JP4473667B2 - Hydroxyapatite particle-bonded synthetic resin porous particles, external preparations, cosmetics - Google Patents

Description

    The present invention relates to a porous particle having a novel structure and a method for producing the same. Furthermore, this invention relates to the external preparation or cosmetics which selectively adsorb | suck the unsaturated fatty acid of sebum containing this porous particle.

Hydroxyapatite (or hydroxyapatite or HAP) is a substance represented by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ and is an inorganic substance present in the human body such as a tooth bone. Known are external preparations that adsorb sebum and unsaturated fatty acids in sebum, or cosmetics formulated as pigments for improving the makeup of cosmetic films (see, for example, Patent Documents 1, 2, and 3).
However, when hydroxyapatite is directly blended into cosmetics and external preparations, problems have been pointed out, such as roughening and a feeling of use being deteriorated, and sebum cannot be effectively adsorbed by aggregation. For this reason, techniques for processing hydroxyapatite into a spherical shape (see, for example, Patent Documents 4, 5, and 6) and techniques for depositing hydroxyapatite on the pigment surface (for example, see Patent Document 7) have been developed. However, both of these techniques are desirable because hydroxyapatite is deposited on the surface of the resin or pigment base material by physical treatment (for example, electrostatic treatment or mixed compression treatment), or bonded with a binding agent. Only a sufficient amount of hydroxyapatite could not be coated. Further, there are drawbacks such as the bonding state of hydroxyapatite being unstable, or the bonding of hydroxyapatite non-uniformly to the surface of the particles. For this reason, even sebum, an external preparation that adsorbs unsaturated fatty acids in sebum, or a cosmetic containing hydroxyapatite as a pigment to improve the makeup of the cosmetic film can effectively adsorb sebum. could not.

In the prior art, organic polymer synthetic porous particles made of acrylamide or polyvinyl alcohol polymer are excellent in oil absorption and water absorption speed, and are therefore blended in cosmetics to improve makeup (for example, Patent Document 8). reference). However, simply making it porous is not preferable because it only adsorbs moisture and absorbs some sebum. A preferred external preparation for skin is an agent that effectively adsorbs unsaturated fatty acids that can be irritating to the skin.
In particular, fatty acids, especially unsaturated fatty acids, irritate the skin by being oxidized, but the effect of reducing skin irritation is low if these unsaturated fatty acids are not adsorbed even if only sebum is adsorbed. In addition, since the amount of oil absorption was not sufficient, the effect was also low for makeup. For this reason, it has been desired to improve the fatty acid adsorptivity of sebum of conventional synthetic porous particles.

Japanese Patent No. 173912 JP 63-027411 A JP-A-62-195317 Japanese Examined Patent Publication No. 4-27203 Japanese Patent Publication No. 6-92288 Japanese Patent No. 2818328 Japanese Patent No. 2914460 Japanese Patent Publication No. 4-51522

    In order to remove sebum waste that has an adverse effect on the skin among the sebum components, the present inventors have intensively studied whether there is an effective method for keeping the skin normal, further preventing rough skin, and improving rough skin. , Hydroxyapatite bonded to the surface of porous particles exhibits particularly selective adsorptive properties for free fatty acids and lipid peroxides, which are sebum waste products, preventing rough skin, improving rough skin, and also causing inflammation in acne patients. It has been found that there is an inhibitory effect. However, if the hydroxyapatite powder is blended in the skin external preparation as it is, the hydroxyapatite powder has a strong cohesiveness, so that it does not sufficiently spread to the skin, and the effect of adsorbing sebum waste is not sufficiently exhibited. For this reason, the present inventors have developed novel porous particles in which hydroxyapatite particles having an average particle size of 0.1 to 1 μm are firmly bonded to the surface of the resin, thereby completing the present invention. Accordingly, the present invention provides a porous particle characterized in that a hydroxyapatite particle having an average particle diameter of 0.1 to 1 μm is firmly bonded to the surface of a resin constituting the porous fine particle as described above. The issue is to provide. Furthermore, the present invention provides an external preparation containing porous particles characterized in that hydroxyapatite particles having an average particle size of 0.1 to 1 μm are firmly bonded to the surface of the resin constituting the particles. And cosmetics, particularly makeup cosmetics and skin care cosmetics.

    The present inventors have discovered a novel porous particle in which a part of a hydroxyapatite particle having an average particle size of 0.1 to 1 μm is bonded to the surface of a resin constituting the porous particle, which has been found by the present inventors. Compared to conventional hydroxyapatite and porous particles, it absorbs more sebum and effectively adsorbs unsaturated fatty acids in sebum without affecting the feeling of use or affecting the dosage form. It has been found that reduction of skin irritation and improvement of makeup are realized. These particles are different from conventional particles made of a resin coated with hydroxyapatite, and the hydroxyapatite is firmly bonded to the surface of the porous particles. These porous particles are not pressure-bonded, bonded, or electrostatically bonded as in the past, but the monomer used as the raw material for the target polymer resin is polymerized to synthesize hydroxyapatite in the monomer. It is obtained by adopting a completely new method of coexistence. It is a new technology that has not been disclosed or suggested in the prior art.

