JP5910090B2 - Composite powder, cosmetics and ink - Google Patents

Description

The present invention relates to a composite inorganic powder and a cosmetic and ink obtained by blending the same.

Inorganic powders are often used as fillers and colorants. In recent years, materials having new functions such as ultraviolet ray shielding, heat ray shielding, and catalytic activity have been developed by particle control technology. In particular, materials such as titanium oxide and zinc oxide are often used in sunscreens, cosmetics, paints, and the like as ultraviolet shielding materials by combining fine particle technology and composite powder technology.

However, when these fine particles of titanium oxide or zinc oxide are blended into plastics, inks, cosmetics, etc., the inorganic powder itself reacts with other blends, or the chemical activity of other components is caused by the catalytic activity of the surface. Problems such as destruction occurred.

In order to solve these problems, it has been proposed to inactivate silica by coating fine particle zinc oxide or fine particle titanium oxide with silica as in Patent Document 1, Patent Document 2, and Patent Document 3. However, these silica-treated composite powders give a feeling of squeakiness to the touch and adversely affect the feeling of use of cosmetics and sunscreens. It has been proposed to impart water repellency and improve the feel by silicone treatment, but the squeaky feeling derived from silica remains.

In Patent Document 4, it is proposed to improve the feel and optical characteristics by attaching spherical barium sulfate to the base particles. However, it is difficult to cover the entire base particle with only spherical barium sulfate, and it is considered that it does not contribute to inactivation of the particle. Furthermore, the size of spherical barium sulfate prepared in Patent Document 4 is 0.5 to 5.0 μm, and the particle size (10 to 200 nm) of fine particle titanium oxide or fine particle zinc oxide used for sunscreen is the size. There is also a problem that the technical scope that can be applied is narrow.

Patent Documents 5 and 6 propose cosmetics in which fine particle titanium oxide or fine particle zinc oxide and barium sulfate particles are mixed. It describes the effect that dispersibility and finish are improved by adding barium sulfate. However, when barium sulfate is present alone, when barium sulfate, zinc oxide, and titanium oxide are fine particles, the touch derived from the fine particles may adversely affect cosmetics. In addition, when particles of the order of μm such as plate-like barium sulfate are used, there is a problem that caking is likely to occur in cosmetics due to the high specific gravity of barium sulfate.

JP 2007-16111 A JP-A-3-183620 JP 11-217219 A JP 2004-300080 A JP-A-8-217617 JP 2002-212032 A

In view of the above, the present invention provides a composite powder that improves the feel of silica-treated zinc oxide and titanium oxide and can be suitably used in cosmetics, inks, coating compositions, resin compositions, and the like. It is for the purpose.

The present invention is a composite powder having an average particle diameter of 10 to 250 nm, which is formed by forming a coating layer composed of barium sulfate and silica and / or silica hydrate on the surface of zinc oxide particles or titanium oxide particles. is there.
In the coating layer, barium sulfate is preferably present on the surface and / or pores of silica and / or silica hydrate.

The composite powder is preferably 2 to 30% by weight of silica and / or silica hydrate and 2 to 15% by weight of barium sulfate with respect to 100% by weight of the composite powder.
The average particle size of the composite powder is preferably 10 to 250 nm.

The composite powder further has a surface coating layer of at least one compound selected from the group consisting of silicone, alkylsilane, amino acid, polyamide and salts thereof, metal soap, and water-repellent resin. Is preferred.

The present invention includes a step (1) of treating the surface of zinc oxide particles or titanium oxide particles with silica and / or silica hydrate, and a step of impregnating the obtained silica-treated zinc oxide particles or titanium oxide particles with barium ions ( It is also a method for producing the above-mentioned composite powder comprising 2) and the step (3) of neutralizing with sulfuric acid and / or water-soluble sulfate to precipitate barium sulfate.

The present invention is also a cosmetic obtained by blending the above-described composite powder.
The present invention is also an ink obtained by blending the above-described composite powder.

In view of the above-mentioned problems, the present inventors have conducted earnest development research to form a coating layer composed of barium sulfate and silica and / or silica hydrate on zinc oxide and titanium oxide. The present invention has been completed by discovering that it is possible to relieve the feeling of squeaking that has been a problem with zinc and titanium oxide and to obtain a composite powder with a good touch.

