JP4884280B2 - COMPOSITE PARTICLE AND COSMETICS CONTAINING THE SAME - Google Patents

Description

  The present invention relates to a composite particle having a vivid color and a cosmetic containing the same.

With the diversification of needs for cosmetics, development of each cosmetic ingredient is underway. Among these, cosmetic powders are attracting attention for surface treatment and complexation depending on the purpose.
For example, makeup cosmetics such as foundations are required to obtain a finish with a feeling of bare skin and transparency while covering spots and freckles. In order to obtain such cosmetics, various composite powders have been studied (for example, Patent Document 1 and Patent Document 2). These composite powders contain a coloring pigment such as iron oxide, but are liable to agglomerate, so that it is difficult to obtain a clear color tone, resulting in a dull finish and the skin feeling is significantly impaired. In addition, the effect of covering spots and freckles was not sufficient.

Although composite particles with reduced aggregation (Patent Document 3) have also been studied, vivid color development cannot be obtained, and the effect of making color unevenness and pores inconspicuous is not sufficient.
JP 2002-3744 A JP 2003-300809 A JP 2005-298228 A

  An object of the present invention is to provide composite particles and a cosmetic material that give a transparent feeling to the skin by vivid color development and realize a finish that does not make skin problems such as spots and freckles stand out.

  The present inventors have found that composite particles that solve the above problems can be obtained by coating specific fine particle-encapsulating plate-like particles with specific color pigments, fine particles, and organic polymer compounds.

The present invention includes the following components (A), (B), (C) and (D):
(A) An average of 5 to 50% by mass of fine particles having an average primary particle diameter of 0.01 to 0.1 μm and a refractive index of 2 or more inside plate-like particles having a refractive index of 1.3 to 1.8 Plate-like particles having a primary particle diameter of 5 to 25 μm,
(B) a colored pigment having an average primary particle size of 0.1 to 1 μm,
(C) Fine particles having an average primary particle diameter of 0.01 to 0.1 μm and a refractive index of 2 or more,
(D) It is comprised with an organic polymer compound, the average primary particle diameter of a component (B) is 10 to 100 times the average primary particle diameter of a component (C), and the surface of a component (A) is made into a component (B). The composite particles coated with (C) and (D) are provided.
The present invention also provides a cosmetic containing the composite particles.

  Since the composite particles of the present invention have a bright and clear color development and a high blurring effect, the cosmetics containing them can provide a feeling of bare skin, can make spots and freckles inconspicuous, and It has excellent adhesion.

  In the present invention, the average particle diameter is an average value of 10 particles with respect to the biaxial average particle diameter calculated from the minor axis and the major axis in a scanning electron micrograph (magnification: 25000 times).

The plate-like particles of component (A) used in the present invention contain fine particles. The plate-like particles have a refractive index of 1.3 to 1.8. For example, silica (refractive index 1.5), aluminum oxide (refractive index 1.76), barium sulfate (refractive index 1.64), polyester Resin (refractive index 1.6-1.7), styrene resin (refractive index 1.5-1.6), nylon resin (refractive index 1.5-1.6), epoxy resin (refractive index 1.4- 1.7), phenol resin (refractive index 1.6), silicone resin (refractive index 1.4 to 1.6), acrylic resin (refractive index 1.5), polyolefin resin (refractive index 1.5), Examples include fluororesins (refractive index: 1.3 to 1.6), amino acid powders, and silica is particularly preferable.
The plate-like particles of component (A) have an average primary particle diameter of 5 to 25 μm, preferably 5 to 15 μm, from the viewpoint of obtaining a fine finish without glare. Furthermore, those surfaces may be subjected to a surface treatment such as a hydrophobic treatment or a hydrophilic treatment.