That is, the present invention is as shown in the following 1 to 6 .
1. Hydroxyapatite particles having an average particle diameter of 0.1 to 1 μm on the surface of the porous synthetic resin particles are porous particles made of an organic polymer synthetic resin having a porosity of 5 to 50% and an average particle diameter of 1 to 20 μm. A skin external preparation formulated with bonded porous particles , wherein the organic polymer synthetic resin is an acrylate resin, and the porous particles obtained by polymerization while coexisting hydroxyapatite are blended An external preparation for skin.
2. 1 porous particles, characterized in that hydroxyapatite is porous particles bound 10 to 50% by weight relative to the weight of the porous resin. The skin external preparation as described.
3. 1. The shape of the porous particles is almost spherical. Or 2. The skin external preparation as described.
4). 1. ~ 3. A method for producing porous particles to be blended with the external preparation for skin according to any one of the above, wherein the hydroxyapatite particles are dispersed in a solution of a synthetic resin monomer used as a raw material in the synthesis of the porous particles, followed by a polymerization reaction step A method for producing porous particles to be blended in an external preparation for skin , characterized by performing a porosification step and a particle formation step.
5). 1. An external preparation for skin selectively adsorbs unsaturated fatty acids in sebum . ~ 3. The external preparation for skin according to any one of the above .
6). 1. An external skin preparation is a cosmetic. ~ 3,5. The external preparation for skin according to any one of the above .

By carrying out the present invention, it is characterized in that a novel hydroxyapatite particle body having an average particle size of 0.1 to 1 μm is bonded to the surface of a new resin constituting porous fine particles. Porous particles and methods for making the same are provided.
Furthermore, by carrying out the present invention, the porous material is characterized in that a part of hydroxyapatite particles having an average particle size of 0.1 to 1 μm are bonded to the surface of the resin constituting the particles in a state of being embedded. External preparations and cosmetics, in particular makeup cosmetics and skin care cosmetics, containing the functional particles are provided.
The external preparation or cosmetic containing the particles of the present invention has an excellent feeling of use and inflammation suppression compared to conventional external preparations and cosmetics. The cosmetic of the present invention is excellent in makeup and adhesion, has high oil absorption and sebum fatty acid selective adsorption. As a material for supporting oils and fats, it can be added to foods and general industrial materials.

Hydroxyapatite used in the present invention is a substance represented by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ and is an inorganic substance present in the human body such as a tooth bone. The hydroxyapatite powder is usually prepared by, for example, the following wet method or dry method.
That is, as an example of a wet method, a method obtained by reacting calcium hydroxide and phosphoric acid in an aqueous solution, and as an example of a dry method, calcium carbonate and calcium phosphate are reacted in air or in a steam atmosphere at a high temperature. There are ways to get it. Hydroxyapatite used in the present invention preferably has a particle diameter of 0.1 μm to 1 μm and a spherical or irregular shape. For this reason, preparation by a wet method is preferable, but any synthesis method can be used as long as it satisfies the desired conditions. When the particle diameter of hydroxyapatite is less than 0.1 μm, the hydroxyapatite particles having an average particle diameter of 0.1 to 1 μm are partially embedded in the surface of the resin constituting the porous fine particles. Aggregation is likely to occur during the synthesis of the porous particles, and is not effective in absorbing the target fatty acid. On the other hand, when the particle diameter of hydroxyapatite exceeds 1 μm, it becomes difficult to bond to the surface of the resin constituting the porous fine particles. Moreover, by making the shape of hydroxyapatite spherical or irregularly shaped, it is possible to obtain porous particles that selectively adsorb more unsaturated fatty acids with less roughness on the skin and excellent usability.

The porous particles made of the organic polymer synthetic resin of the present invention are prepared by dispersing hydroxyapatite particles in a synthetic resin monomer solution, and then performing each step of polymerization reaction, porosification reaction, and particle formation in parallel or independently. Can be obtained by doing
In the following, acrylate is exemplified as the synthetic resin, and the porous particles are composed of the organic polymer synthetic resin of the present invention, the porosity is 5 to 50%, the pore diameter is 5 to 5,000 nm, and the average of the particles Porous, characterized in that a part of hydroxyapatite particles having an average particle diameter of 0.1 to 1 μm are embedded in the surface of the resin constituting the fine particles having a particle diameter of 1 to 20 μm and embedded therein. A method for preparing the particles will be described. The present invention is not limited to this, and necessary embodiments can be carried out according to conventional methods according to the purpose.

    The acrylate resin is composed of 50 to 99.9% by weight of alkyl (meth) acrylate, 0.1 to 30% by weight of a polyfunctional monomer having two or more vinyl groups in the molecule, and 0 to 49. It is obtained by subjecting a mixture of 9% by weight of monomer and hydroxyapatite particles to a granulating step while copolymerizing in the presence of a dispersion stabilizer and a porosifying agent. Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl (meth). Those having 1 to 10 carbon atoms in the alkyl group such as acrylate are preferred. When the alkyl group has more than 10 carbon atoms, it is difficult to obtain spherical particles when the particles are synthesized by the suspension method described below.

