JP2002003517A - Spherical resin particle, manufacturing method thereof and external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high function resin particle which is excellent in an optical property such as light collecting, light scattering to a certain direction or the like and a frictional property such as slipping property and which is capable of applying to wide fields and to provide an excellent feeling external preparation. SOLUTION: The object is resolved by the spherical resin particle characterized by satisfying the formulas [0.8<d/D<1.0 (I) and 0.1 (μm)<=D<=500 (μm) (II)] when a particle size of the transverse direction is D (μm) and the maximum height of the longitudinal direction is d (μm) in a side view wherein a bowl-like depression exists on a particle surface and a boundary line in opening of depression is the transverse direction. The object is also resolved by the external preparation blended with the particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of electronics such as LCD spacers, surface modifiers for silver salt films, film modifiers for magnetic tapes, thermal paper running stabilizers, etc., inks and adhesives, antigen-antibody. It has a bowl-shaped depression suitable for applications in the medical field such as particles for reaction inspection, cosmetics such as slip agents and extender pigments, and general industrial fields such as low shrinkage agents, paper, dental materials, and resin modifiers. The present invention relates to a spherical resin particle, a method for producing the same, and an external preparation containing the spherical resin particle.

[0002]

2. Description of the Related Art Without improving the mechanical properties of plastics or changing the chargeability of a developer, the cleaning properties of the plastics can be improved, the mattability and concealment of paints can be improved, and the quality of cosmetics can be improved. Various resin particles are used for various purposes, such as improving the slipperiness. Since such resin particles are produced by a pulverization method, an emulsion polymerization method, a suspension polymerization method, a seed polymerization method, a dispersion polymerization method, etc., usually only amorphous resin particles or spherical resin particles are obtained, It has not been sufficiently satisfactory for applications in which further functionalization is required.

[0003] Therefore, porous resin particles, resin particles having a distorted depression on the particle surface, composite resin particles having a bowl-shaped depression, and a composite having a bowl-shaped depression containing a large amount of additives in the particles. Although resin particles and the like have been proposed,
The particles may be porous (Japanese Patent Application Laid-Open No. 10-7704), or the resin particles may be a composite (Japanese Patent Application Laid-Open No. 5-884).
No. 09), the shape of the dent is distorted (Japanese Patent Application Laid-Open No. H11-140139), so its use is limited, and its function is not sufficiently satisfactory.

As external preparations containing particles, makeup cosmetics such as foundations, white powders, blushers, eye shadows, etc., body cosmetics such as body powders and baby powders, and lotions such as pre-shave lotions and body lotions are used. In these external preparations, to improve the elongation on the skin, to improve the feel, to impart functions such as wrinkle concealing effects, as particles, nylon particles, polymethyl methacrylate particles, cross-linked polystyrene particles, silicone particles, urethane particles, Spherical resin particles such as polyethylene particles or spherical inorganic particles such as silica particles and titania particles are blended.

However, when these particles are blended as they are, although the lubricating properties are improved, the properties of the particles directly affect the blended external preparations, which may deteriorate the feel of the external preparations. There were restrictions. Therefore, in order to improve the feel of the external preparation, the particles have been subjected to a surface treatment in advance and then blended into the external preparation. However, even with such particles, the feel of the external preparation could not be sufficiently improved.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin particle having a higher function and more suitable for various purposes of use and a method for producing the same, and to provide an external preparation having an excellent feel. Is what you do.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, in the absence of a crosslinking agent, 100 parts by weight of a polymerizable vinyl monomer and 100 parts by weight of the polymerizable vinyl monomer. And 1 to less than 5 parts by weight of a hydrophobic liquid compound having a viscosity of 3 to 1,000,000 cSt at 25 ° C. and having no copolymerizability, and then performing aqueous suspension polymerization to form a smooth surface on the particles. Spherical resin particles having a bowl-shaped depression are obtained, and it has been found that the resin particles are suitable for the above-mentioned purpose. Further, the external preparation containing the resin particles has a smooth, non-squeaking feel. The inventors have found that the present invention has excellent homogeneity and completed the present invention.

Thus, according to the present invention, when the particle surface has a bowl-shaped depression on the surface thereof and the boundary line at the opening of the depression is horizontal, the particle diameter in the horizontal direction is D (μ).
m), when the maximum height in the vertical direction is d (μm), the following formula is satisfied: 0.8 <d / D <1.0 (I) 0.1 μm ≦ D ≦ 500 μm (II) And a method for producing the same, and an external preparation prepared by blending the spherical resin particles.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The spherical resin particles of the present invention have a bowl-shaped dent on the particle surface, and the lateral particle size in the side view when the boundary at the dent opening is set to the horizontal direction. Since D (μm) satisfies the following formula: 0.1 μm ≦ D ≦ 500 μm (II), conventional porous particles having fine pores on the particle surface, and spherical resins having distorted dents Unique optical properties not found in particles, composites of resin and resin or composite resin particles having bowl-shaped depressions containing a large amount of additives in the particles, such as light reflectivity and light condensing properties It has friction characteristics such as optical characteristics of light scattering in a specific direction and excellent slipperiness. Furthermore, spherical resin particles to be blended in external preparations such as whitening, foundation, lipstick,
It is preferable that the formula: 1.0 μm ≦ D ≦ 100 μm (II ′) is satisfied, and the spherical resin particles to be blended in an external preparation such as a scrub cosmetic are those satisfying the formula: 100 μm <D ≦ 400 μm (II ″) Is preferred.

