved 1 g of ink for color printers (BJI20LM-magenta by Canon Corporation) in 99 g of ethanol was used.

The ink discoloration test sample was placed at a position of 5 cm from the glass window, and blue water was observed on the cumulative third day over the glass, and the degree of discoloration was visually determined.

(2) hydrogen sulfide deodorization test

The sample was placed in a Tedla® bag (AAK-5, manufactured by DL Science Co., Ltd.) having a capacity of 5 L so that the total area of the photocatalyst surface to be irradiated with light was 400 cm 2. Next, 5L charge and blow of dry air containing 60 volume ppm of hydrogen sulfide were carried out at least once, 5 L of dry air containing hydrogen sulfide of the same density | concentration were again filled, and the internal gas was fully substituted. Dry air containing 60 volppm of hydrogen sulfide was prepared in Pamietta (manufactured by Gastech Co., Ltd., PD-1B) using commercially available compressed air.

Then, the initial hydrogen sulfide concentration C _0T (volume ppm) was measured using a detection tube (Gas Tech Co., Ltd., NO. 4LL). Then, light irradiation was started so that the light of the ultraviolet intensity of 0.5 mW / cm <2> in wavelength 365nm may be irradiated to the photocatalyst surface from the outside of the bag. From this time point, the hydrogen sulfide concentration C _1T (volume ppm) in the bag after 4 hours was measured. On the other hand, as a control experiment, the test which hold | maintained for 4 hours in the dark by the above operation was also performed. The initial hydrogen sulfide concentration at that time was C _0B (volume ppm) and the hydrogen sulfide concentration after 4 hours was C _1B (volume ppm).

In addition, black light (National Corporation, FL20S / BL-B) is used as a light source, and Ushio Electric Co., Ltd. ultraviolet integration photometer, UIT-150 is used for the measurement of the light intensity in 365 nm. did. In addition, when using a white fluorescent lamp as a light source, Hitachi GE Lighting Co., Ltd. and High White FL20SS-N / 18-B were used, for example. UVT-365 made by Atex Corporation was used for the measurement of light intensity. Using this, the weak light intensity at 365 nm can be measured. At this time, the white light fluorescent lamp was adjusted and irradiated so that the light of ultraviolet-ray intensity of 6 mA / cm <2> in wavelength 365nm may be irradiated to the photocatalyst surface.

The decomposition rate D ₁ of hydrogen sulfide excluding adsorption is

D ₁ = {(C _0T -C _1T )-(C _0B -C _1B )} / C _0T × 100 (%)

Is defined by The greater the D _1, the photocatalytic property can be determined to be larger.

(3) Weather resistance test (weather resistance of film)

A portion of the film made for the ink bleach test was used for the weather resistance test. In the weather resistance test, the plate was multiplied by a Suga Tester Co., Ltd. Sunshine Super Ron Graph Weser Meter WEL-SUN-HCH type for 48 hours. In accordance with JIS K 7350-4 (Plastic-Laboratory Light Exposure Test Method Open Frame Carbon Arc Lamp), using a type I filter, the black panel temperature is 63 ± 3 ° C., and the moisture spray time is 18 ± 0.5 minutes / 60 minutes. The test was done on condition.

Evaluation of weather resistance measured the glossiness of the flat plate before and behind a Sunshine Superlon Graphe Wager meter with GLOSS CHECKER IG-320 by Horiba Corporation, and performed it by the glossiness retention rate. Glossiness retention rate, if the glossiness of the film before the weather resistance test is BL ₀ (%), the glossiness of the film after the weather resistance test is BL ₁ (%),

Glossiness retention = BL ₁ / BL ₀ × 100 (%)

Calculated by

(4) Evaluation of marital status

In the present invention, XPS (X-ray photoelectron spectroscopy) is adopted as a method for confirming the mixed state of magnetic particles. For details, see A. Yu. Stakehee et al, J. Phys. Chem., 97 (21), 5668-5672 (1993) and the like.