Porous particles made of the organic polymer synthetic resin of the present invention, having a porosity of 5 to 50%, a pore diameter of 5 to 5,000 nm, and an average particle size of 1 to 20 μm and constituting porous fine particles In the synthesis of porous particles bonded with a portion of hydroxyapatite particles having an average particle size of 0.1 to 1 μm embedded on the surface of the resin, methods such as emulsion polymerization, suspension polymerization, and dispersion polymerization are used. Is used. Preferably, suspension polymerization is performed by adding hydroxyapatite to the monomer solution.
Suspension polymerization can stabilize the particle shape and can provide a product in which hydroxyapatite is uniformly arranged on the surface of the porous particles.
Suspension polymerization is performed using the monomer mixture, dispersion stabilizer, surfactant, oil-soluble radical polymerization initiator, porosifying agent, and the like described above.

It is desirable that the oil-soluble radical polymerization initiator and the porosifying agent are previously dissolved or dispersed in the monomer mixture described above.
Examples of the polyfunctional monomer having two or more vinyl groups in the molecule used in the preparation using the alkyl methacrylate include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene Alkane polyols such as glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, diallyl itaco Examples thereof include monomers having different reactive vinyl groups such as nates, other urethane di (meth) acrylates, and epoxy (meth) acrylates. Other copolymerizable monomers include aromatic vinyl such as styrene, vinyl toluene, α-methylstyrene, vinyl cyanide such as aromatic vinylidene, acrylonitrile, methacrylonitrile, vinylidene cyanide, urethane (meth) acrylate, etc. Can be mentioned.

In this case, a monomer having a functional group can also be copolymerized. For example, monomers having an epoxy group such as glycidyl methacrylate, monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meta ) Monomers having an amino group such as acrylate.
It is desirable to use trimethylolpropane tri (meth) acrylate as the polyfunctional monomer having two or more vinyl groups in the molecule.

    Examples of the dispersion stabilizer include water-soluble gelatin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyacrylic acid salt, sodium alginate, and partially saponified products of polyvinyl alcohol. Polymers, inorganic substances such as titanium oxide, calcium carbonate, silicon dioxide and the like are used. These dispersion stabilizers can be used alone or in combination of two or more.

    As the surfactant, anionic surfactants such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate and sodium lauryl sulfate, and nonionic surfactants such as polyethylene glycol nonylphenyl ether are used. These surfactants can be used alone or in combination of two or more.

    Examples of the oil-soluble radical polymerization initiator include organic peroxides such as benzoyl peroxide, O-methoxybenzoyl peroxide, O-chlorobenzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and 2,2′-azobisiso An azo compound such as butyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, or the like is used. Moreover, these oil-soluble radical polymerization initiators can use one type or two or more types.

The porosifying agent is a substance that makes the organic polymer crosslinked particles porous, and several types can be appropriately selected. One of them is a solvent that dissolves in the monomer mixture but does not dissolve in the polymer after polymerization, such as toluene, isooctane, methyl isobutyl ketone, and the like. In this case, the amount of the solvent used is about 20 to 200 parts by weight with respect to 100 parts by weight of the monomer mixture.
The used porosifying agent is removed in the particle drying step, and the portions where the solvent is removed become pores. As another porosifying agent, for example, a linear polymer that dissolves in the monomer mixture, such as alkyl poly (meth) acrylate, is used. The amount of the linear polymer used in this case is about 1 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture, and the linear chain dissolved in the process of proceeding the polymerization of the monomer mixture described above. Cause phase separation with the polymer, and the particles become porous. The type of linear polymer used is not particularly limited, but the shape and size of the pores vary depending on the type of polymer. One kind or two or more kinds of porous agents for obtaining these surface-treated porous spherical powders can be used.
The formation of particles varies depending on the type, amount, and stirring speed of each additive added to the mixed solution. In order to obtain particles having a desired size, it is necessary to carefully control the stirring speed. However, an optimum state can be appropriately selected and determined according to the target resin and particle diameter.

In the process of the above synthesis, the hydroxyapatite particles are not present inside the synthesized porous resin, but are oriented on the surface of the resin, and the hydroxyapatite particles are firmly embedded in the resin. Combine. Such porous resin particles have not been known at all.
A porous particle comprising the organic polymer synthetic resin of the present invention, wherein a hydroxyapatite particle having an average particle size of 0.1 to 1 μm is firmly bonded to the surface of the resin. The average particle size is preferably in the range of 1 to 20 μm, particularly preferably 5 to 10 μm. When the average particle diameter is less than 1 μm, hydroxyapatite does not bind effectively, and the adsorptivity of fatty acids also decreases. When the average particle size exceeds 20 μm, when used as an external preparation or when used in cosmetics, the skin may have a rough feeling, and a good usability may be impaired. The “spherical shape” in the particles of the present invention does not necessarily have to be a spherical shape, and means a particle shape close to a spherical shape without a large protrusion. In addition, the irregular shape means a polymorphic shape having no sharp tip angle.