The composite powder obtained in the present invention can increase the degree of inactivation because the pores of silica are filled with barium sulfate as well as the touch improvement, and the surface potential is changed by barium sulfate, Dispersion is easy even in a pH range where silica-treated zinc oxide and silica-treated titanium oxide are difficult to disperse. Further, even when the outermost layer is subjected to a surface treatment with silicone or the like, a water-repellent powder in which the feeling improving effect derived from barium sulfate is maintained can be obtained.

2 is a scanning electron micrograph of the composite powder of the present invention obtained in Example 1. FIG. 2 is an image showing mapping of the composite powder of the present invention obtained in Example 1 according to wavelength dispersion X-ray analysis of Zn. 2 is an image showing mapping of the composite powder of the present invention obtained in Example 1 by Si wavelength dispersion X-ray analysis. 3 is an image showing mapping of Ba of the composite powder of the present invention obtained in Example 1 by wavelength dispersion X-ray analysis. 2 is a transmission electron micrograph of the composite powder of the present invention obtained in Example 1. FIG. 3 is an image showing mapping of Zn of the composite powder of the present invention obtained in Example 1 by energy dispersive X-ray analysis of Zn. 2 is an image showing mapping of the composite powder of the present invention obtained in Example 1 by energy dispersive X-ray analysis of Si. 2 is an image showing mapping of Ba of the composite powder of the present invention obtained in Example 1 by energy dispersive X-ray analysis.

The composite powder of the present invention is obtained by forming a coating layer made of barium sulfate and silica and / or silica hydrate on the surface of zinc oxide particles or titanium oxide particles. By suppressing the surface activity with silica and / or silica hydrate and using barium sulfate in combination, a good feel can be imparted. Since an inorganic material called barium sulfate is used to improve the touch, the composite powder has higher thermal stability than other composite powders that have been improved in touch with organic substances.

The coating layer is made of barium sulfate and silica and / or silica hydrate. Here, as a state of the coating layer, barium sulfate is preferably present on the surface or pores of silica and / or silica hydrate. In addition to the touch improvement effect, a more highly inactivated composite powder can be obtained. Therefore, it is considered that inactivation is also promoted by the presence of barium sulfate in the pores to fill the pores.

Such a state of barium sulfate will be described with reference to the drawings. FIG. 1 is a scanning electron micrograph of the composite powder 1 obtained in Example 1. 2 to 4 are images showing mapping by wavelength dispersion X-ray analysis of Zn, Si, and Ba, respectively. It can be seen from the Ba mapping data in FIG. 4 that there is no single barium sulfate particle.

Next, FIG. 5 is a transmission electron micrograph of the composite powder 1 obtained in Example 1. 6 to 8 are images showing mappings of Zn, Si, and Ba by energy dispersive X-ray analysis, respectively. It can be seen from the Zn mapping data in FIG. 6 and the Si mapping data in FIG. 7 that silica is coated on the outside of zinc oxide. Moreover, it can be seen from the Ba mapping data in FIG. 8 that barium sulfate is present on and / or inside the zinc oxide particles that are uniformly silica-treated.

As the silica coating layer, one formed by any known method can be used. Silica surface-treated zinc oxide particles and titanium oxide particles are commercially available, and these commercially available products may be used as raw materials.

The shape of the barium sulfate coating layer is not particularly limited, but is preferably in the form of particles having a particle diameter of about 0.5 to 20 nm. In the case of such a shape, since the particle diameter of barium sulfate is small, it can be suitably coated even when fine particle zinc oxide and fine particle titanium oxide having excellent ultraviolet shielding effect are used as core particles.

In the composite powder coating layer, the content of silica and / or silica hydrate is preferably 2 to 30% by weight, with the total weight of the composite powder being 100% by weight. If it is less than 2% by weight, the amount of silica itself is small and the amount of impregnated barium ions is small, so that there is a possibility that the inactivation and the improvement in touch are insufficient. If it exceeds 30% by weight, the contents of zinc oxide and titanium oxide are decreased, and the ultraviolet shielding property becomes insufficient, which is not preferable. The content is more preferably 4 to 20% by weight.

In the composite powder coating layer, the barium sulfate content is preferably 2 to 15% by weight, with the total weight of the composite powder being 100% by weight. If it is less than 2% by weight, the feel-improving effect may be insufficient. If it exceeds 15% by weight, the contents of zinc oxide and titanium oxide serving as the core may be reduced, and the ultraviolet shielding effect may be reduced. The content is more preferably 5 to 10% by weight.