Example 1

Gas containing 100% by volume of gaseous titanium tetrachloride 9.4 Nm ³ / hour (N means the same as below.) And 100% by volume of gaseous silicon tetrachloride 0.25Nm ³ / hour were mixed at 1,000 ° C. , 8Nm ³ / hour of oxygen and a mixed gas of 20Nm ³ / hour of water vapor 1, each preheated to O0O ℃, by using a coaxial parallel flow nojeulreul, introduced to each flow velocity 49m / sec, 60m / second reaction tube.

In addition, the reaction introduced gas so that the inner side of the coaxial parallel flow nozzle might be a mixed gas of titanium tetrachloride-silicon tetrachloride. The inner diameter of the reaction tube was 100 mm, and the tube flow rate at the reaction temperature of 1,300 ° C. was 10 m / sec in the calculated value.

After the reaction, cooling air was introduced into the reaction tube so that the high temperature residence time in the reaction tube was 0.3 seconds or less, and then ultra-fine particle powder produced using a polytetrafluoroethylene bug filter was collected. The collected powder was heated in an oven at 500 ° C for 1 hour under an air atmosphere, and dechlorination was performed.

The obtained ultra-fine particle mixed crystal oxide had a BET specific surface area of 24 m ₂ / g, a SiO ₂ content of 2.2 mass%, an average primary particle diameter of 0.06 µm and a chlorine content of 0.01 mass% in terms of BET specific surface area. Silicon bonds were identified. This ultrafine particle mixed crystal oxide was used as a magnetic particle.

On the other hand, 800g of alumina balls of diameter 5mm were put into the nylon container of diameter 12.5cm. Here, 190 g of aluminum hydroxide (Hydrite® H-10C: average particle diameter: 85 µm) manufactured by Showa Denko Co., and titanium dioxide-silica composite fine particles (average particle diameter in terms of BET specific surface area: 0.06 µm, 10 g of SiO ₂ = 2.2% by mass) was added. This was capped and pulverized and mixed for 2 hours at 50 revolutions per minute. The energy constant at this time is 3,000.

After the pulverized mixing treatment, the processed product was observed with a scanning electron microscope. The particles of glass were few, and most of the particles were composited, and aluminum hydroxide was used as the parent particles (average particle diameter measured by laser diffraction / scattering particle size analysis method). Is about 60 µm and is not largely changed) and the composite particles in which the titanium dioxide-silica composite fine particles are carried on the surface of the parent particle as self particles (the average particle diameter converted from the BET specific surface area is not changed). What was obtained was confirmed.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 90%. In addition, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide was 40%.

Example 2

800 g of alumina balls having a diameter of 5 mm were placed in a nylon container having a diameter of 12.5 cm. 190 g of aluminum hydroxide manufactured by Showa Denko Co., Ltd. (average particle diameter 9 μm measured by Heidilite HS-320: laser diffraction / scattering particle size analysis) and 10 g of titanium dioxide-silica composite fine particles used in Example 1 were added thereto. This was capped and pulverized and mixed for 30 minutes at 50 revolutions per minute. The energy constant at this time is 750.

After the pulverized mixing treatment, the processed product was observed with a scanning electron microscope. The particles of glass were few, and most of the particles were composited, and aluminum hydroxide was used as the parent particles (average particle diameter measured by laser diffraction / scattering particle size analysis method). Is not significantly changed), and the composite particles in which the titanium dioxide-silica composite fine particles are supported on the surface of the parent particle as self particles (the average particle diameter converted from the BET specific surface area is not changed) can be obtained. Confirmed.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 80%. In addition, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide was 60%.

Example 3

800 g of alumina balls having a diameter of 5 mm were placed in a nylon container having a diameter of 12.5 cm. 190 g of spherical nylon powder KG-10 (average diameter of 10 µm, melting point of 165 ° C) manufactured by Toray Corporation and 10 g of titanium dioxide-silica composite fine particles used in Example 1 were added thereto. This was capped and mixed for 8 hours at 50 revolutions per minute. The energy constant k at this time is 12,000.