    Porous particles comprising the organic polymer synthetic resin of the present invention, wherein the hydroxyapatite particles having an average particle size of 0.1 to 1 μm are firmly bonded to the surface of the resin, In the range of 5 to 5,000 nm, the average diameter of the pores observed when observed with an electron microscope after dissolving hydroxyapatite by the acid dissolution method with a porosity of 5 to 50% when measured by mercury porosimetry It is preferable that The average diameter of the holes can be determined by image analysis processing or the like based on the result of observation with an electron microscope. If the pore diameter is 5 nm or less, the desired absorption effect cannot be obtained. If the pore diameter is 5000 nm or more, the particles are brittle and the desired amount of hydroxyapatite does not bind.

    The particles of the present invention are coated with hydroxyapatite bonded to the surface of a spherical porous resin. The bonding rate of the hydroxyapatite to the resin is defined in the present invention as the bonding rate or the covering rate based on the weight of the hydroxyapatite added to the weight of the resin monomer. As described above, the hydroxyapatite added in the resin forming step is substantially entirely oriented on the surface of the porous spherical particles. Accordingly, the percentage by weight of hydroxyapatite per monomer is defined in the present invention as the binding ratio of hydroxyapatite to the porous particles of the present invention. In addition, the hydroxyapatite binding rate (coverage) when calculated by the weight conversion method defined in this manner is preferably 10 to 50% by weight in the present invention. Absorbability, in particular, selective adsorption of unsaturated fatty acids cannot be obtained.

    The particles of the present invention are characterized in that a part of the hydroxyapatite particles are firmly bonded to the resin. As explained in the prior art, the spherical synthetic resin particles bonded with the hydroxyapatite particles obtained by the conventional method are bonded or pressure-bonded to the surface of the resin by physical force, or They are only bonded via a binding agent. The bonding state is relatively gentle and is only bonded to the resin surface as shown in FIG. 2 or FIG. On the other hand, in the particles made of the porous polymer resin of the present invention, a part of the hydroxyapatite particle body is embedded in the resin. For this reason, the resin and the hydroxyapatite particles are firmly bonded. This bonded state cannot be dissociated by physical impact. On the other hand, in the particles coated with hydroxyapatite prepared by the conventional technique, hydroxyapatite is dissociated by physical impact. The difference in the bonding state is that the particles of the present invention exhibit the particle size distribution inherent in the porous particles when the particle size distribution is measured after the particles are processed with a device that gives physical impact such as a hammer mill. On the other hand, the particles prepared by the conventional technique can be confirmed by showing a bimodal distribution of the particle size of the resin particles and the particle size of the hydroxyapatite peeled off due to physical impact.

    Further, the hydroxyapatite particles are oriented on the surface of the porous particles in the process of crosslinking the monomers constituting the resin. Accordingly, the resin and hydroxyapatite exhibit a bonding state different from that of the prior art. That is, in the prior art, hydroxyapatite comes into contact with the resin surface at a point, but in the case of the present invention, hydroxyapatite comes into contact with the resin surface on the surface or bonds in an embedded state. The difference in this state is that the contact surface between the resin and the hydroxyapatite is in close contact when the particle is cut, for example, on a plane passing through the center line of the particle and the cross section is observed with an electron microscope or a high-resolution microscope. It can be confirmed by contact.

    Porous particles comprising the organic polymer synthetic resin of the present invention, wherein porous particles characterized in that individual bonded hydroxyapatite particles are firmly bonded to the resin are used as a skin external preparation. Can effectively adsorb fatty acids and suppress skin inflammation and acne. The compounding ratio to an external preparation and cosmetics is 0.01 to 30 weight% normally, Preferably it is 0.1 to 10 weight%. If the blending ratio is less than 0.01% by weight, sufficient sebum absorbability and unsaturated fatty acid adsorbability cannot be obtained. When the blending ratio exceeds 30% by weight, a rough feeling is generated and a good feeling in use is impaired.

    Porous particles made of the organic polymer synthetic resin of the present invention, characterized in that hydroxyapatite particles having an average particle size of 0.1 to 1 μm are firmly bonded to the surface of the resin constituting the porous fine particles. The porous particles can be widely applied to all external preparations and cosmetics, particularly makeup cosmetics and skin care cosmetics. In blending, it can be blended into external preparations and cosmetics in the same manner as conventional pigment blending. In particular, the cosmetics of the present invention thus provided include makeup cosmetics such as foundations, lipsticks, cheeks, eyeliners, eye shadows, eyebrows, eyebrows, powdered and face powders, And skin care cosmetics such as lotions, essences, emulsions, gels and powders for controlling the sebum of the scalp.