On the other hand, the fine particles encapsulated in the plate-like particles are measured by observing the cross section of the particles with a microscopic thin section method, and have an average primary particle diameter of 0.01 to 0.1 μm, preferably 0.01 to 0.00. It is 05 μm and has a refractive index of 2 or more. Examples of such fine particles include zinc oxide, titanium oxide, yellow iron oxide, black iron oxide, bengara, iron oxide / titanium oxide sintered product, cerium oxide, and zirconium oxide, and titanium oxide is particularly preferable.
Such fine particles are included in the plate-like particles in an amount of 5 to 50% by mass, preferably 20 to 40% by mass.

  As such fine particle-encapsulating plate-like particles, for example, commercially available products such as titanium oxide-encapsulating silica flakes NTS30K3TA, NPT30K3TA (manufactured by Nippon Sheet Glass Co., Ltd.) can be used.

The color pigment of component (B) has an average primary particle size of 0.1 to 1 μm, preferably more than 0.2 μm and 0.8 μm or less. Examples of such color pigments include titanium oxide, yellow iron oxide, black iron oxide, bengara, bitumen, ultramarine blue, and chromium oxide. A coloring pigment can be used 1 type or in combination of 2 or more types.
In particular, it is preferable to use iron oxide in order to obtain a skin-colored foundation, and to use titanium oxide in order to increase brightness.

  The fine particles of component (C) have an average primary particle diameter of 0.01 to 0.1 μm, preferably 0.01 to 0.05 μm, and a refractive index of 2 or more. Examples of such fine particles include zinc oxide, titanium oxide, yellow iron oxide, black iron oxide, bengara, iron oxide / titanium oxide sintered product, cerium oxide, zirconium oxide and the like, and zinc oxide is particularly preferable.

  In the present invention, the average primary particle diameter of the component (B) is 10 to 100 times, preferably 20 to 80 times the average primary particle diameter of the component (C). When the average primary particle sizes of the component (B) and the component (C) are in such a relationship, a uniform and vivid color can be obtained without aggregating the colored pigment.

  The organic polymer compound of component (D) is preferably a fluorine polymer compound or a silicone polymer compound from the viewpoint of improving the water repellency and feel of the composite particles.

  The composite particles of the present invention are prepared by mixing a composite powder comprising components (A), (B), and (C) with a polymer solution and spray drying; from components (A), (B), and (C) A method of mixing a composite powder and a polymer solution, drying and then pulverizing; in the presence of a composite powder comprising components (A), (B), and (C) and supercritical carbon dioxide or liquefied carbon dioxide It can be produced by various methods such as a method of contacting with an organic polymer compound. When manufacturing using supercritical carbon dioxide or liquefied carbon dioxide as described later, it is preferable that the fluorine-based polymer compound and / or the silicone-based polymer compound be dispersed or dissolved in supercritical carbon dioxide or liquefied carbon dioxide. . In particular, it is a substance having in its molecule a fluorocarbon group or silicone group which is a parent carbon dioxide group. These polymer compounds coat part or all of the surfaces of the components (A) to (C), make the structures of the components (A) to (C) stronger, and make the composite particles water repellent and feelable. Can be improved.

  The fluorine-based polymer may be a polymer compound having a fluorine atom. For example, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyltrimethylammonium salt, perfluoroalkylbetaine, perfluoroalkyl. Amine oxide, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl-containing oligomer, perfluoroalkyl phosphate diethanolamine salt, fluorosilicone, homopolymer or copolymer of (meth) acrylate having fluoroalkyl group or perfluoroalkyl group , Perfluoropolyether, polytetrafluoroethylene and the like.

  The fluorine atom content in the fluorine-based polymer compound is preferably 9 to 80% by mass, particularly 20 to 70% by mass, and more preferably 40 to 65% by mass from the viewpoint of water repellency and feel.

  Among the fluorine-based polymer compounds, a (meth) acrylic acid ester polymer having a fluoroalkyl group or a perfluoroalkyl group, and a (meth) acrylic acid ester-long chain alkyl having a fluoroalkyl group or a perfluoroalkyl group ( A (meth) acrylate copolymer is preferable from the viewpoint of facilitating dispersion and dissolution in carbon dioxide. In addition, a (meth) acrylate homopolymer having a perfluoroalkyl group having 4 or more carbon atoms, a polyfluoroalkyl group or a perfluoropolyether group, and (meth) having this compound and an alkyl group having 8 to 22 carbon atoms. A copolymer with an acrylate is most preferable because it easily disperses and dissolves in carbon dioxide.