[0010] Further, the spherical resin particles of the present invention have a large specific surface area, so that the surface reactivity and the ability to carry functional substances and the like are increased. Therefore, the resin particles of the present invention not only have unique optical properties that could not be expected with conventional spherical particles, but also can be expected to improve chemical properties due to surface modification and the like and physical properties such as fluidity. . For various applications, in order to sufficiently exhibit these effects, it is necessary to have a bowl-shaped depression on the surface of the particle, and to set the boundary line in the depression opening portion to the horizontal direction in a side view. When the particle diameter of D is μm and the maximum height in the vertical direction is d (μm), spherical resin particles satisfying the following formula are preferable. 0.8 <d / D <1.0 (I)

As shown in FIGS. 1 and 2, the particle diameter D in a side view of an arbitrary dent when the boundary line at the dent opening is set to the horizontal direction is shown in FIG.
Represents the particle size (maximum width) in the lateral direction. Among these, those having one depression on the particle surface are preferable in order to impart light reflection, light condensing, and light scattering in a specific direction to the particles while having good slipperiness. In order to improve the characteristics, it is more preferable that d / D satisfies the following expression. 0.85 ≦ d / D ≦ 0.95 (I ′)

Further, in order to impart excellent sliding properties, light scattering properties, surface reflection properties, and the ability to carry a functional substance to the particles,
Assuming that the particle surface has a plurality of bowl-shaped depressions and the average diameter of the openings of the depressions is E (μm), spherical resin particles satisfying the following expression are more preferable. 0.01 ≦ E / D ≦ 0.6 (III) 0.1 μm ≦ D <100 μm (IV) In the following description, E / D is referred to as “opening ratio”.

Further, in order to improve these characteristics,
Those satisfying the following formulas are more preferable. 0.02 ≦ E / D ≦ 0.5 (III ′) 2.0 μm ≦ D ≦ 70 μm (IV ′) The number of dents can be determined by observing one side of n particles using a microscope or a micrograph. When a total of m observations are made, it is calculated by the formula (m / n) × 2. And
When 1.0 ≦ (m / n) × 2 ≦ 2.0, the number of depressions is one, and when 2.0 <(m / n) × 2,
It was assumed that the number of depressions was plural.

When the m / n is lower than 0.1 or the dent is distorted, the spherical resin particles exhibit properties similar to those of conventional spherical particles or porous particles, and it is difficult to obtain the effects aimed at by the present invention. Is not preferred. The above-mentioned numerical values of the particle diameter D and the aperture ratio (E / D) are obtained by observing with an electron microscope or an optical microscope, or by measuring or calculating by an image analysis method thereof. The average value means a number average value. The spherical resin particles of the present invention have 100 parts by weight of a polymerizable vinyl monomer in the absence of a crosslinking agent, have no copolymerizability with the polymerizable vinyl monomer, and have a viscosity of 3 to 10,000 at 25 ° C.
It is obtained by mixing and dissolving 1 to less than 5 parts by weight of a hydrophobic liquid compound of 00 cSt and then subjecting it to aqueous suspension polymerization. According to this method, a wide variety of resin types can be easily manufactured at low cost without requiring a special manufacturing apparatus. Hereinafter, the method for producing the spherical resin particles of the present invention will be described in detail.

The polymerizable vinyl monomer used in the present invention dissolves in a hydrophobic liquid compound described below.
Any compound that does not undergo a polymerization reaction or a crosslinking reaction with the liquid compound may be used. Such vinyl monomers include, for example, styrene monomers such as styrene, p-methylstyrene, p-tert-butylstyrene; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-acrylate Acrylic ester monomers such as ethylhexyl and lauryl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, phenyl methacrylate Methacrylate monomers such as isobornyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, hydrofurfuryl methacrylate, lauryl methacrylate; polyethylene glycol mono (meth) acrylate, methyl biacrylate Alkyl vinyl ether monomers such as vinyl ether; vinyl ester monomers such as vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl benzoate and vinyl neodecanoate; N-alkyls such as N-methylacrylamide and N-ethylacrylamide Substituted acrylamide monomers; acrylonitrile,
Monofunctional hydrophobic vinyl monomers having one vinyl group in the molecule, such as nitrile monomers such as (meth) acrylonitrile, and halogen (eg, fluorine, bromine, chlorine) -substituted products, etc. No. The vinyl monomer is appropriately selected from the above depending on the purpose, and is used alone or in combination of two or more.

The hydrophobic liquid compound used in the present invention has a viscosity of 3 to 1,000,000 cSt at 25 ° C., does not undergo a copolymerization reaction with a polymerizable vinyl monomer, and does not undergo a crosslinking reaction with a functional group present in the vinyl monomer. And those which do not react with water, which is the medium of the suspension polymerization reaction, and are not degraded by water. Such hydrophobic liquid compounds include, for example, hydrocarbons such as paraffinic hydrocarbons, olefinic hydrocarbons, alicyclic hydrocarbons, and hydrocarbon-based liquid polypropylene, liquid polybutene, and liquid polyisobutylene. Examples of the liquid polymer include liquid polysiloxanes having a siloxane bond. Among them, normal paraffin having a viscosity of 50 to 100000 cSt at 25 ° C.,
Isoparaffin, monocyclic cycloparaffin, bicyclic cycloparaffin, liquid polypropylene, liquid polybutene, liquid polyisobutylene, or a viscosity at 25 ° C of 5
Polysiloxanes of 100,000 cSt are preferred.
And, more specifically, the viscosity at 25 ° C.
100000 cSt liquid paraffin, hydrogenated polybutene, hydrogenated polyisobutylene, or 25 ° C.
Further, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane having a viscosity of 5 to 100,000 cSt are more preferable. These hydrophobic liquid compounds can be used alone or in combination of two or more.