There are no particular restrictions on the particle size of the zinc oxide particles and titanium oxide particles used in the present invention, but a particle size of 10 to 200 nm is preferable in order to effectively provide ultraviolet shielding properties. Moreover, it is more preferable in it being 15-100 nm from the balance of transparency and UV shielding property. This particle size measurement method is a method of measuring the particle size of 200 particles randomly selected with an electron microscope and calculating the average of the primary particle sizes.

The shapes of the zinc oxide particles and the titanium oxide particles are not particularly limited, and those having an arbitrary shape such as a spherical shape, a rod shape, a needle shape, a spindle shape, or a plate shape can be used. The average particle diameter in the case of rod-like, needle-like, and spindle-like particles is defined by the length on the short axis side, and in the case of plate-like particles, the average of the diagonal lengths of the surfaces.

The zinc oxide particles and titanium oxide particles are zinc oxide particles and titanium oxide particles doped with foreign elements such as manganese, calcium, and nitrogen, such as lead oxide particles and titanium oxide particles doped with Fe. May be. Alternatively, zinc oxide particles or titanium oxide particles coated with aluminum hydroxide or silicone may be used.

The composite powder can be further subjected to a surface treatment with an inorganic compound or an organic compound by a known method. For example, inorganic surface treatments such as aluminum hydroxide, aluminum oxide, titanium oxide, zirconium oxide, silica, and cerium oxide can be performed. Examples of organic surface treatment agents that can be used for the surface treatment include dimethylpolysiloxane, methylhydrogenpolysiloxane, (dimethicone / methicone) copolymer, methylphenyl silicone, amino-modified silicone, triethoxysilylethylpolydimethylsiloxy. Silicone oils such as ethyl dimethicone, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, alkyl silanes such as caprylyl silane, decyl silane, perfluorooctyl silane, alkyl titanates, alkyl aluminates, polyolefins, polyesters, amino acids such as lauroyl lysine, polyamides, And metal salts such as salts thereof, aluminum stearate, aluminum isostearate and zinc stearate , As well as nylon, polyester, water-repellent resin polyacrylic, and the like. Moreover, coupling agents, such as a silane coupling agent and a titanium coupling agent, can also be used. The surface treatment may be performed with at least one compound selected from these organic compounds. It is also possible to combine additional inorganic and organic surface treatments. In particular, it is very effective to perform organic surface treatment when it is desired to blend the composite powder into oil or resin.

The method for producing the composite powder is not particularly limited. For example, the step (1) of treating the surface of zinc oxide particles or titanium oxide particles with silica and / or silica hydrate, and the obtained silica-treated zinc oxide particles Alternatively, a production method comprising a step (2) of impregnating titanium oxide particles with barium ions and a step (3) of neutralizing with water-soluble sulfate to precipitate barium sulfate can be mentioned. Such a manufacturing method is also one aspect of the present invention.

The step (1) for surface treatment with the silica and / or silica hydrate is not particularly limited, and a known method can be used. For example, a method in which an aqueous sodium silicate solution is added to an aqueous slurry of zinc oxide particles or titanium oxide particles, followed by neutralization by adding sulfuric acid to precipitate silica and / or silica hydrate, or zinc oxide or titanium oxide Is dispersed in alcohol, water, or a mixed solvent of alcohol and water, to which alkoxysilane such as tetraethoxysilane is added, and hydrolyzed by acid, base, heating, etc. to produce silica and / or silica hydrate. Examples thereof include a method for precipitation and a method for firing silica-treated powder to produce silica. In order to enhance the deactivation of the zinc oxide particles or titanium oxide particles, it is important to coat the silica as uniformly as possible.

The step (2) is a step of impregnating the obtained silica-treated zinc oxide particles or titanium oxide particles with barium ions. The silica-treated zinc oxide particles or silica-treated titanium oxide particles are dispersed in water, and an aqueous solution in which a water-soluble barium compound is dissolved is added thereto, whereby barium ions are added to the silica-treated zinc oxide particles or silica-treated titanium oxide particles. Can be impregnated. It is preferred to heat the system to promote impregnation.

The water-soluble barium compound is not particularly limited as long as it is easily soluble in water, and examples thereof include barium hydroxide, barium nitrate, barium acetate, barium oxalate, and barium chloride. Any salt readily reacts with sulfuric acid to produce barium sulfate, but it is most suitable to use barium hydroxide whose by-product is water.