  The weight average molecular weight of the fluorine-based polymer compound is preferably 3,000 to 500,000, more preferably 5,000 to 300,000, from the viewpoint of more firmly covering the composite powder and being solid at 25 ° C. 000.

  Examples of the silicone-based polymer compound are those that dissolve or disperse in supercritical carbon dioxide alone, liquefied carbon dioxide alone, or supercritical carbon dioxide or a mixture of liquefied carbon dioxide and a cosolvent. Or what is necessary is just to be soluble and dispersible in a volatile solvent, and it does not specifically limit.

  Examples of silicone polymer compounds include methylpolysiloxane, dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane, and dimethylsiloxane as the modified silicone shown below. -Methyl (polyoxyethylene) siloxane copolymer, dimethyl siloxane-methyl (polyoxypropylene) siloxane copolymer, polyether-modified silicone, methylstyryl-modified silicone, alkyl-modified silicone, fluorine-modified silicone, higher fatty acid ester-modified silicone, Higher alkoxy-modified silicone, alcohol-modified silicone, amino-modified silicone, mercapto-modified silicone, epoxy-modified silicone, carbo Modified silicone, and silicone-modified acrylic resin. In particular, modified silicone is preferable because it is easily dispersed and dissolved in carbon dioxide. More preferably, the end of the molecular chain and / or the side chain of the organopolysiloxane has the formula (I) or (II):

Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, X ⁻ represents a counter ion of a quaternary ammonium salt, and Cl ^-, Br ^- and a halogen ion, CH ₃ SO ₄ in _{^{-, CH 3 CH 2 SO 4}} - sulfuric acid esters ions such like)

(Wherein R ¹ , R ² and X ⁻ represent the same meaning as described above)
Through a group represented by formula (III):

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is 2 Or 3)
The molecular chain of poly (N-acylalkyleneimine) consisting of repeating units represented by the formula is bonded, and the weight ratio of the molecular chain of poly (N-acylalkylenimine) to the molecular chain of organopolysiloxane is 1 / A silicone polymer compound having a weight average molecular weight of 50 to 50/1 and a weight average molecular weight of 500 to 500,000 is particularly preferable from the viewpoint of being easily dispersed and dissolved in carbon dioxide. For example, poly (R ¹ and R ² in formula (I) are each a hydrogen atom, X ⁻ is CH ₃ CH ₂ SO ₄ ⁻ , R ³ in formula (III) is CH ₂ CH ₃ , and n is 2. N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer.

  The weight average molecular weight of the silicone-based polymer compound is preferably 500 to 500,000, more preferably 1,000 to 300,000, from the viewpoint of more firm coating.

The composite particle of the present invention is composed of the components (A) to (D), and the surface of the component (A) is coated with the components (B), (C) and (D). Here, the term “covered” refers to a structure in which components (B) and (C) are attached to the surface of component (A) via component (D); Any of the structures in which (B) and (C) are attached and the component (D) covers a part or all of them may be used.
Thus, since the composite particle | grains of this invention have coat | covered a part or all of the surface with the high molecular compound, there is little aggregation and water repellency is high. Moreover, there is little glare, it is fine, it is highly transparent, it is excellent in the feeling of skin, and there is no feeling of roughness in the touch which touched the hand.

  In the composite particles of the present invention, the total coating amount of the components (B) and (C) with respect to the component (A) is 20 to 45% by mass from the viewpoint of facilitating uniform coating on the surface of the component (A). In particular, it is preferably 25 to 40% by mass.