As the polymerization initiator used in the present invention, oil-soluble peroxide-based or azo-based ones used for suspension polymerization are usually used. Specifically, for example, benzoyl peroxide, benzoyl peroxide, Lauroyl, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide polymerization initiators such as diisopropylperoxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2′-azobisisobutyronitrile, ,
2′-azobis (2,4-dimethylvaleronitrile),
2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile) , 2,2'-azobis (2-isopropylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2-
(Carbamoylazo) isobutyronitrile, 4,4'-
Azobis (4-cyanovaleric acid), dimethyl-2,
2'-azobisisobutyrate and the like. Among these, benzoyl peroxide, lauroyl peroxide, 2,
Polymerization initiators such as 2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferred.

The spherical resin particles of the present invention are prepared by mixing and dissolving 100 parts by weight of a polymerizable vinyl monomer and 1 to less than 5 parts by weight of a hydrophobic liquid compound, and then adding a polymerization initiator thereto to obtain an aqueous suspension polymer. It can be produced by subjecting it to a reaction. The polymerization initiator is preferably added in an amount of about 0.01 to 2.0 parts by weight, more preferably about 0.1 to 1.0 part by weight, based on 100 parts by weight of the polymerizable vinyl monomer. In the aqueous suspension polymerization of the present invention, in order to stabilize suspended particles, 100 to 1000 parts by weight of water is used as a dispersion medium with respect to 100 parts by weight of a polymerizable vinyl monomer, and a dispersion stabilizer is used as a dispersion medium. Is preferably added.

Examples of the dispersion stabilizer include water-soluble organic polymer compounds, calcium phosphate, magnesium phosphate,
Phosphates such as aluminum phosphate and zinc phosphate, pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate and zinc pyrophosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide And poorly water-soluble inorganic compounds such as calcium metasilicate, calcium sulfate, barium sulfate and colloidal silica. Among them, the use of tricalcium phosphate, magnesium pyrophosphate, calcium pyrophosphate, and colloidal silica produced by a double decomposition method is preferred in that the resin particles of the present invention can be obtained stably. These dispersion stabilizers may be used alone or in combination of two or more kinds.
The amount is about 0.5 to 15 parts by weight with respect to 00 parts by weight. it can.

In the present invention, in addition to the dispersion stabilizer, a surfactant such as an anionic surfactant, a cationic surfactant, a zwitterionic surfactant or a nonionic surfactant may be used in combination. Good. Examples of the anionic surfactant include an alkyl sulfate ester salt such as sodium oleate, sodium lauryl sulfate and ammonium lauryl sulfate, an alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, an alkyl naphthalene sulfonate, an alkane sulfonate, and a dialkyl. Sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene alkyl sulfates, and the like.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of the amphoteric surfactant include lauryl dimethylamine oxide. Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene -Oxypropylene block copolymers and the like. These surfactants can be used alone or in combination of two or more, and the amount of the surfactant is usually about 0.001 to 0.1 part by weight based on 100 parts by weight of the dispersion medium. ,
The type and amount of the spherical resin particles can be appropriately selected in consideration of the particle diameter of the obtained spherical resin particles and the dispersion stability during polymerization.

The aqueous suspension polymerization in the present invention includes, for example,
A hydrophobic liquid compound and a polymerizable vinyl monomer in which a polymerization initiator is dissolved are added to a dispersion medium containing a dispersion stabilizer and a surfactant, and the monomer droplets are dispersed using a propeller blade, a homomixer, or an ultrasonic disperser. It is performed by dispersing in a medium. In order to make the particle size of the obtained resin particles uniform, a microfluidizer, a high-pressure dispersing machine utilizing the collision force between droplets such as a nanomizer or a vessel wall, or
A method of press-fitting a polymerizable vinyl monomer into a dispersion medium through an MPG (microporous glass) porous film is preferable. Next, an aqueous suspension polymerization reaction is performed by heating a dispersion medium in which a mixture containing a polymerizable vinyl monomer and a hydrophobic liquid compound is dispersed as spherical droplets. During the polymerization, it is preferable to perform gentle stirring so as to prevent floating of the monomer droplets and sedimentation of the resin particles generated by the polymerization.

The reaction temperature of the aqueous suspension polymerization is usually from 30 to
100 ° C is preferable, and 40 to 80 ° C is more preferable.
The reaction time is usually about 0.1 to 10 hours. After completion of the polymerization reaction, if necessary, the dispersion stabilizer is decomposed with hydrochloric acid or the like, and the resin particles are isolated from the dispersion medium by suction filtration, centrifugation, centrifugal filtration, or the like. The resulting water-containing cake of resin particles is further washed with water and dried to obtain target resin particles. Although the resin particles thus obtained contain a hydrophobic liquid compound, a hydrophobic liquid compound that does not hinder the effects of the present invention, such as dimethylpolysiloxane or liquid paraffin, is not removed. It can also be used as it is in an external preparation.