    Further, the porous particles are composed of the organic polymer synthetic resin of the present invention, and the porosity is 5 to 50%, the average particle diameter is 1 to 20 μm, and the average particle diameter is 0 on the surface of the resin constituting the porous fine particles. Porous particles characterized by being bonded in a state where a part of .1-1 μm hydroxyapatite particles are embedded can absorb a large amount of oil and selectively adsorb unsaturated fatty acids. Therefore, it can be used in cosmetics and can be used in a wide range of fields such as external preparations, pharmaceuticals, foods, paints, etc. It can be applied as a fatty acid selective adsorbent.

    External preparations and cosmetics of the present invention include fats and oils such as vegetable oils, higher fatty acids, higher alcohols, silicon, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, preservatives, Contains sugars, sequestering agents, polymers such as water-soluble polymers, thickeners, powder components, UV absorbers, UV blockers, moisturizers such as hyaluronic acid, fragrances, pH adjusters, etc. Can be made. Vitamins, skin activators, blood circulation promoters, resident bacteria control agents, active oxygen scavengers, anti-inflammatory agents, whitening agents, bactericides, and other medicinal and physiologically active components can also be included.

As fats and oils, for example, camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, glycerin trioctanoate, etc., cocoa butter, coconut oil, Hardened coconut oil, palm oil, palm kernel oil, owl, owl kernel oil, hardened oil, hardened castor oil and other solid fats, beeswax, candelilla wax, cotton wax, nutca wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax Waxes.
Examples of hydrocarbons include liquid paraffin, squalene, squalane, and microcrystalline wax.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like.

Examples of the higher alcohol include linear alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, and cetostearyl alcohol, and branched chain alcohols such as monostearyl glycerol ether, lanolin alcohol, cholesterol, phytosterol, and octyldodecanol.
Examples of silicon include linear polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, and cyclic polysiloxanes such as decamethylcyclopentasiloxane.

Examples of the anionic surfactant include fatty acid salts such as sodium laurate, higher alkyl sulfates such as sodium lauryl sulfate, alkyl ether sulfates such as POE lauryl sulfate triethanolamine, N-acyl sarcosine acid, sulfosuccinate , N-acyl amino acid salts and the like.
Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, benzalkonium chloride, and benzethonium chloride.
Examples of amphoteric surfactants include betaine surfactants such as alkyl betaines and amide betaines.
Examples of nonionic surfactants include sorbitan fatty acid esters such as sorbitan monooleate and hydrogenated castor oil derivatives.

Examples of preservatives include methyl paraben and ethyl paraben.
Examples of the sequestering agent include edetates such as disodium ethylenediaminetetraacetate, edetic acid, and sodium edetate.
Examples of polymers include gum arabic, gum tragacanth, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, pullulan, carboxymethyl starch, collagen, casein, gelatin, methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, carboxymethylcellulose Examples thereof include vinyl polymers such as sodium (CMC), sodium alginate, and carboxyvinyl polymer (such as CARBOPOL).
Examples of the thickener include carrageenan, tragacanth gum, quince seed, casein, dextrin, gelatin, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, xanthan gum, bentonite and the like.
Examples of powder components include talc, kaolin, mica, silica, zeolite, polyethylene powder, polystyrene powder, cellulose powder, inorganic white pigment, inorganic red pigment, titanium oxide coated mica, titanium oxide coated talc, and colored titanium oxide coated mica. And organic pigments such as Red No. 201 and Red No. 202.

Examples of the ultraviolet absorber include paraaminobenzoic acid, phenyl salicylate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2,4-dihydroxybenzophenone, and the like.
Examples of the ultraviolet blocking agent include titanium oxide, talc, carmine, bentonite, kaolin, and zinc oxide.
Examples of humectants include polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, glycerin, diglycerin, polyglycerin, xylitol, maltitol, maltose, sorbitol, glucose, fructose. , Sodium chondroitin sulfate, sodium hyaluronate, sodium lactate, pyrrolidone carboxylic acid, cyclodextrin and the like.

As medicinal components, for example, vitamin A oil, vitamin A such as retinol, vitamin B ₂ such as riboflavin, B ₆ such as pyridoxine hydrochloride, L- ascorbic acid, L- ascorbic acid phosphoric acid ester, L- ascorbic Vitamin C such as acid monopalmitate, L-ascorbic acid dipalmitate, L-ascorbic acid-2-glucoside, pantothenic acid such as calcium pantothenate, vitamin D such as vitamin D ₂ and cholecalciferol, Vitamins such as vitamin E such as α-tocopherol, tocopherol acetate and DL-α-tocopherol nicotinate can be mentioned.
Whitening agents such as placenta extract, glutathione, and yukinoshita extract; skin activators such as royal jelly and beech tree extract; Examples include glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, anti-inflammatory agents such as azulene, amino acids such as arginine, serine, leucine, and tryptophan, maltose sucrose condensates of resident bacteria control agents, and lysozyme chloride.
In addition, chamomile extract, parsley extract, wine yeast extract, grapefruit extract, honeysuckle extract, rice extract, grape extract, hop extract, rice bran extract, loquat extract, buckwheat extract, yakuinin extract, assembly extract, merilot extract, birch extract, licorice extract, peony extract , Savonso extract, loofah extract, capsicum extract, lemon extract, gentian extract, perilla extract, aloe extract, rosemary extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, carrot extract, carrot extract, maronier extract, Examples include various extracts such as chammel extract and mulberry extract.