Further, the coating amount of the component (B) relative to the component (A) is preferably 10 to 20% by mass, particularly 12 to 18% by mass in order to obtain high color developability, and the component (C) relative to the component (A). The coating amount is preferably 10 to 35% by mass, particularly 15 to 30% by mass in order to obtain high light scattering properties.
Furthermore, the mass ratio of the component (B) and the component (C) is 2 from the viewpoint of suppressing aggregation of the component (B), uniformly covering the component (A) with the component (B), and facilitating color development. Is preferably 1: 1 to 1: 3, and particularly preferably 1: 1 to 1: 2.

  In the composite particles of the present invention, it is preferable that the coating amount of the component (D) with respect to the component (A) is 0.1 to 10% by mass, particularly 3 to 8% by mass because a good feel is obtained.

  Carbon dioxide is generally non-toxic and has a critical temperature of 304.2K. Supercritical carbon dioxide and subcritical carbon dioxide in the vicinity of the critical point have the property that the density changes suddenly by a slight pressure change.

  When the pressure and / or temperature of the fluid is increased, the density of the fluid increases rapidly. Therefore, when the solute is a fluorine-based polymer compound and / or a silicone-based polymer compound, the solubility of the solute in the fluid increases rapidly, and vice versa. When the pressure and / or temperature of the fluid is decreased, the solubility of the solute in the fluid can be drastically decreased. Therefore, the operation of the component (A) on the plate-like particle surface can be achieved only by the operation of the pressure and / or temperature. Solute deposition and separation of solute and fluid are possible.

  The temperature at which the supercritical carbon dioxide is brought into contact with the components (A) to (D) is preferably 308 to 373 K from the viewpoint of efficiently removing the supercritical carbon dioxide after the contact and reducing the pressure. In particular, 313 to 353K is preferable. In addition, the initial pressure of supercritical carbon dioxide when starting depressurization is preferably 7.2 to 50 MPa, more preferably 10 to 40 MPa from the viewpoint of efficiently depressurizing supercritical carbon dioxide.

  On the other hand, the temperature at which the liquefied carbon dioxide is brought into contact with the components (A) to (D) is preferably 233 to 304 K from the viewpoint of efficiently removing the liquefied carbon dioxide and reducing the pressure, and particularly 273. ~ 304K is preferred. Moreover, the initial pressure of the liquefied carbon dioxide when starting depressurization is preferably 1 to 50 MPa, more preferably 3.5 to 40 MPa, from the viewpoint of efficiently depressurizing the liquefied carbon dioxide.

  In the present invention, depressurization means reducing the pressure of supercritical carbon dioxide, liquefied carbon dioxide or carbon dioxide.

As described above, when supercritical carbon dioxide or liquefied carbon dioxide is used, the operation can be performed at a low temperature. Therefore, the operation is easy, and carbon dioxide is non-toxic, non-hazardous, and inexpensive. Thus, the manufacturing cost can be reduced.
Supercritical carbon dioxide is preferable because it can make the polymer compound more soluble than liquefied carbon dioxide.

  Thus, supercritical carbon dioxide or liquefied carbon dioxide and a mixture of components (A) to (D) (hereinafter referred to as “mixture A”) are obtained. A mixture of supercritical carbon dioxide or liquefied carbon dioxide and (D) a polymer compound may be in a homogeneous phase depending on conditions such as temperature and pressure. Thus, the mixture which becomes a uniform phase is preferable since the film of the polymer compound to be formed becomes uniform.

Next, supercritical carbon dioxide or liquefied carbon dioxide is removed from the obtained mixture A.
The supercritical carbon dioxide or liquefied carbon dioxide can be removed, for example, after the mixture A is produced in the container, and then the exhaust valve provided in the container is opened, the inside of the container is decompressed, and the composite particles are removed in the container. Examples thereof include a method of obtaining the mixture A, producing the mixture A in the container, and discharging the mixture A together with the fluid out of the container.

  According to the former method, the composite particles in which the components (B) to (D) are present on the surface of the component (A) can be obtained in the container without containing a solvent without performing heat treatment or the like. Can do.

  The time required for reducing the pressure in the container to atmospheric pressure is preferably 2 from the viewpoint of controlling the particle size of the resulting composite particles, the coating thickness of the polymer compound, and suppressing by-product particles. Second to 600 minutes, more preferably 5 seconds to 360 minutes.