On the other hand, when the hydrophobic liquid compound is removed, the resulting mixture is distilled or the liquid compound is dissolved, but the resin is washed with a solvent that does not dissolve the resin. Can be removed.
In the case where the hydrophobic liquid compound is liquid paraffin that can be removed by distillation, the slurry after the polymerization is heated as it is, distillation, vacuum distillation or steam distillation, or resin particles separated from the dispersion medium. A method of dispersing in water or the like and performing distillation is preferred.

The hydrophobic liquid compound is a polysiloxane,
When it is difficult to remove by distillation such as polybutene,
It is preferable to remove by washing with a suitable solvent. As such a solvent, although it depends on the type of the hydrophobic liquid compound and the type of the resin particles, generally, lower alcohols such as methanol, ethanol, isopropanol and isobutanol, pentane, hexane, heptane and octane are used. , Lower hydrocarbons such as cyclohexane, diethyl ether,
Ethers such as dibutyl ether are used.

By appropriately repeating such operations, purified resin particles can be obtained. Particle size of the resin particles of the present invention, mixing conditions of polymerizable vinyl monomer and water,
It can be appropriately adjusted by the amount of the dispersion stabilizer and the like, stirring conditions, dispersion conditions, and the like. The shape of the obtained resin particles can be controlled by adjusting the type and amount of the hydrophobic liquid compound.

The number of depressions in the spherical resin particles according to the present invention depends on the size of the spherical particles. The smaller the particle diameter, the more likely it is to have one, and the larger the particle diameter, the more likely it is to have a plurality. For example, when the particle diameter is 10 μm or less, particles having one depression are easily obtained, and the particle diameter is 50 μm.
If it exceeds m, particles having a plurality of depressions are likely to be obtained.
The external preparation of the present invention can be obtained by blending the spherical resin particles obtained as described above into an external preparation.

Examples of the external preparation in the present invention include external preparations and cosmetics.
There is no particular limitation as long as it is applied to the skin, but specific examples include creams, ointments, and emulsions. As cosmetics, for example, soap, body shampoo,
Cosmetics for washing such as facial cleansing cream, scrub face wash, toothpaste; makeup cosmetics such as whitening, foundation, lipstick, lip balm, blush, eyebrows cosmetics, nail polish; lotion preparations such as pre-shave lotion, body lotion; body powder, baby External preparations for body such as powder; lotion, cream, milky lotion, packs, shampoo, hair dye, hair styling, aromatic cosmetics, bath, antiperspirant, sunscreen, suntan products, shave cream And the like.

The mixing ratio of the spherical resin particles in the external preparation is not particularly limited, and is appropriately adjusted depending on the type of the external preparation.
Usually, about 0.5 to 80% by weight is preferable, and about 2 to 30% by weight is more preferable. When the blending ratio of the spherical resin particles is less than 0.5% by weight, the effect is not clearly recognized. Conversely, when the blending ratio is more than 80% by weight, even if the blending amount is further increased, it is commensurate with it. It is not preferable because the effect is not enhanced. The spherical resin particles may be treated in advance with a surface treatment agent such as an oil agent, a silicone compound and a fluorine compound, an organic powder, an inorganic powder, and the like.

As the oil agent, any oil agent may be used as long as it is usually used in external preparations, for example, hydrocarbon oils such as liquid paraffin, squalane, petrolatum, paraffin wax, lauric acid, myristic acid, palmitic acid, and the like.
Esters such as higher fatty acids such as stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids, glyceryl trioctanoate, propylene glycol dicaprate, cetyl ethyl ethylhexanoate, and isocetyl stearate. Waxes such as oil, beeswax, whale wax, lanolin, carnauba wax, candelilla wax, linseed oil, cottonseed oil, castor oil, egg yolk oil, oils such as palm oil, metal soaps such as zinc stearate and zinc laurate, cetyl Higher alcohols such as alcohol stearyl alcohol and oleyl alcohol are exemplified.

The method of treating the spherical resin particles with an oil agent is not particularly limited. For example, a dry method of coating the oil agent by adding the above oil agent to the spherical resin particles and stirring with a mixer or the like, Utilizing a wet method of coating oils by heating and dissolving in a suitable solvent such as ethanol, propanol, ethyl acetate, hexane, etc., adding particles to the mixture, mixing and stirring, and then removing the solvent under reduced pressure or heating. Can be.

As the silicone compound, any compounds can be used as long as they are usually used in external preparations, such as dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acryl-silicone graft polymer, and organic silicone resin. Partially crosslinked organopolysiloxane polymers and the like can be mentioned. The method of treating the particles with the silicone compound is not particularly limited, and for example, the above-mentioned dry method and wet method can be used. If necessary, a baking treatment may be performed, or a reaction catalyst or the like may be appropriately added in the case of a reactive silicone compound.

The fluorine compound may be any compound as long as it is usually compounded in an external preparation. Examples thereof include perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, and polymers having a perfluoro group. Can be The method of treating the particles with a fluorine compound is not particularly limited, either. For example, the above-mentioned dry method or wet method can be used. If necessary, a baking treatment may be performed, or a reaction catalyst or the like may be appropriately added in the case of a reactive silicone compound.