The amount of the water-soluble barium compound added is preferably 3 to 30% by weight in terms of BaSO _{4 with} respect to silica-treated zinc oxide particles or silica-treated titanium oxide particles, and finally obtained composite powder It is preferable to adjust so that it may become 2 to 15 weight% with respect to 100 weight% of a body. If it is less than the above lower limit, the feeling improving effect becomes insufficient, and if it exceeds the upper limit, many unimpregnated barium ions are generated, which is not preferable. Depending on the amount of surface-treated silica and silica hydrate, even if an excessive amount of water-soluble barium salt is added, the impregnation is limited to a fixed amount. Excess water-soluble barium salt can be removed by washing in a later step.

After the impregnation with barium ions, it is preferable to perform a filtration and water washing step for the purpose of removing unimpregnated barium ions. In the presence of unimpregnated barium ions, single barium sulfate is produced, which may not be preferable for use. The method of filtration and a water-washing process is not specifically limited, A well-known method can be used. For example, a filter press, an Oliver type filter, a centrifugal filter and the like are preferable from the viewpoint of efficiency. The washed product obtained here may be dried with hot air or the like. At that time, care should be taken because barium ions are deposited from the inside of the particles to the surface with drying, but there is also an advantage that the surface of the particles can be coated with a smaller amount of barium ions.

After the water washing step or the drying step, a step (3) of repulping, dispersing again in water, neutralizing with sulfuric acid and / or water-soluble sulfate, and precipitating barium sulfate is performed. Moreover, when the barium ion which is not impregnated does not exist or is a trace amount which does not affect the use, the filtration / water washing step can be omitted and the sulfuric acid neutralization step can be directly entered.

The method of neutralization is not particularly limited, and a method of neutralizing sulfuric acid and / or water-soluble sulfate aqueous solution into a dispersion slurry of particles impregnated with barium ions, and sulfuric acid and / or water-soluble sulfate aqueous solution. A method in which a dispersion slurry of particles impregnated with barium ions is charged and neutralized, a dispersion slurry of particles impregnated with sulfuric acid and / or a water-soluble sulfate aqueous solution and barium ions is prepared in separate containers, and these are further added. For example, a method of neutralizing by simultaneously charging in another container can be mentioned.

The water-soluble sulfate may be anything as long as it is easily soluble in water. For example, sodium sulfate, potassium sulfate, ammonium sulfate, sulfate of lower amine, etc. are mentioned. From the viewpoint of easy removal of by-products, use of sulfuric acid or ammonium sulfate is preferred. Moreover, the sulfuric acid whose by-product is water is more preferable.

The pH after neutralization with sulfuric acid and / or water-soluble sulfate is not particularly limited as long as it is a pH region in which barium sulfate is precipitated. However, since zinc oxide is easily dissolved in an acid, it is preferable to keep the pH at 5 or more.

After the step (3), it is dried again through a filtration / water washing step to obtain a composite powder. Depending on the application, a pulverization step may be added after the drying step and fine pulverization may be performed, or a wet pulverization step may be added without the drying step to form a dispersion in which the composite powder is dispersed.

The average particle size of the obtained composite powder is preferably 10 to 250 nm, and more preferably 15 to 100 nm. If it is smaller than 10 nm, the ultraviolet shielding property may be insufficient, and if it is larger than 250 nm, the visible light transparency may be insufficient. In addition, the said average particle diameter can be measured similarly to the above-mentioned zinc oxide particle and titanium oxide particle.

Further, it is preferred that the specific surface area of the obtained composite powder is 10 to 150 m ² / g, more preferably 15~110m ² / g. When it is smaller than 10 m ² / g, both the ultraviolet shielding property and the visible light transparency may be insufficient, and when it is larger than 150 m ² / g, the ultraviolet shielding property may be insufficient.

The composite powder of the present invention can also be blended in cosmetics, inks, paints, resin compositions and the like. Further, the composite powder of the present invention can be dispersed in water or oil and used as a raw material. Since barium sulfate is present on the powder surface, it is expected that the charged state of the powder will change, and it is expected that the dispersibility will be improved depending on the dispersion solvent, surfactant and dispersant. The cosmetics and inks are also one aspect of the present invention.

The cosmetic is not particularly limited, and by mixing a cosmetic raw material with such a composite powder as necessary, an ultraviolet protective cosmetic such as a sunscreen agent; a base makeup cosmetic such as a foundation; a lipstick Point makeup cosmetics and the like can be obtained.