  The method of depressurizing is not particularly limited, but the temperature lowers due to the adiabatic expansion action at the time of depressurization, but the temperature above the critical temperature of carbon dioxide prevents fluid liquefaction and agglomeration due to capillary phenomenon that tends to occur in liquids It is preferable from the viewpoint of preventing.

  Further, according to the latter method, the mixture in the container is discharged out of the container through a nozzle or the like, and the carbon dioxide is instantaneously separated and removed from the nozzle and the like, and composite particles without aggregation are produced. be able to.

  Examples of the method for discharging the mixture A outside the container include a method for ejecting the mixture A through a nozzle or the like.

  The conditions for discharging are not particularly limited, but it is preferable from the viewpoint of supercritical carbon dioxide that the temperature at the inflow portion of the nozzle is higher than the critical temperature and the pressure is higher than the critical pressure.

  There is no limitation on the shape and size of the container, as long as it can withstand the temperature and pressure used.

  The container only needs to have an exhaust mechanism such as a valve when obtaining composite particles in the container after removing the fluid.

  In order to dissolve or disperse the components (A) to (D) in the fluid, the container preferably has a stirring mechanism. Typical examples of the container include an autoclave and a pressure cell.

  In addition, when putting the components (A) to (C) into the container, by stirring or applying shear stress, after pulverizing alone or mixing and pulverizing them, and eliminating aggregates, It is preferable to put in the container.

  When mixing the components (A) to (C), a commonly used container rotating type, fixed container type, or fluid motion type mixer can be used. In the mixer, the agglomeration of particles is crushed by the shearing force at the time of mixing, and the particles can be mixed more uniformly and the dispersibility of the components (B) and (C) on the surface of the component (A) can be improved. . A high-speed fluid mixer is preferable because it has a high shearing force.

  When obtaining a premix of components (A) to (C), components (B) and (C) are premixed and the aggregate of component (B) is pulverized, then component (A) is added, and further It is preferable to mix uniformly.

  In addition, the mass ratio [(D) / ((A) + (B) + (C))] of the (D) polymer compound in the mixture A and the total amount of the components (A) to (C) From the viewpoint of developing the characteristics of the polymer compound, it is preferably 1/1000 to 2/1, particularly 3/1000 to 1/1, and more preferably 3/1000 to 3/10. In addition, it is preferable that the (D) polymer compound is dissolved in supercritical carbon dioxide or liquefied carbon dioxide from the viewpoint of the components (B) and (C) covering the surface of the component (A) as uniformly as possible.

  Further, the total content of the components (A) to (C) in the mixture A is not particularly limited, but is preferably 0.01 to 70% by mass from the viewpoint of improving the dispersibility in the mixture A. 0.1-50 mass% is preferable.

  In the case where it is difficult to dissolve or disperse the polymer compound in supercritical carbon dioxide or liquefied carbon dioxide, the polymer compound is mixed with supercritical carbon dioxide or liquefied carbon dioxide so that the polymer compound is supercritical carbon dioxide or liquefied carbon dioxide. It can be dissolved or dispersed in liquefied carbon dioxide.

  As the cosolvent, a polar solvent is preferable. Among polar solvents, alcohol and water are preferred because they are considered almost harmless to the human body. As the alcohol, methanol, ethanol and 1-propanol are preferable, and ethanol is more preferable.

  As described above, the method using supercritical carbon dioxide or liquefied carbon dioxide is different from the method using organic solvent or resin emulsion, and there is little aggregation between particles, and it is not necessary to perform a desolvation operation by heat treatment or the like. The number of processing steps can be reduced, and the manufacturing efficiency is very excellent.

  In this way, the composite particles of the present invention comprising the components (A) to (D) and having the surface of the component (A) coated with the components (B), (C) and (D) are obtained. Can do. In addition to the components (A) to (D), the composite particles may contain one or more other components. Examples of such components include stabilizers, colorants, UV protection agents and the like. These components can be contained in the composite particles by dissolving or dispersing them in supercritical carbon dioxide or liquefied carbon dioxide.