As the organic powder, for example, gum arabic,
Tragacanth gum, guar gum, locust bean gum,
Natural polymer compounds such as karaya gum, iris moth, quince seed, gelatin, shellac, rosin, casein, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose, etc. Semi-synthetic polymer compound, polyvinyl alcohol,
Polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether,
Resin particles such as polyamide resin, silicone oil, nylon particles, polymethyl methacrylate particles, cross-linked polystyrene particles, silicon particles, urethane particles, polyethylene particles, and fluorine particles.

Examples of the inorganic powder include iron oxide, ultramarine,
Konjo, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide,
Talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica,
Zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, hydroxyapatite,
Ceramic powder and the like can be mentioned.

These organic powders and inorganic powders may have been subjected to a surface treatment in advance. As the surface treatment method, known surface treatment techniques as described above can be used.
In addition, as long as the effects of the present invention are not impaired, ordinary additives generally used in external preparations may be appropriately blended according to the purpose. Such components include, for example, water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, humectants, surfactants, polymer compounds, coloring materials Raw materials, fragrances, preservatives / bactericides, antioxidants, ultraviolet absorbers, and other special compounding ingredients are included.

Oils and waxes include avocado oil,
Almond oil, olive oil, cocoa butter, beef tallow, sesame butter,
Wheat germ oil, safflower oil, shea butter, turtle oil,
Camellia oil, persic oil, castor oil, grape oil, macadamia nut oil, mink oil, egg yolk oil, mokuro, coconut oil, rosehip oil, hydrogenated oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil , Montan wax, beeswax, lanolin and the like.

Examples of the hydrocarbons include liquid paraffin, vaseline, paraffin, ceresin, microcrystalline wax, squalane and the like. Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid,
Examples include oxystearic acid, linoleic acid, lanolin fatty acids, and synthetic fatty acids. As higher alcohols, lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, decyltetradeca Knol and the like.

Sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like. Fatty acid esters include ethyl linoleate, isopropyl myristate, isopropyl lanolin fatty acid, hexyl laurate, myristyl myristate, cetyl myristate, octyl dodecyl myristate, decyl oleate, octyl dodecyl oleate, hexyl decyl dimethyl octanoate, isooctane Cetyl acid,
Decyl palmitate, glyceryl trimyristate, glycerin tri (caprylate / caprate), propylene glycol dioleate, glycerin triisostearate, glyceryl triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate, cholesteryl isostearate, 12 And cyclic alcohol fatty acid esters such as cholesteryl hydroxystearate.

Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc undecylenate and the like. Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylitol, maltitol and the like.

Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, and cationic surfactants such as amine salts and quaternary ammonium salts. Agents, betaine type, amino acid type, imidazoline type, amphoteric surfactant such as lecithin, fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, nonionic interface such as ethylene oxide condensate Activators.

As the high molecular compound, gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, irismos, quince seed, gelatin,
Shellac, rosin, natural polymer compounds such as casein, sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose,
Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles And synthetic polymer compounds such as resin particles such as polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, polyethylene particles and silica particles.

The coloring material materials include iron oxide, ultramarine, konjo, chromium oxide, chromium hydroxide, carbon black,
Manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate ( Inorganic pigments such as calcined gypsum, calcium phosphate, hydroxyapatite, and ceramic powder; azo, nitro, nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, pyrene, etc. And tar dyes. In addition, as a powder raw material such as a powder raw material or a coloring material raw material of these polymer compounds, those that have been subjected to a surface treatment in advance can be used.

As the surface treatment method, known surface treatment techniques can be used. For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. Silicone treatment, perfluoroalkyl group-containing ester, perfluoroalkylsilane,
Fluorine compound treatment with perfluoropolyether and polymer having a perfluoroalkyl group, etc., silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc., isopropyl triisostearoyl titanate Titanium coupling agent treatment with isopropyltris (dioctyl pyrophosphate) titanate, etc., metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin treatment with hydrogenated egg yolk lecithin, etc., collagen treatment, polyethylene treatment, moisturizing treatment, inorganic compound treatment And a treatment method such as mechanochemical treatment.

As the fragrance, for example, anisaldehyde,
Benzyl acetate, geraniol and the like can be mentioned. Examples of the antiseptic / bactericide include methyl parapen, ethyl parapen, propyl parapen, benzalkonium, benzethonium and the like. Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and tocopherol.

Examples of the ultraviolet absorber include inorganic absorbers such as fine titanium oxide, fine zinc oxide, fine cerium oxide, fine iron oxide, fine zirconium oxide, benzoic acid, para-aminobenzoic acid, anthranilic acid, and the like.
Organic absorbents such as salicylic acid, cinnamic acid, benzophenone, and dibenzoylmethane may be used. As special compounding ingredients, for example, estradiol, estrone,
Hormones such as ethinyl estradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, and vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, aluminum potassium potassium sulfate, allantoinchlorohydroxyalumnium, Skin astringents such as zinc paraphenol sulfonate and zinc sulfate, tincture tincture tincture, tincture tincture,
Ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, glyceride pentadecanoate, vitamin E, estrogen, hair growth promoters such as photosensitizers, whitening agents such as magnesium phosphate-L-ascorbate, kojic acid, etc. No.