After the pulverized mixing treatment, the processed material was observed with a scanning electron microscope. The particles of glass were few and most of the particles were composited. The average particle diameter measured by the laser diffraction / scattering particle size analysis method It was confirmed that composite particles carrying the titanium dioxide silica composite fine particles as self particles (the average particle diameter converted from the BET specific surface area did not change) were obtained on the surface of the mother particles.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 85%. In addition, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide was 55%.

Example 4

27 kg of calcium carbonate Pyton B (average particle diameter 14 micrometers measured by the laser diffraction / scattering particle size analysis method) made from Shiraishi calcium Co., Ltd. was injected | poured into the super mixer SMG-100 (100 volume volume) made by Kawata Corporation. 3 kg of the titanium dioxide-silica composite fine particles used in Example 1 were added thereto, and a lid was covered. The complexing process for 1500 minutes / minute and 3 minutes was performed at room temperature. The energy constant k2 at this time was 4,500.

After the compounding treatment, the processed product was observed with a scanning electron microscope. The particles of glass were few and most of the particles were compounded. The average particle diameter measured by the laser diffraction / scattering particle size analysis method It is confirmed that the composite particles carrying the titanium dioxide-silica composite particles as small particles (the average particle diameter converted from the BET specific surface area is not changed) can be obtained on the surface of the mother particles. It became.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 85%. Further, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide was 50%.

Example 5

1.5 kg of calcium carbonate Pyton B (average particle size 14 탆 measured by laser diffraction / scattering particle size analysis) manufactured by Shiraishi Calcium Co., Ltd. was introduced into Asada Iron Works Co., Ltd. paint shaker (5 L of inner volume). 200 g of the titanium dioxide silica composite fine particles used in Example 1 were added thereto, and a lid was covered. The compounding process for 5 minutes was performed at room temperature. The energy constant (k3) at this time is about 600.

After the compounding treatment, the processed product was observed with a scanning electron microscope. The particles of glass were few and most of the particles were compounded. The average particle diameter measured by the laser diffraction / scattering particle size analysis method It was confirmed that the composite particles carrying the titanium dioxide silica composite particles as small particles (the average particle diameter converted from the BET specific surface area did not change) were obtained on the surface of the parent particles. .

The composite particles thus obtained were filmed by the above method, and when the ink discoloration test was conducted, magenta almost disappeared. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the glossiness retention rate of the obtained film was 80%, and was favorable. In addition, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide was 65%.

Example 6

50 liters of pure water (hereinafter, denoted as liters L) previously weighed were heated while stirring to maintain the temperature at 98 ° C. 3.6 kg of titanium tetrachloride aqueous solution (made by Sumitomo Titanium Co., Ltd.) of 15 mass% of Ti concentration was dripped there over 120 minutes. The white suspension obtained after dropping was dechlorinated over an electrodialysis machine, and the pH of the slurry was set to 4. A part of the photocatalyst slurry thus obtained was collected, and the solid content concentration was measured by a dry weight method, and found to be 2 mass%.

As a result of structural analysis of the dry powder by an X-ray diffraction apparatus, the powder obtained was brookite-type titanium dioxide. This was 89 mass% of brookite content and 11 mass% of anatase content.

Next, 100 g of sodium pyrroline acid (manufactured by Daihei Chemical Co., Ltd., food additives) was dissolved in pure water to obtain 2 kg of a 5% by mass aqueous sodium pyrroline solution.

50 L of 2 mass% titanium dioxide slurries obtained in this way were injected into a reaction tank, and sufficient stirring was performed while cooling. 2 kg of 5 mass% soda pyrroline aqueous solution and 10 mass% caustic soda aqueous solution were added there over 1 hour, preparing so that pH after mixing might be 8-9. At this time, the reaction temperature was 20 to 25 ° C.

The obtained dioxide slurry containing pyrroline acid was maintained at 22-28 degreeC for 1 hour. The electrical conductivity at that time was 10, OOOO µS / cm. Subsequently, the obtained slurry was filtered and washed with a rotary filter press (manufactured by Kotobuki Institute of Technology, Inc.), washed sufficiently with water until the electrical conductivity of the filtrate was 50 µS / cm, and then concentrated to obtain a photocatalytic slurry. It was 7.8 when the pH of the obtained photocatalyst slurry was measured by pH in total (D-22 by Horiba Corporation).