The average particle diameter of the obtained composite particles is preferably 0.1 to 1000 μm, particularly 0.5 to 500 μm, and more preferably 5 to 50 μm from the viewpoint of handling as particles.
The obtained composite particles may be appropriately subjected to operations such as pulverization and pulverization.

  The cosmetic of the present invention contains composite particles obtained as described above. From the viewpoint of expressing the effect of the composite particles in terms of finish and feel, the composite particles are preferably contained in an amount of 0.01 to 95 mass%, particularly 5 to 70 mass% in the total composition of the cosmetic.

  The cosmetic of the present invention can contain components used in ordinary cosmetics in addition to the composite particles. Examples of such components include inorganic powders such as alumina, silica, zirconia, titanium oxide, zeolite, barium sulfate, and powders such as colored pigments and pearl luster pigments; polyethylene wax, microcrystalline wax, ceresin wax, petrolatum, etc. Hydrocarbons; ester oils such as diisostearyl malate and neopentyl glycol dicaprate; vegetable oils such as candelilla wax, jojoba oil and olive oil; silicone oils such as cyclomethicone and dimethicone; high grades such as cetanol and oleyl alcohol Alcohols; fatty acids such as stearic acid and oleic acid; polyhydric alcohols such as glycerin and 1,3-butanediol; interfaces such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants Activator; low grade such as ethanol Lucols; Thickeners such as carbopol; UV absorbers such as octyl methoxycinnamate; Preservatives, antioxidants, dyes, moisturizers, whitening agents, blood circulation promoters, antiperspirants, fungicides, skin activators And other medicinal ingredients, and fragrances.

  The cosmetic of the present invention is a conventional method using, for example, a disper, a homomixer, a combimix, a azimuth homomixer, a Henschel mixer, a retro mixer, a Hobart mixer, a planetary mixer, a kneader, an extruder, a nauter mixer, a rocking mixer, etc. For example, foundation, powder powder, solid powder, makeup base, eye shadow, lipstick, blusher, eyebrow, moisturizing cream, UV protection cream, whitening cream, lotion, milky lotion, face wash, pack, etc. Various cosmetics. Particularly, it is suitable as makeup cosmetics for foundations, powder powder, solid powder, makeup base, eye shadow, lipstick, blusher, eyebrow and the like.

Example 1
[Dissolution / dispersion process]
The apparatus shown in FIG. 1 was used.
4.51 g of zinc oxide (average particle size of about 0.01 μm, manufactured by Sakai Chemical Co., Ltd.), yellow iron oxide (average particle size of about 0.35 μm, manufactured by Titanium Industry Co., Ltd.) 0.9 g, sintered iron oxide / titanium oxide [ Homogeneously mix 0.7 g of average particle size of 0.24 μm, manufactured by Nikko Rica Co., Ltd. and 1.37 g of titanium oxide (average particle size of about 0.31 μm, manufactured by Ishihara Sangyo Co., Ltd.) using a super mixer (produced by Kawata Corp.). After that, 22.53 g of titanium oxide-encapsulated silica flakes NTS30K3TA [average particle diameter of about 10 μm, manufactured by Nippon Sheet Glass Co., Ltd.] was added and further mixed to obtain a premixed powder.

In an autoclave 10 [content 500 mL: manufactured by AKICO], 20 g of premixed powder and silicone polymer compound [(N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer (molecular weight) : 1 × 10 ⁵ )] 0.46 g. The molecular structure of the (N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer is represented by the following formula (IV).

(Wherein p: q: r = 270: 0.3: 0.1 and x = 12)

  After filling, after removing dust in the carbon dioxide gas or liquefied carbon dioxide through the filter 2 from the cylinder 1, the carbon dioxide is condensed in the condenser 3 through which the refrigerant controlled to −5 ° C. is passed from the cooler 5. Thereafter, the pressure was raised by the pressure-boosting pump 4 whose pump head was cooled. The pressure at the time of pressurization was measured with the pressure gauge 6a. In addition, in order to ensure safety, the safety valve 7a was arrange | positioned in the downstream part of the pressure gauge 6a. The pressure was adjusted with the pressure holding valve V-1.