The cosmetics can be in any form of oily cosmetics, aqueous cosmetics, O / W cosmetics, and W / O cosmetics. Especially, it can use especially suitably in a sunscreen agent. Moreover, it is also suitable to mix | blend with makeup bases taking advantage of the touch.

The cosmetic may be used in combination with any aqueous component or oily component that can be used in the cosmetic field. The aqueous component and the oil component are not particularly limited, and examples thereof include oil agents, surfactants, humectants, higher alcohols, sequestering agents, natural and synthetic polymers, water-soluble and oil-soluble polymers, UV shielding agents, Various extracts, colorants such as organic dyes, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, cooling agents, antiperspirants, fungicides, skin activators, various powders, etc. It may contain a component.

The oil agent is not particularly limited. For example, natural animal and vegetable oils and fats (for example, olive oil, mink oil, castor oil, palm oil, beef tallow, evening primrose oil, coconut oil, castor oil, cacao oil, macadamia nut oil, etc.); wax (for example, Jojoba oil, beeswax, lanolin, carnauba wax, candelilla wax, etc.); higher alcohols (eg, lauryl alcohol, stearyl alcohol, cetyl alcohol, oleyl alcohol, etc.); higher fatty acids (eg, lauric acid, palmitic acid, stearic acid, olein) Acids, behenic acid, lanolin fatty acids, etc .; higher aliphatic hydrocarbons such as liquid paraffin, solid paraffin, squalane, petrolatum, ceresin, microcrystalline wax, etc .; synthetic ester oils (eg, butyl stearate, hexyl laurate, diisopropyl azimuth) , Diisopropyl sebacate, octyldodecyl myristate, isopropyl myristate, isopropyl palmitate isopropyl myristate, cetyl isooctanoate, neopentyl glycol dicaprate); silicone derivatives (eg, silicones such as methyl silicone and methyl phenyl silicone) Oil) and the like. Furthermore, oil-soluble vitamins, preservatives, whitening agents, and the like can be added.

Examples of the surfactant include a lipophilic nonionic surfactant and a hydrophilic nonionic surfactant. The lipophilic nonionic surfactant is not particularly limited. For example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate. Sorbitan fatty acid esters such as diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, mono-cotton oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, α, α '-Glycerol polyglycerin fatty acids such as glyceryl oleate pyroglutamate, glyceryl monostearate malate, propylene glycol monostearate Glycol fatty acid esters, hardened castor oil derivatives, glycerin alkyl ethers and the like.

The hydrophilic nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene (hereinafter abbreviated as POE) sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, and POE sorbitan tetraoleate. POE sorbitan fatty acid esters, POE sorbite monolaurate, POE sorbite monooleate, POE sorbite monooleate, POE sorbite fatty acid esters such as POE sorbite monostearate, POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin fatty acid esters such as POE glycerin triisostearate, POE monooleate, POE distearate, POE monodiolate, ethylene glycol stearate POE fatty acid esters such as Pole, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE2-octyldodecyl ether, POE cholesterol ether, and other POE alkyl ethers, POE octylphenyl ether, POE nonylphenyl POE alkylphenyl ethers such as ether, POE dinonylphenyl ether, pluronic types such as brulon, POE / polyoxypropylene (hereinafter abbreviated as POP) cetyl ether, POE / POP2-decyltetradecyl ether, POE / POP mono POE / POP alkyl ethers such as butyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, Tetra POE / Tora POP ethylenediamine condensates, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE hydrogenated castor oil POE castor oil hardened castor oil derivatives such as maleic acid, POE beeswax / lanolin derivatives such as POE sorbit beeswax, alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, POE propylene glycol fatty acid ester, POE Alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenyl formaldehyde condensate, alkylethoxydimethylamine oxide, trioleyl A phosphoric acid etc. can be mentioned.

Examples of other surfactants include anionic surfactants such as fatty acid soaps, higher alkyl sulfates, POE lauryl sulfate triethanolamine, alkyl ether sulfates, alkyltrimethylammonium salts, alkylpyridinium salts, alkyl quaternary salts. Stabilizes cationic surfactants such as ammonium salts, alkyldimethylbenzylammonium salts, POE alkylamines, alkylamine salts, polyamine fatty acid derivatives, and amphoteric surfactants such as imidazoline-based amphoteric surfactants and betaine-based surfactants. And you may mix | blend in the range which does not have a problem in skin irritation.