[0047]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 Magnesium pyrophosphate 2 by metathesis method in 200 g of water
The dispersion medium in which 0 g was generated was placed in a 500 ml separable flask, and 0.25 g of sodium lauryl sulfate was dissolved therein. Separately, methyl methacrylate (MM
A) 98 g, dimethylpolysiloxane [viscosity 1000 c
St (25 ° C.)] 2 g and 2,2′-azobis (2,
A monomer composition obtained by uniformly mixing and dissolving 0.3 g of 4-dimethylvaleronitrile) was added to the above dispersion medium.
This mixture was mixed with a homomixer (ULTRA manufactured by IKA).
TURRAX T-25) at approx.
Finely dispersed for 0 seconds. The flask was equipped with a stirrer, a thermometer and a cooler, and placed in a 60 ° C. water bath. After sufficiently replacing the inside of the flask with nitrogen gas, the stirring speed is 200 rpm.
m for 10 hours to carry out a polymerization reaction.

After confirming that the polymerization reaction was completed, the reaction solution was cooled, and hydrochloric acid was added until the pH of the slurry reached about 2 to decompose the dispersant. The particles were suction-filtered with a Buchner funnel using filter paper, and washed with 1.2 liters of ion-exchanged water to remove the dispersant. After the dehydrated cake after suction filtration was dried, it was dispersed in cyclohexane and suction filtration was repeated several times to obtain desired resin particles, and the shape was observed with an electron microscope and photographed. The resin particles were spherical resin particles having one smooth bowl-shaped depression as shown in an electron micrograph (FIG. 3). 50 particles were arbitrarily selected from the photograph, the diameter of the particles was measured, and the number average central particle diameter was calculated. Furthermore, for 20 particles belonging to a range of 30% above and below the center particle diameter,
The number of depressions (calculated value), the particle diameter D (μm), and d / D were measured, and the average value was calculated. The following results were obtained. Number of depressions: 1.3 D = 8.4 d / D = 0.89

Example 2 Resin particles were obtained in the same manner as in Example 1 except that the rotation speed of the homomixer was changed to 20,000 rpm. The resin particles were spherical having one smooth bowl-shaped depression, and the number of the depressions (calculated value) and the average values of D and d / D were as follows. Number of depressions: 1.8 D = 2.5 d / D = 0.82 Example 3 Dimethylpolysiloxane having a viscosity of 10 at 25 ° C.
Except that it was replaced with 0000 cSt dimethylpolysiloxane.
Resin particles were obtained in the same manner as in Example 1. The resin particles were spherical having one smooth bowl-shaped depression, and the number of the depressions (calculated value) and the average values of D and d / D were as follows. Number of depressions: 1.3 D = 26.3 d / D = 0.92

Example 4 Resin particles were prepared in the same manner as in Example 1 except that 200 g of the dispersion in which magnesium pyrophosphate was dispersed was replaced with a dispersion consisting of 100 g of a 10% dispersion of tribasic calcium phosphate and 100 g of deionized water. Obtained. The resin particles were spherical having one smooth bowl-shaped depression, and the number of the depressions (calculated value) and the average values of D and d / D were as follows. Number of depressions: 1.6 D = 6.6 d / D = 0.85

Example 5 Resin particles were obtained in the same manner as in Example 1 except that styrene was used instead of methyl methacrylate. The resin particles were spherical having one smooth bowl-shaped depression, and the number of the depressions (calculated value) and the average values of D and d / D were as follows. Number of depressions: 1.5 D = 20.3 d / D = 0.92 Example 6 Resin particles were obtained in the same manner as in Example 1 except that the rotation speed of the homomixer was changed to 1000 rpm. As shown in the electron micrograph (FIG. 4), the resin particles are spherical having a plurality of smooth bowl-shaped depressions, the number of depressions, the particle diameter D (μm), d / D, and the opening. The average ratios were as follows. Number of depressions: 290 D = 65.3 d / D = 0.99 Aperture ratio: 0.07

Example 7 Dimethylpolysiloxane having a viscosity of 10 c at 25 ° C.
Resin particles were obtained in the same manner as in Example 1, except that St was changed to dimethylpolysiloxane. The resin particles were spherical having a plurality of smooth bowl-shaped depressions, and the number of the depressions (calculated value), D, d / D, and the average value of the aperture ratio were as follows. Number of depressions: 2.4 D = 13.2 d / D = 0.92 Aperture ratio: 0.49

Example 8 Dimethylpolysiloxane having a viscosity at 25 ° C. of 130
Instead of liquid paraffin of cSt, instead of removing dimethylpolysiloxane with cyclohexane, after polymerization,
Resin particles were obtained in the same manner as in Example 1 except that liquid paraffin was removed by a distillation operation. The resin particles were spherical having a plurality of smooth bowl-shaped depressions, and the number of the depressions (calculated value), D, d / D, and the average value of the aperture ratio were as follows. Number of depressions: 5.2 D = 14.9 d / D = 0.93 Aperture ratio: 0.29

Comparative Example 1 Dimethylpolysiloxane was prepared with a viscosity of 0.65 cSt (25
C), and resin particles were obtained in the same manner as in Example 1 except that dimethylpolysiloxane was used. The resin particles had an average particle diameter of 7.2 μm, had no dents, and were spherical. Comparative Example 2 Resin particles were obtained in the same manner as in Example 1, except that the amount of MMA was changed to 99.9 g and the amount of dimethylpolysiloxane was changed to 0.1 g. These resin particles have an average particle diameter of 7.
0 μm, no dents, and a spherical shape. Comparative Example 3 98 g of methyl methacrylate was mixed with 90 g of styrene and divinylbenzene [trade name: DV, manufactured by Nippon Steel Chemical Co., Ltd.]
B-810] Resin particles were obtained in the same manner as in Example 8, except that 8 g was used. The resin particles have an average particle size of 1
It was 2.9 μm, had no dents, and was spherical.