Then, a part of the obtained slurry was extract | collected and the powder was obtained by the dry weighing method at 120 degreeC. It was 10 mass% when the solid content concentration of the slurry was measured in this. The powder obtained was then analyzed by FT-IR (manufactured by Parkin-Elma, Inc., FT-IR1650). As a result, absorption of pyrroline acid was observed. Next, the dry powder was analyzed by ICP (manufactured by Shimadzu Corporation, ICPS-100V) to find that 0.7% by mass of Na and 1.2% by mass of phosphorus were present. In addition, when the ZETA potential measured by the electrophoretic light scattering method was measured using ELS-8000 by Otsuka Electronics Co., Ltd., the isoelectric point was 2.1. The result of BET specific surface area measurement (Flow Sorb II 2300 by Shimadzu Corporation) was 140 m <2> / g.

70 kg of pure water and 20 kg of calcium carbonate Pyton B (average particle diameter 14 micrometers measured by the laser diffraction / scattering particle size analysis method) which were made into 10 kg of said slurry were prepared, and it fully stirred. The slurry was dried in a medium flow dryer (Okawara Co., Ltd., slurry dryer) to obtain a composite particle composed of small particles having Bronstedate on the surface of the titanium dioxide fine particles and calcium carbonate mother particles.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 80%. Further, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide when the black light was used as the light source was 75%.

In addition, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide when the main white fluorescent lamp was used as a light source was 12%, and was also decomposed in light of a weak fluorescent lamp.

Example 7

40 kg of pure water and 50 kg of calcium carbonate Pyton B (14 µm in average particle size measured by laser diffraction / scattering particle size analysis method) were added to 10 kg of the small particle slurry obtained in the same manner as in Example 6, and the mixture was sufficiently stirred. Composite particles were obtained.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 80%. Further, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide when the black light was used as the light source was 90%.

In addition, the decomposition rate D ₀ excluding the adsorption of hydrogen sulfide when the main white fluorescent lamp was used as the light source was 19%, and the light was decomposed even in the light of a weak fluorescent lamp.

Example 8

Into a small particle slurry obtained in the same manner as in Example 6, 5 kg of pure water and 135 kg of pure water and calcium carbonate Pyton B (14 µm in average particle size measured by laser diffraction / scattering particle size analysis) were added and stirred. Composite particles were obtained.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Moreover, the gloss retention of the obtained film was favorable at 85%. The decomposition rate D ₀ excluding adsorption of hydrogen sulfide when the black light was used as the light source was 70%.

In addition, the decomposition rate D ₀ excluding the adsorption of hydrogen sulfide when the main white fluorescent lamp was used as a light source was 10%, and the decomposition was performed even in light of a weak fluorescent lamp.

Example 9

The small particle slurry obtained in the same manner as in Example 6 was dried with a medium flow dryer (manufactured by Okawara Co., Ltd., slurry dryer) to obtain small particles. This was carried out in the same manner as in Example 4 to obtain a composite particle.

Magenta was almost disappeared when the composite particles thus obtained were formed into a film by the above method and subjected to an ink discoloration test. In addition, the bleaching test was performed at the same time in the cow, but no bleaching was observed. Therefore, it was confirmed that discoloration in the above-described ink discoloration test is due to a photocatalytic effect. Similarly, the gloss retention of the obtained film was also good at 80%. Similarly, the decomposition rate D ₀ excluding adsorption of hydrogen sulfide when black light was used as the light source was 71%, and the decomposition rate D ₀ excluding adsorption of hydrogen sulfide when the white light fluorescent lamp was used as the light source was 12%. It was decomposed even in light.

Comparative Example 1

27 kg of calcium carbonate Pyton B (average particle diameter 14 micrometers measured by the laser diffraction / scattering particle size analysis method) made from Shiraishi calcium Co., Ltd. was injected | poured into the super mixer SMG-100 (100 volume volume) made by Kawata Corporation. 3 kg of the titanium dioxide-silica composite fine particles used in Example 1 were added thereto, and a lid was covered. The complexing process was performed at room temperature for 200 revolutions / minute for 30 seconds. The energy constant k2 at this time was 100.