The moisturizing agent is not particularly limited, and examples thereof include xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl- Examples thereof include pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Isaiyobara extract, Achillea millefolium extract, and Merirot extract.

The higher alcohol is not particularly limited, and examples thereof include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol), 2-decyl. Examples thereof include branched chain alcohols such as tetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, and the like.

The sequestering agent is not particularly limited. For example, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, sodium citrate, sodium polyphosphate, metaphosphoric acid Examples thereof include sodium, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid and the like.

The natural water-soluble polymer is not particularly limited. For example, arabia gum, tragacanth gum, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (rice, rice, Corn, potato, wheat), plant polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan and pullulan, and animal polymers such as collagen, casein, albumin and gelatin. .

The semi-synthetic water-soluble polymer is not particularly limited. For example, starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, Examples thereof include cellulose polymers such as hydroxypropylcellulose, sodium carboxymethylcellulose (CMC), crystalline cellulose, and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.

The synthetic water-soluble polymer is not particularly limited, and examples thereof include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, and polyvinyl pyrrolidone, and polyoxyethylene polymers such as polyethylene glycol 20,000, 40,000, and 60,000. Polymer, polyglycerin, polyoxyethylene polyoxypropylene copolymer copolymer polymer, acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, polyethyleneimine, cationic polymer, carboxyvinyl polymer, alkyl Examples thereof include modified carboxyvinyl polymer.

The inorganic water-soluble polymer is not particularly limited, and examples thereof include bentonite, silicate A1Mg (beegum), laponite, hectorite, and silicic anhydride.

The ultraviolet screening agent is not particularly limited. For example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl Benzoic acid UV screening agents such as PABA ethyl ester, N, N-dimethyl PABA butyl ester, 4-bis (polyethoxy) PABA polyethoxyethyl ester, diethylaminohydroxybenzoyl hexyl benzoate; homomenthyl-N-acetylanthranylate, etc. Anthranilic acid UV screening agent: amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate Salicylic acid-based UV-screening agents such as octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinna Mate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano Cinnamic acid-based UV screening agents such as -β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate; 2,4-dihydroxy Benzophenone, 2, 2 '-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy Benzophenone-based UV screening agents such as -4-n-octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone; 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1 , 3,5-triazine, 3- (4′- Tylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenyl Benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenylbenzotriazole), dibenzalazine, dianisoylmethane, 4-methoxy-4 ′ -T-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one and the like can be mentioned.

Other drug components are not particularly limited and include, for example, vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, nicotinic acid DL-α-tocopherol, magnesium ascorbate, 2 Vitamins such as -O-α-D-glucopyranosyl-L-ascorbic acid, vitamin D2 (ergocaciferol), dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid, biotin; estradiol, ethinylestradiol, etc. Hormones; amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptophan; anti-inflammatory agents such as allantoin and azulene; whitening agents such as arbutin; astringents such as tannic acid; L Menthol, cooling agents and sulfur camphor such as, lysozyme chloride, can be mentioned pyridoxine chloride, and the like.

There are no particular limitations on the various extracts, for example, Dokudami extract, Oat extract, Merirot extract, Odorikosou extract, Licorice extract, Peonies extract, Soap extract, Loofah extract, Kina extract, Yukinoshita extract, Clara extract, Kouhone extract, Fennel Extract, Primrose Extract, Rose Extract, Giant Extract, Lemon Extract, Shikon Extract, Aloe Extract, Shobu Root Extract, Eucalyptus Extract, Horsetail Extract, Sage Extract, Thyme Extract, Tea Extract, Seaweed Extract, Cucumber Extract, Clove Extract, Raspberry Extract, Melissa Extract , Carrot extract, horse chestnut extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, thymus extract, silk extract, licorice Mention may be made of a kiss, etc.

Examples of the various powders include bengara, yellow iron oxide, black iron oxide, titanium mica, iron oxide-coated mica titanium, titanium oxide-coated glass flakes and other bright colored pigments, mica, talc, kaolin, sericite, titanium dioxide, Inorganic powder such as silica, alumina, aluminum hydroxide, barium sulfate, zinc oxide, calcium carbonate, magnesium carbonate, magnesium silicate, boron nitride, polyethylene powder, polyamide powder, crosslinked polystyrene, polymethyl methacrylate, cellulose powder, silicone powder, etc. And organic powders. Preferably, a part or all of the powder component is hydrophobized by a known method with a substance such as silicones, fluorine compounds, metal soaps, oils, acyl glutamates in order to improve sensory characteristics and cosmetic durability. Used. Moreover, you may mix and use the other composite powder which does not correspond to this invention.