Further, the present invention is a porous particle made of an organic polymer synthetic resin having a porosity of 5 to 50% and an average particle diameter of 1 to 20 μm, and having an average particle diameter of 0. Porous particles characterized by binding of 1 to 1 μm hydroxyapatite particles have excellent adsorption characteristics and are porous, so they can be used as molecular sieves and adsorbents as chromatographic carriers. Is possible.
Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited thereto.

[Production Example 1]
Preparation of Porous Particles Composed of Organic Polymer Synthetic Resin Bonded with Hydroxyapatite of the Present Invention An average particle diameter of 0.2 μm in an aqueous solution in which 5 g of polyvinyl alcohol (Kuraray Poval 205, Kuraray Co., Ltd.) is dissolved in 555 g of water A mixed liquid consisting of 50 g of hydroxyapatite powder, 190 g of methyl (meth) acrylate, 10 g of trimethylolpropane tri (meth) acrylate, 1 g of lauroyl peroxide and 100 g of methyl isobutyl ketone is added, and this is stirred using a homomixer and mixed with monomers. A liquid dispersion was prepared. At this time, the homogenizer was stirred at a rotation speed of the stirring blade of 3,000 rpm to prepare a dispersion solution. This dispersed solution was transferred to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, heated to 60 ° C. with stirring at a rotational speed of 100 rpm under a nitrogen stream, and suspended for 3 hours. The suspension polymerization reaction was performed.
After cooling the resulting particle suspension to room temperature, the particles were filtered and washed with water, and the cake collected on the filter was dried at 110 ° C. for 24 hours to obtain a portion of the hydroxyapatite particles having an average particle size of 8 μm. 238 g of porous particles bonded in the embedded state were obtained. An electron micrograph of the obtained porous particles of the present invention is shown in FIG. The pore diameter of this particle was about 100 nm. The hydroxyapatite coverage was 23.2%.

[Comparative Production Example 1]
Production Example of Nonporous Particles In order to confirm the effect of the presence or absence of pores in the resin particles on the oil absorbency of the particles and the absorption of fatty acids, nonporous particles were prepared. That is, no porous agent was added, and the following conditions were used under the same conditions to prepare particles in which a portion of the hydroxyapatite particles were embedded. The preparation method is as follows.
In an aqueous solution in which 5 g of polyvinyl alcohol (made by Kuraray Poval 205 Co., Ltd.) was dissolved in 555 g of water, 120 g of hydroxyapatite powder having an average particle size of 0.2 μm, 190 g of methyl (meth) acrylate, 10 g of trimethylolpropane tri (meth) acrylate A mixed solution of 1 g of lauroyl peroxide was added. This was stirred using a homomixer to prepare a dispersion solution of the monomer mixture. At this time, the stirring strength of the homomixer was set to 3,000 rpm in the same manner as in Production Example 1 to prepare a dispersion solution. This dispersion solution is transferred to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing port, heated to 60 ° C. while stirring under a nitrogen stream, and allowed to undergo a suspension polymerization reaction for 3 hours. It was. The obtained suspension was cooled to room temperature, filtered and washed with water, and the cake collected on the filter was dried at 110 ° C. for 24 hours to obtain a non-porous structure having an average particle size of 8 μm and a hydroxyapatite coverage of 15.8%. Particles were obtained.
An electron micrograph of the obtained non-porous particles is shown in FIG.

[Comparative Production Example 2]
Preparation of surface-treated porous spherical powder by mechanochemical method In order to confirm the effect of the binding state of hydroxyapatite on the absorption of fatty acids, particles in which hydroxyapatite was bonded to the particle surface were prepared by conventional techniques.
In an aqueous solution obtained by dissolving 5 g of polyvinyl alcohol (Kuraray Poval 205, Kuraray Co., Ltd.) in 555 g of water, 190 g of methyl (meth) acrylate, 10 g of trimethylolpropane tri (meth) acrylate, 1 g of lauroyl peroxide, 100 g of methyl isobutyl ketone A mixed solution consisting of the following was added, and this was stirred using a homomixer to prepare a dispersion of the monomer mixed solution. At this time, the homogenizer was stirred at a rotation speed of the stirring blade of 3,000 rpm to prepare a dispersion solution. This dispersion was transferred to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing port, heated to 60 ° C. while stirring under a nitrogen stream, and allowed to undergo a suspension polymerization reaction for 3 hours. It was. The obtained suspension was cooled to room temperature, filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain a porous spherical powder having an average particle size of 8 μm. 60 parts of the obtained porous spherical powder is mixed with 40 parts of hydroxyapatite powder having an average particle size of 0.2 μm, mixed with a Henschel mixer for 10 minutes, and then mixed with a rotary ball mill for 24 hours. Particles were obtained.
An electron micrograph of the resulting prior art particles is shown in FIG.