  The valve V-2 was opened and carbon dioxide was preheated to a predetermined temperature through the preheater 8 and sent to the autoclave 10 to which the safety valve 7b was attached via the valve V-3. Using the cartridge heater 12, the temperature in the autoclave 10 is adjusted by the temperature controller 13, and the temperature and pressure in the cell are adjusted to a temperature of 338K and a pressure of 25MPa by the thermometer 11 and the pressure gauge 6b, respectively. The carbon state was assumed. Under this condition, the stirrer 9 was rotated and dissolved and dispersed for 0.5 hour to obtain a mixture.

[Composite process]
The exhaust valve V-4 was gradually opened, exhausted from the exhaust line 15 (inner diameter 2.5 mm), and the pressure was reduced for 15 minutes. At this time, the temperature in the container was lowered by adiabatic expansion, but the pressure in the container was reduced so that the temperature in the container did not become 313.2K or less. In addition, the heater 14 was heated to prevent the exhaust line from freezing. Further, the composite particles slightly leaking from the exhaust line 15 are captured by the bag filter 16. After reducing the container pressure in the autoclave 10 to atmospheric pressure, composite particles 17 were obtained from the autoclave 10.

  A scanning electron micrograph of the obtained composite particles is shown in FIG. 2 (magnification: 3000 times). From the photograph in FIG. 2, it can be seen that composite particles in which fine particle zinc oxide and a colored pigment are dispersed on titanium oxide-containing silica having a particle size of about 15 μm are obtained.

Examples 2-4, Comparative Examples 1-4
Composite particles were produced in the same manner as in Example 1 except that the composition shown in Table 1 was used.

Test Example 1 (Evaluation of vividness of composite particles)
The vividness of the composite particles obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was determined by the method shown below. That is, the composite particles are applied to white synthetic leather (for example, Laforet S2923 No. 1 manufactured by Okamoto Shinwa Co., Ltd.) with a cosmetic sponge so that each composite particle is 1 g / m ^2. CIE 1976 L * a * b * chromaticity coordinates L * of the color space when the incident light angle is 45 ° and the light receiving angle is 0 °, using a variable angle spectrocolorimeter GCMS-4) manufactured by Murakami Color Science Laboratory. Measure a * and b *. Then, each saturation is calculated from the formula C * ab = (a * ² + b * ² ) ^1/2 . The results are shown in Table 1.

Examples 5-8, Comparative Examples 5-8 (powder foundation)
A powder foundation having the composition shown in Table 2 was produced, and the use of the obtained foundation was evaluated. The results are also shown in Table 2.

(Manufacturing method)
Components (1) to (18) were mixed and pulverized with a pulverizer. This was transferred to a high-speed blender, and components (19) to (24) mixed and dissolved at 80 ° C. were added and mixed uniformly. The powder was crushed again, passed through a sieve, and compression molded into a metal pan to obtain a powder foundation.

(Evaluation methods)
10 expert panelists give “good” for each item regarding the feeling of use when applying each powder foundation to the face (brightness of skin color, inconspicuous spots and freckles, feeling of bare skin, feeling of close contact with the skin) Sensory evaluation was performed with 5 points, “slightly good” 4 points, “normal” 3 points, “slightly bad” 2 points, and “bad” 1 point, and the average value was shown.

It is a schematic explanatory drawing which shows one embodiment of the apparatus used in the Example. 2 is a scanning electron micrograph showing the particle structure of the composite particles obtained in Example 1. FIG.