After the treatment, the treatment was observed on a scanning electron microscope, and no difference was found between the simple mixture and the powder.

Magenta was not disappeared when this particle | grain was film-formed by the said method and the ink discoloration test was done. Moreover, the gloss retention of the obtained film was 40% or less, and it was very bad. Since this is not complexed, it is thought that the titania-silica particles are in direct contact with the resin, and the weather resistance is deteriorated by the photocatalytic action.

Comparative Example 2

27 kg of calcium carbonate Pyton B (average particle diameter 14 micrometers measured by the laser diffraction / scattering particle size analysis method) made from Shiraishi calcium Co., Ltd. was injected | poured into the super mixer SMG-100 (100 volume volume) made by Kawata Corporation. 3 kg of titanium dioxide-silica composite fine particles used in Example 1 were added thereto, and a lid was covered. The compounding process of 1500 rotation / min and 45 minutes was performed at room temperature. The energy constant k2 at this time is 67,500.

After this treatment, the workpiece was firmly fixed to the surface of the super mixer. This is a solid aggregate of powder due to excessive processing. This powder is difficult to agglomerate and cannot withstand its use.

Comparative Example 3

50 L of pure water measured beforehand was heated, stirring, and temperature was maintained at 98 degreeC. 3.6 kg of titanium tetrachloride aqueous solution (made by Sumitomo Titanium Co., Ltd.) of 15 mass% of Ti concentration was dripped there over 120 minutes. The white suspension obtained after dripping was dechlorinated by the electrodialysis machine, and pH of the slurry was 4. A part of the photocatalyst slurry thus obtained was collected, and the solid content concentration was measured by a dry weight method, and found to be 2 mass%. As a result of structural analysis of the dried powder by an X-ray diffraction apparatus, the powder obtained was brookite titanium dioxide. This was 89 mass% of brookite content and 11 mass% of anatase content.

A part of this slurry was dried with the medium flow dryer (Okawara Co., Ltd. slurry slurry), and the small particle was obtained. This was carried out in the same manner as in Example 4 to obtain a composite particle.

When the particle | grains were filmed by the said method and the ink discoloration test was carried out, magenta disappeared, but the gloss retention of the obtained film was 30% or less, and was very bad. Since the small particles are not pyrroline treated, they are not complexed, and the small particles are in direct contact with each other by dispersion in the resin, which is considered to deteriorate weather resistance by photocatalytic action.

Comparative Example 5

100 g of calcium carbonate Pyton B (14 µm average particle diameter measured by laser diffraction / scattering particle size analysis method) manufactured by Shiraishi Calcium Co., Ltd. was added to 10 kg of the small particle slurry obtained in the same manner as in Example 6, and the mixture was sufficiently stirred. Got it.

When the composite particles thus obtained were filmed by the above method and subjected to an ink discoloration test, magenta almost disappeared, but the gloss retention of the obtained film was very bad at 18%.

The composite particle of this invention is added to an organic polymer, and it is set as a polymer composition, and the molded object which has an ultraviolet shielding ability can be obtained by shape | molding this polymer composition. As such a molded object, the molded object, such as a fiber, a film, plastic, etc. are mentioned, for example.

When the composite particles of the present invention are kneaded with a resin to form a film or when a film is formed on the surface of a structure together with a resin binder, the particles having a photocatalytic ability with the resin are exposed, that is, particles capable of effectively "drawing out". . For this reason, a photocatalytic ability can fully be exhibited, suppressing decomposition | disassembly of resin used as a composite particle carrier to the minimum. Therefore, it is possible to set it as the structure, film, etc. which are excellent in weatherability. In addition, it is possible to simultaneously solve the inexpensive supporting construction and durability of the photocatalyst particles.

As small particles of the composite fine particles, when titanium dioxide fine particles or titanium dioxide composite fine particles containing Bronsted acid salts are used, it is possible to obtain a practical article exhibiting sufficient photocatalytic ability even under weak light in a room.