    As is apparent from FIGS. 1, 2 and 3, the particles according to the present invention have hydroxyapatite intimately bonded to each other, whereas particles obtained based on the conventional technique have irregularities on the surface. (FIG. 2), and a phenomenon in which hydroxyapatite falls off was observed.

[Physical property measurement]
The particle shape, average particle size, hydroxyapatite coating state, and porosity of the particles of the present invention (Production Example 1), Comparative Production Example 1 and Comparative Production Example 2 were measured. The measurement results are shown in Table 1.
The average particle diameter (μm) was measured by Coulter Multisider II (manufactured by Coulter Co., Ltd.), and the value of the arithmetic diameter of the weight distribution was adopted.
The porosity (%) of the holes formed in the synthetic resin particles was determined by a mercury intrusion method.
Further, the coating state of hydroxyapatite was observed with an electron micrograph, and according to the bonding state, ◯: almost no unattached particles, Δ: some unattached particles, x: many unattached particles.
The results are shown in Table 1 below.

As shown in Table 1, the particles of the present invention have a porous spherical shape, an average particle size of 8.2 μm, a porosity of 25%, and uniform hydroxyapatite with almost no hydroxyapatite unattached particles. Was obtained.
Further, in order to confirm whether or not hydroxyapatite is present in a portion other than the surface, the particle powder of Production Example 1 was dispersed and hardened in an epoxy resin, and then the resin was cut and the fractured surface of the powder was as shown in FIG. Were confirmed with a transmission electron microscope. The white part was hydroxyapatite, and it was confirmed that only the periphery of the spherical powder was coated in a uniform state.
In addition, the mechanochemical method particles of Comparative Production Example 2 and the present invention particles of Production Example 1 were observed with an optical microscope. Appropriate amount of “LOCTITE Multipurpose Pro-use Type Co., Ltd.” is applied to the acrylic resin plate, and then the particles by the mechanochemical method of Comparative Production Example 2 and the present invention particles of Production Example 1 are placed flat on it and dried thoroughly. Let Thereafter, the sample was cut flat with a diamond cutter in the horizontal direction, and the section was observed with an optical microscope.
As a result, the particles of Comparative Production Example 2 are porous inside, and the surface (outer periphery) is similarly uneven (FIG. 8). Although it is porous, the surface (outer periphery) is flat, and it can be seen that the surface is particularly densely coated with hydroxyapatite (FIG. 9).

[Hydroxyapatite binding confirmation test]
After 100 g of each of the particles obtained in Production Example 1 and Comparative Production Example 1 were pulverized 3 times with a hammer mill (Fuji Powder), the particle size distribution was measured with Coulter Multicider II (Coulter Co., Ltd.).
The particles of Production Example 1 have no particles of 1 μm or less and are concentrated at 8 to 9 μm. (FIG. 5). On the other hand, when the particle size distribution was measured by treating the particles of Comparative Production Example 1 in the same manner, the particle size distribution was bimodal, with the original particle size of 10 μm peak and the hydroxyapatite particle size of about 0.5 μm peak. Shown (FIG. 6). This is because the particles of Comparative Production Example 1 were detached from hydroxyapatite due to physical impact.

[Particle porosity confirmation test]
10 g of the particles obtained in Production Example 1 were washed with 10N hydrochloric acid three times to obtain particles from which the bonded hydroxyapatite was removed. The obtained particles were observed with an electron microscope to obtain the image of FIG. It was confirmed that the resin particles had slightly rough surface as compared with the case where the hydroxyapatite was not coated, and formed porous particles.

[Oil absorption measurement]
The oil absorption of squalane and oleic acid of the particles obtained in Production Example 1, Comparative Production Example 1 and Comparative Production Example 2 was measured. Squalane is known as the saturated fatty acid contained in sebum, and oleic acid is known as the unsaturated fatty acid contained in sebum. By measuring the oil absorption and wet point for these two oils, the unsaturated fatty acid in sebum It is possible to know about the selective adsorptivity of.
The amount of oil absorption is precisely weighed in a beaker with 5 g of each sample. Squalane or oleic acid is gradually added dropwise, and kneaded thoroughly with a spatula each time, and the amount when the whole becomes a putty-like mass is measured as the wet point. Then, the amount of oil required until fluidity was obtained was defined as oil absorption = pour point−wet point (ml / 100 g). The lower the wet point, the easier it is to adjust to the oil, and the higher the oil absorption, the more oil can be retained. The measurement results are shown in Table 2 below.

    As shown in Table 2, it was found that the particles of the present invention had an oil absorption of squalane of 125.3 and an oil absorption of oleic acid as high as 220.5, and in particular, an oil absorption of oleic acid was high. Moreover, the wet point of oleic acid was as low as 23.2, and it was confirmed that it was easy to be familiar with oleic acid. The particles of the present invention were confirmed to be particles that can selectively adsorb unsaturated fatty acids, particularly oleic acid, as compared with conventional particles.