Explanation of symbols

1 Cylinder 2 Filter 3 Condenser 4 Booster Pump 5 Cooler 6a Pressure Gauge 6b Pressure Gauge 7a Safety Valve 7b Safety Valve 8 Preheater 9 Stirrer 10 Autoclave 11 Thermometer 12 Cartridge Heater 13 Temperature Controller 14 Heater 15 Exhaust Line 16 Bug Filter 17 Compounding

Claims (10)

The following components (A), (B), (C) and (D):
(A) in the portion, are averaged encapsulated primary particle diameter 5 to 50 mass% of titanium oxide of 0.01 to 0.1 m, an average primary particle size 5~25μm silica,
(B) a color pigment having an average primary particle size of 0.1 to 1 μm selected from titanium oxide, iron oxide, and sintered iron oxide / titanium oxide ;
(C) Zinc oxide or titanium oxide having an average primary particle size of 0.01 to 0.1 μm,
(D) At the terminal and / or side chain of the molecular chain of the organopolysiloxane, the formula (I) or (II):

Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, X ⁻ is a counter ion of a quaternary ammonium salt, and a halogen ion Or sulfate ester ion)

(Wherein R ¹ , R ² and X ⁻ represent the same meaning as described above)
Through a group represented by formula (III):

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is 2 Or 3)
The molecular chain of poly (N-acylalkyleneimine) consisting of repeating units represented by the formula is bonded, and the weight ratio of the molecular chain of poly (N-acylalkylenimine) to the molecular chain of organopolysiloxane is 1 / It is composed of a silicone-based polymer compound having a weight average molecular weight of 50 to 50/1 and a weight average molecular weight of 500 to 500,000, and the average primary particle size of component (B) is the average primary particle size of component (C) 10 to 100 times, and the composite particles in which the surface of the component (A) is coated with the components (B), (C) and (D).   The composite particle according to claim 1, wherein the total coating amount of components (B) and (C) with respect to component (A) is 20 to 45 mass%.   The composite particle according to claim 1 or 2, wherein the coating amount of the component (B) with respect to the component (A) is 10 to 20% by mass.   The composite particle according to any one of claims 1 to 3, wherein a coating amount of the component (C) with respect to the component (A) is 10 to 35% by mass.   The composite particle according to any one of claims 1 to 4, wherein a coating amount of the component (D) with respect to the component (A) is 0.1 to 10% by mass.   The composite particle according to any one of claims 1 to 5, wherein a mass ratio of the component (B) and the component (C) is 2: 1 to 1: 3. The component (D) is one that is dissolved or dispersed in supercritical carbon dioxide alone, liquefied carbon dioxide alone, or supercritical carbon dioxide or a mixture of carbon oxide and a co-solvent for liquefaction. The composite particle according to Item 1. In the presence of supercritical carbon dioxide or liquefied carbon dioxide, the following components (A), (B), (C) and (D):
(A) in the portion, are averaged encapsulated primary particle diameter 5 to 50 mass% of titanium oxide of 0.01 to 0.1 m, an average primary particle size 5~25μm silica,
(B) a color pigment having an average primary particle size of 0.1 to 1 μm selected from titanium oxide, iron oxide, and sintered iron oxide / titanium oxide ;
(C) Zinc oxide or titanium oxide having an average primary particle size of 0.01 to 0.1 μm,
(D) At the terminal and / or side chain of the molecular chain of the organopolysiloxane, the formula (I) or (II):

Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, X ⁻ is a counter ion of a quaternary ammonium salt, and a halogen ion Or sulfate ester ion)

(Wherein R ¹ , R ² and X ⁻ represent the same meaning as described above)
Through a group represented by formula (III):

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is 2 Or 3)
The molecular chain of poly (N-acylalkyleneimine) consisting of repeating units represented by the formula is bonded, and the weight ratio of the molecular chain of poly (N-acylalkylenimine) to the molecular chain of organopolysiloxane is 1 / The composite particle according to any one of claims 1 to 7 , which is obtained by contacting a silicone polymer compound having a weight average molecular weight of 50 to 50/1 and a weight average molecular weight of 500 to 500,000 . Cosmetics containing the composite particles according to any one of claims 1 to 8 . The ingredients were mixed (B) and (C), added component (A), further were uniformly mixed, by contacting the component (D), composite of any one of claims 1-7 for composite Particle production method.