Claims (26)

A composite particle in which small particles are supported on large particles, wherein the small particles are photocatalyst-containing fine particles having an average particle diameter of 0.005 μm to 0.5 μm in terms of BET specific surface area, and the large particles are laser diffraction / scattering particle sizes. The composite particle which has an average particle diameter of 2-200 micrometers measured by the analytical method. The composite particle according to claim 1, wherein the small particles contain titanium dioxide as a photocatalyst. The composite particle according to claim 1, wherein the small particle is a composite particle of titanium dioxide and an inorganic compound that does not express photocatalytic ability. 4. The composite particle according to claim 3, wherein the inorganic compound that does not exhibit photocatalytic ability is silica, and the proportion of silica contained in the small particles is 0.5% by mass or more and 50% by mass or less. The multiparticulate according to any one of claims 1 to 4, wherein the small particles contain Bronsted acid salt. 6. The composite particle according to claim 5, wherein the small particles are titanium dioxide particles in which Brönstedate is present on the surface. The multiparticulate according to claim 6, wherein the Brönstedate is a condensed phosphate. The multiparticulate according to any one of claims 5 to 7, wherein the small particles contain 0.01% by mass to 50% by mass of Bronsted Salt. The composite particle according to any one of claims 2 to 8, wherein the titanium dioxide contains a brookite crystal phase. The composite particle according to any one of claims 1 to 9, wherein the large particles are spherical resin particles having a melting point of 150 ° C or higher. The composite particle according to any one of claims 1 to 9, wherein the large particles are hydroxides, oxides, or carbonates containing at least one member selected from the group consisting of Al, Mg, Ca, and Si. The composite particle according to any one of claims 1 to 11, wherein the ratio of the small particles to the large particles is 0.5% by mass or more and 40% by mass or less. In the method of dry mixing a material containing large particles and small particles with a ball mill, and manufacturing the composite particles, the energy constant (k) of the dry mixing is defined as wp (g), the total mass of the particles to be mixed. When wm (g), ball mill vessel inner diameter (m), rotation speed n (rpm), and mixing time t (minutes), k = (wm / wp) × d × n × t (1) The process for producing the composite particles according to any one of claims 1 to 12, wherein dry mixing is performed under the condition that k represented by the relation to be 50 or more and 50,000 or less. Using a powder processing apparatus of a type that mixes, pulverizes and stirs materials containing large particles and small particles by rotating the blades, the blade rotation speed is n (rpm) and the mixing time is t (minutes). When, k2 = n × t (2) The method of manufacturing the composite particle according to any one of claims 1 to 12, wherein the blade is rotated under the condition that k2 represented by such a relationship is 250 or more and 50,000 or less. When using a powder processing apparatus of the type which mixes, grinds and stirs materials containing large particles and small particles by vibration, and sets the vibration frequency (times / minute) to n and the mixing time to t (minutes), k3 = n × t (3) The method for producing a composite particle according to any one of claims 1 to 12, wherein the vibration is performed under the condition that k3 represented by the relation to be 50 or more and 50,000 or less. An organic polymer composition comprising an organic polymer and the composite particles according to any one of claims 1 to 12, wherein the content of the composite particles is 0.01 to 80% by mass in the total mass of the organic polymer composition. Organic polymer composition. The organic polymer composition according to claim 16, wherein the organic polymer is at least one resin selected from the group consisting of a synthetic thermoplastic resin, a synthetic thermosetting resin, and a natural resin. 18. The organic polymer composition of claim 16 or 17, wherein the organic polymer composition is a compound. 18. The organic polymer composition of claim 16 or 17, wherein the organic polymer composition is a master batch. The molded object formed by shape | molding the organic polymer composition in any one of Claims 16-19. The coating agent containing the composite particle in any one of Claims 1-12. A coating material comprising the composite particle according to any one of claims 1 to 12. The structure provided with the composite particle in any one of Claims 1-12 on the surface. A cosmetic comprising a composite particle according to any one of claims 1 to 12. The fiber containing the composite grain | particle of any one of Claims 1-12. 13. The film containing the composite particle of any one of Claims 1-12.