Example 9 [Production of external preparation (powder foundation)] (Powder part) Resin particles (Example 1) 10 Mica 22 Talc 40 Titanium oxide 10 Red iron oxide 0.6 Yellow iron oxide 1 Black iron oxide 0 .1 (oil part) cetyl 2-ethylhexanoate 15 sorbitan sesquioleate 1 preservative 0.2 fragrance 0.1 powder part is mixed with Henschel mixer, and the mixture obtained by mixing and dissolving the oil part is added thereto. Was mixed. After further adding a flavor and mixing, the mixture was pulverized and passed through a sieve. This was compression-molded on a metal plate to obtain a powder foundation.

Comparative Example 4 A dispersion medium in which 20 g of magnesium pyrophosphate was formed by metathesis method with respect to 200 g of water was placed in a 500 ml separable flask, and 0.25 g of sodium lauryl sulfate was added thereto.
Was dissolved. Separately, methyl methacrylate (M
A monomer composition obtained by uniformly mixing and dissolving 100 g of MA) and 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the above dispersion medium. This mixture is mixed with a homomixer (ULTRA TUR manufactured by IKA).
(RAX T-25) at 10,000 rpm for about 10 seconds. The flask was equipped with a stirrer, a thermometer, and a cooler, and placed in a 60 ° C. water bath. After sufficiently replacing the inside of the flask with nitrogen gas, the stirring speed was 1 rpm at 200 rpm.
Heating was continued for 0 hour to carry out a polymerization reaction. After confirming that the polymerization reaction was completed, the reaction solution was cooled, and hydrochloric acid was added until the pH of the slurry became about 2, to decompose the dispersant. The particles are suction-filtered with a Buchner funnel using filter paper,
The dispersant was removed by washing with 1.2 liters of ion-exchanged water. The dehydrated cake after suction filtration was dried to obtain resin particles. The average particle size of the resin particles was measured with a Coulter counter, and the shape of the resin particles was observed with an electron microscope. The obtained resin particles were spherical particles having a D of 7.7 μm and having no depression. Example 9 except that the resin particles obtained above were used instead of the resin particles obtained in Example 1.
In the same manner as in the above, a powder foundation was obtained. Comparative Example 5 To 100 g of the resin particles obtained in Comparative Example 4, 2 g of dimethylpolysiloxane [viscosity: 10 cSt (25 ° C.)] was added and mixed with a small mixer for several minutes.
By performing heat treatment for 2 hours, dent-free resin particles surface-treated with dimethylpolysiloxane were obtained. A powder foundation was obtained in the same manner as in Example 9, except that the resin particles obtained above were used instead of the resin particles obtained in Example 1.

Example 10 [Production of solid paste] (powder part) Resin particles (Example 1) 30.0 kaolin 10.0 titanium dioxide 8.0 talc 20.0 magnesium stearate 3.0 (oil part) Liquid paraffin 5.0 Cetyl isooctanoate 3.3 Isopropyl lanolin fatty acid 0.5 Sorbitan monoisostearate 0.2 Preservatives Appropriate amount Perfume Appropriate amount The powder part was mixed with a Henschel mixer, and the oil part and the preservative were mixed and dissolved. The ingredients were added and mixed uniformly. After further adding a flavor and mixing, the mixture was pulverized and passed through a sieve. This was compression molded on a metal plate to obtain a solid paste.

Example 11 [Production of emulsified foundation] Resin particles (Example 1) 15.0 Talc 6.0 Titanium dioxide 3.0 Stearic acid 2.0 Cetyl alcohol 0.3 Liquid paraffin 15.0 Polyethylene (10 Mol) monooleate 1.0 sorbitan trioleate 1.0 propylene glycol 5.0 polyethylene glycol 4000 5.0 triethanolamine 1.0 pea gum 0.5 purified water 50.2 pigment appropriate amount perfume appropriate amount preservative appropriate amount First, resin particles, talc, titanium dioxide, and a pigment are mixed in a kneader (powder part). Separately, polyethylene glycol, triethanolamine, propylene glycol, and pea gum are added to purified water and dissolved by heating. Then, a powder portion is added, and the powder is uniformly dispersed using a homomixer.
Keep at 0 ° C (aqueous phase). Separately, components other than the above are mixed, dissolved by heating, and kept at 70 ° C. (oil phase).
The aqueous phase was added to the oil phase, uniformly emulsified and dispersed with a homomixer, and then cooled while stirring to obtain a foundation.

Example 12 [Production of cosmetic emulsion] Resin particles (Example 1) 10.0 Stearic acid 2.5 Cetyl alcohol 1.5 Vaseline 5.0 Liquid paraffin 10.0 Polyethylene (10 mol) monooleate 2.0 Polyethylene glycol 1500 3.0 Triethanolamine 1.0 Purified water 64.5 Fragrance 0.5 Preservatives qs First, stearic acid, cetyl alcohol, petrolatum, liquid paraffin and polyethylene monooleate are heated and dissolved. The resin particles are added to this. This is mixed with a kneader and kept at 70 ° C. (oil phase). Separately, polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C. (aqueous phase). The oil phase was added to the aqueous phase, preliminarily emulsified, and then uniformly emulsified with a homomixer, and then cooled to 30 ° C. with stirring to obtain a cosmetic emulsion.