The composite particles of the present invention can also be used as a blending component of ink. Since the composite powder has an excellent ultraviolet shielding effect and dispersibility, it is particularly useful as a component for sunscreen ink. The ink may be used in combination with known components. For example, colored pigments such as titanium oxide, zinc oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, and calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc, etc. Pigment components such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments; shellac resins, acrylic resins, styrene-acrylic resins, styrene- It can be used in combination with a binder resin such as a maleic acid resin, a styrene-acrylic-maleic acid resin, a polyurethane resin, a polyester resin, a polyamide resin or the like; a water-miscible organic solvent or the like.

When blending the composite particles of the present invention into a coating composition, the resin in the coating composition may be curable or non-curable. The coating composition may be a solvent-based one containing an organic solvent or a water-based one in which a resin is dissolved or dispersed in water.

When the composite particle of the present invention is used as an additive component to a coating composition, a film-forming resin such as an acrylic resin, a polyester resin, or an epoxy resin; various pigments such as a color pigment, an extender pigment, or a glitter pigment; a curing catalyst , Surface conditioners, antifoaming agents, pigment dispersants, plasticizers, film-forming aids, ultraviolet absorbers, antioxidants, and the like.

The composite powder of the present invention can be mixed with a resin and used as a resin composition. In this case, the resin used may be a thermoplastic resin or a thermosetting resin, and an epoxy resin, a phenol resin, a polyphenylene sulfide (PPS) resin, a polyester resin, polyamide, polyimide, polystyrene, polyethylene, Polypropylene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polymethyl methacrylate, ethylene / ethyl acrylate copolymer (EEA) resin, polycarbonate, polyurethane, polyacetal, polyphenylene ether, polyetherimide, acrylonitrile-butadiene-styrene Examples of the resin include polymer (ABS) resin, liquid crystal resin (LCP), silicone resin, and acrylic resin.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.
(Example 1)
500 g of silica-coated zinc oxide (composite powder of zinc oxide having an average particle diameter of 20 nm of 75 wt% and silica of 25 wt%) was dispersed in 4 L of pure water. In another container, 60 g of barium hydroxide was dissolved in 500 ml of pure water. Next, an aqueous barium hydroxide solution was added to the zinc oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered and the filter cake was washed with water. The washed cake was dispersed in 4 L of pure water, and neutralized to pH 7.5 while adding sulfuric acid at 5 ml / min. This solution was filtered, washed with water, and dried to obtain composite powder 1. The average particle diameter observed with a transmission electron microscope was 27 nm.

(Example 2)
100 g of silica-coated zinc oxide (composite powder of 90 wt% zinc oxide having an average particle diameter of 20 nm and 10 wt% silica) was dispersed in 1 L of pure water. In another container, 12 g of barium hydroxide was dissolved in 100 ml of pure water. Next, an aqueous barium hydroxide solution was added to the zinc oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered and the filter cake was washed with water. The washed cake was dispersed in 1 L of pure water and neutralized to pH 8 while adding sulfuric acid at 1 ml / min. This liquid was filtered, washed with water, and dried to obtain composite powder 2. The average particle diameter observed with a transmission electron microscope was 24 nm.

(Example 3)
100 g of silica-coated zinc oxide (composite powder of 95 wt% zinc oxide having an average particle diameter of 35 nm and 5 wt% silica) was dispersed in 1 L of pure water. In another container, 12 g of barium hydroxide was dissolved in 100 ml of pure water. Next, an aqueous barium hydroxide solution was added to the zinc oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered and the filter cake was washed with water. The washed cake was dispersed in 1 L of pure water and neutralized to pH 7.5 while adding sulfuric acid at 1 ml / min. This liquid was filtered, washed with water and then dried to obtain a composite powder 3. The average particle diameter observed with a transmission electron microscope was 40 nm.

Example 4
100 g of silica-coated zinc oxide (composite powder having an average particle diameter of 20 nm of zinc oxide of 78 wt% and silica of 22 wt%) was dispersed in 1 L of pure water. In another container, 3 g of barium hydroxide was dissolved in 100 ml of pure water. Next, an aqueous barium hydroxide solution was added to the zinc oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered to obtain a filter cake. The filter cake was dispersed in 1 L of pure water and neutralized to pH 7.5 while adding sulfuric acid at 1 ml / min. This solution was filtered, washed with water, and dried to obtain composite powder 4. The average particle diameter observed with a transmission electron microscope was 26 nm.