[Real use test]
A powder foundation, a cream foundation, and an eye shadow containing the particles of Production Example 1 of the present invention and the particles of Comparative Production Examples 1 and 2 were prepared, and an actual use test was performed.

Composition of powder foundation containing particles of Example 1 and Comparative Examples 1 and 2
(Manufacturing method) After stirring 1-7 with a Henschel mixer for 5 minutes, 8-9 mixed well is gradually added and pulverized with a hammer mill. Thereafter, it was pressed into an intermediate dish to prepare a sample.

Composition of eye shadow containing the particles of Example 1 and Comparative Examples 1 and 2
(Manufacturing method) After stirring 1-8 with a Henschel mixer for 5 minutes, 9-10 mixed well is gradually added and pulverized with a hammer mill. Thereafter, it was pressed into an intermediate dish to prepare a sample.

Cream foundation composition containing the particles of Example 1 and Comparative Examples 1 and 2
(Manufacturing method) 1-5 is grind | pulverized with a hammer mill. Thereafter, 6 to 8 are added and dispersed with a homomixer until uniform. 9-10 mixed well is added thereto and stirred for 10 minutes with a homomixer. Thereafter, the sample was deaerated to prepare a sample.

    Table 6 shows the evaluation results of Formulation Examples 1 to 3 and Comparative Examples 1 to 6 using the present particles. The test method was that 20 women were allowed to use the samples of Formulation Examples 1 to 3 and Comparative Examples 1 to 6 for 1 week, and evaluated for spread, roughness, stickiness, makeup, and adhesion. The evaluation score was a maximum of 5 points, 1 point was evaluated as bad to 5 points, and an average score was calculated. Regarding skin irritation, the case where irritation was felt by one or more persons by self-report was evaluated as x, and the case where no irritation was felt or improvement effects such as improvement of inflammation and acne were observed was evaluated as ◯.

Evaluation results of blending examples 1 to 3 and comparative examples 1 to 6 using the present particles

    As shown in the results shown in Table 6, it was confirmed that the cosmetic containing the particles of the present invention had good spread and was excellent in adhesion and makeup without stickiness or roughness. In addition, no one complained of skin irritation. Moreover, it has confirmed that it had the improvement effect of an inflammatory state.

A scanning electron micrograph of the particles of the present invention is shown. The scanning electron micrograph of the particle | grains of the comparative manufacture example 1 is shown. The scanning electron micrograph of the particle | grains of the comparative manufacture example 2 is shown. The image which observed the cut surface with the transmission electron microscope in the state which cut | disconnected this invention particle | grains in the surface which passes along the center is shown. The bright white part of the screen is hydroxyapatite particles, and the black circular part is the resin. It can be confirmed that the hydroxyapatite is in close contact with the resin. The result of having measured the particle size distribution after grind | pulverizing the particle | grains of this invention obtained by manufacture example 1 of this invention 3 times with the hammer mill by Coulter multi-cider II is shown. The result of having measured the particle size distribution after grind | pulverizing the particle | grains obtained by the comparative manufacture example 1 3 times with a hammer mill by the Coulter multicider II is shown. The scanning electron micrograph which observed the shape of the particle | grains after wash | cleaning this invention particle | grains obtained by the manufacture example 1 of this invention with 10N hydrochloric acid is shown. The optical micrograph of the particle | grain cross section obtained by the comparative manufacture example 2 is shown. The optical micrograph of this invention particle | grain cross section obtained by the manufacture example 1 of this invention is shown.

Claims (6)

Hydroxyapatite particles having an average particle diameter of 0.1 to 1 μm on the surface of the porous synthetic resin particles are porous particles made of an organic polymer synthetic resin having a porosity of 5 to 50% and an average particle diameter of 1 to 20 μm. It is a skin external preparation formulated with bound porous particles ,
A skin external preparation characterized in that the organic polymer synthetic resin is an acrylate resin, and porous particles obtained by polymerizing hydroxyapatite in the presence of hydroxyapatite are blended. Porous particles, skin external preparation according to claim 1, characterized in that the porous particles hydroxyapatite is bonded 10 to 50% by weight relative to the weight of the porous resin. The skin external preparation according to claim 1 or 2, wherein the porous particles have a substantially spherical shape. It is a manufacturing method of the porous particle mix | blended with the skin external preparation in any one of Claims 1-3, Comprising: In the synthesis | combination of a porous particle, a hydroxyapatite particle is disperse | distributed in the solution of the synthetic resin monomer used as a raw material. A method for producing porous particles to be blended in an external preparation for skin , characterized by performing a polymerization reaction step, a porosification step and a particle formation step. The external preparation for skin according to any one of claims 1 to 3, which selectively adsorbs unsaturated fatty acids in sebum. The skin external preparation according to any one of claims 1 to 3 and 5, wherein the skin external preparation is a cosmetic .