Example 13 Production of Body Lotion Resin Particles (Example 8) 3.0 Ethanol 50.0 Glycyrrhizic Acid 0.1 Perfume 0.5 Purified Water 46.4 Resin Particles, Ethanol, Glycyrrhizic Acid, Fragrance, Purified water was sufficiently mixed with a mixer to obtain a body lotion. A sensory test was conducted on the cosmetics thus manufactured by 10 panelists. As evaluation items in this test, smoothness, squeaky feeling, and homogeneity (appearance test) were selected, and sensory evaluation was performed for each item according to the following criteria. ○ …… Eight or more panelists answered good (no squeakiness) △… 4-7 panelists answered good × …… 3 or less panelists answered good Table 1 shows the results.

[0061]

[Table 1]

Thus, it can be seen that the external preparations of Examples 9 to 13 containing the resin particles of the present invention are smooth, have no squeaky feel, and are also excellent in homogeneity. .

[0063]

The spherical resin particles of the present invention are excellent in characteristics possessed by the spherical particles, for example, light-collecting properties, optical properties of light scattering in a specific direction, and frictional properties such as slipperiness, and can be applied to a wide range of fields. . The external preparation of the present invention containing the spherical resin particles has a smooth, non-creaking feel, and is also excellent in homogeneity.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a spherical resin particle of the present invention.

FIG. 2 is a schematic view showing a spherical resin particle of the present invention.

FIG. 3 is an electron micrograph of the resin particles obtained in Example 1.

FIG. 4 is an electron micrograph of the resin particles obtained in Example 6.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/035 A61K 7/035 C08F 2/18 C08F 2/18 255/10 255/10 283/12 283 / 12 C08L 23/20 C08L 23/20 23/22 23/22 83/04 83/04 83/05 83/05 91/00 91/00 101/00 101/00 F term (reference) 4C083 AA082 AB232 AB242 AB432 AB442 AC012 AC022 AC072 AC102 AC122 AC242 AC352 AC402 AC442 AC542 AD042 AD091 AD092 AD512 AD532 BB26 CC04 CC05 CC11 CC12 DD17 DD21 DD23 DD27 DD31 EE06 EE07 FF01 FF05 FF06 4J002 AE05Y BB12Y BB17Y BB18Y BC03W BC08W BE04W BF01W BF02W BG00 BG04W BG05W BG06W BG07W BG10W BG13W CP03X CP04X DE076 DE086 DE236 DG046 DG056 DH046 DH056 DJ006 DJ016 FA086 FD206 FD317 4J011 JA02 JA03 JA04 JA05 JA13 JB08 JB16 JB26 PA07 PA09 PA56 PA64 PA99 PB06 PB22 PB24 PB38 PB40 PC02 PC07 4J026 AA14 AB44 BA06 B06 A07 BA15 BA19 BA20 BA27 BA31 BA32 DB03 FA02 GA06

Claims (13)

[Claims] 1. A side view in which a particle-shaped surface has a bowl-shaped depression and a boundary line at the depression opening is a horizontal direction, a particle diameter in the horizontal direction is D (μm), and a maximum height in the vertical direction is Spherical resin particles characterized by satisfying a formula: 0.8 <d / D <1.0 (I) 0.1 μm ≦ D ≦ 500 μm (II), where d is a μm. 2. A particle having one depression on its surface.
The spherical resin particles according to the above. 3. When the particle surface has a plurality of bowl-shaped depressions and the average diameter of the openings of the depressions is E (μm), the following formula is satisfied: 0.01 ≦ E / D ≦ 0.6 (III) The spherical resin particles according to claim 1, wherein 0.1 μm ≦ D <100 μm (IV) is satisfied. 4. In the absence of a crosslinking agent, 100 parts by weight of a polymerizable vinyl monomer, having no copolymerizability with the polymerizable vinyl monomer, and having a viscosity of 3 to 100,000 at 25 ° C.
The method for producing spherical resin particles according to any one of claims 1 to 3, wherein 1 to less than 5 parts by weight of a hydrophobic liquid compound of 0 cSt is mixed and dissolved, and aqueous suspension polymerization is performed. 5. The method according to claim 4, wherein a poorly water-soluble inorganic compound is used as a dispersion stabilizer during the aqueous suspension polymerization.
The production method described in 1. 6. The method according to claim 4, wherein the hydrophobic liquid compound is a polysiloxane or a hydrocarbon. 7. The method according to claim 6, wherein the polysiloxane is at least one selected from dimethylpolysiloxane, methylhydrogenpolysiloxane and methylphenylpolysiloxane. 8. The method according to claim 6, wherein the hydrocarbon is at least one selected from liquid paraffin, polybutene, and polyisobutylene. 9. The method according to claim 4, wherein the hydrophobic liquid compound is removed after the aqueous suspension polymerization. 10. The production method according to claim 9, wherein the hydrophobic liquid compound is removed by distillation or washing with a solvent that dissolves the hydrophobic liquid compound but does not dissolve the resin particles. 11. Spherical resin particles obtained by the production method according to claim 4. Description: 12. An external preparation comprising the spherical resin particles according to claim 1, 2, 3 or 11. 13. The external preparation according to claim 12, wherein the external preparation is a makeup cosmetic.