(Example 5)
100 g of silica-coated titanium oxide (a composite powder of spindle-shaped titanium oxide 80 wt% and silica 20 wt% having a major axis of 100 nm × minor axis of 20 nm) was dispersed in 1 L of pure water. In another container, 12 g of barium hydroxide was dissolved in 100 ml of pure water. Next, an aqueous barium hydroxide solution was added to the titanium oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered and the filter cake was washed with water. The washed cake was dispersed in 1 L of pure water and neutralized to pH 7 while adding sulfuric acid at 1 ml / min. This liquid was filtered, washed with water and then dried to obtain composite powder 5. The average particle diameter observed with a transmission electron microscope was 23 nm.

(Comparative Example 1)
100 g of zinc oxide not coated with silica (zinc oxide having an average particle diameter of 20 nm) was dispersed in 1 L of pure water. In another container, 12 g of barium hydroxide was dissolved in 100 ml of pure water. Next, an aqueous barium hydroxide solution was added to the zinc oxide dispersion, and the liquid was heated to 80 ° C. The state was maintained for 2 hours and then cooled to room temperature. The liquid was filtered and the filter cake was washed with water. The washed cake was dispersed in 1 L of pure water and neutralized to pH 8 while adding sulfuric acid at 1 ml / min. This solution was filtered, washed with water and then dried to obtain a comparative powder 1.

Silica-coated zinc oxide (composite powder of 90 wt% zinc oxide with an average particle size of 20 nm and 10 wt% silica) as comparative powder 2, titanium oxide coated with silica (major axis 100 nm × minor axis 20 nm spindle-shaped titanium oxide A composite powder of 80 wt% and silica 20 wt% was used as comparative powder 3.

Table 1 shows the specific surface area of the obtained powder and the composition of each powder. Table 2 shows the results of evaluating the feel of the obtained powder and the feel when dispersed in water by 20 panelists. In this touch test, the feel (good slip) when a powder or dispersion is spread on the skin is evaluated in 5 stages from 1 bad to 5 good for each panel, and the average value is described.

From the results of Table 2, it was shown that the composite powder of the present invention has an excellent feel both when used alone and when used as an aqueous dispersion.

4 g of hydrogen dimethicone was added to the composite powder 1 (100 g) and mixed well with a mixer. Then, the silicone processing powder was obtained by heat-processing at 120 degreeC overnight. An emulsion was prepared using the silicone-treated powder with the materials and parts shown in Table 3. First, after mixing the materials of the oil phase, they were stirred and dispersed with a homogenizer for 15 minutes. Thereafter, the water phase material that had been mixed in advance was added while stirring by the homogenizer was continued, and emulsion was obtained by emulsifying and stirring for 15 minutes. This emulsion had a better feel than an emulsion prepared using zinc oxide that was not surface treated with barium sulfate.

Since the composite powder of the present invention has an excellent ultraviolet shielding effect and a good feel, it can be particularly suitably used for cosmetics, inks and the like.

Claims (7)

A composite powder having an average particle diameter of 10 to 250 nm formed by forming a coating layer made of barium sulfate and silica and / or silica hydrate on the surface of zinc oxide particles or titanium oxide particles. The composite powder according to claim 1, wherein in the coating layer, barium sulfate is present on the surface and / or pores of silica and / or silica hydrate. The composite powder according to claim 1 or 2, wherein the silica and / or silica hydrate is 2 to 30% by weight and the barium sulfate is 2 to 15% by weight with respect to 100% by weight of the composite powder. Furthermore, silicone, alkylsilane, amino acids, polyamides and their salts, metal soaps, as well as, according to claim 1, 2 or 3 and has a surface coating layer of at least one compound selected from the group consisting of water-repellent resin The composite powder described. A step (1) of treating the surface of zinc oxide particles or titanium oxide particles with silica and / or silica hydrate, a step (2) of impregnating the obtained silica-treated zinc oxide particles or titanium oxide particles with barium ions, and The method for producing a composite powder according to claim 1, comprising a step (3) of neutralizing with sulfuric acid and / or water-soluble sulfate to precipitate barium sulfate. A cosmetic obtained by blending the composite powder according to claim 1, 2, 3 or 4 . An ink obtained by blending the composite powder according to claim 1, 2, 3 or 4 .