JP2007112818A - Makeup cosmetics - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide makeup cosmetics that can change color hue of skin without unnatural glaring, and gives sufficient covering power in spite of transparent feeling. <P>SOLUTION: The makeup cosmetics contains (A) specific complex tabular particles comprising titanated mica and organic polymer fine particles, and (B) specific flake-shape composite powders coated with fine particles on the substrate thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a makeup cosmetic that can change the skin hue sensation but does not have an unnatural glare, and has a sufficient covering power while being transparent.

  Conventionally, makeup cosmetics have been combined with a powder having a strong diffuse reflection to obtain a matte finish, or a powder having a strong specular reflection such as mica to have a glossy finish. In addition, in order to cover the dullness of the skin, pigments with high hiding power such as titanium oxide and iron oxide are blended, or redness such as bengara and rake pigment is added to change the skin hue sensation. . Furthermore, to hide the red face and acne scars, a green pigment that is a complementary color of red is used, and a blue or purple pigment is used to give a transparent feeling, thereby changing the skin hue sensation.

However, when a pigment with high hiding power is used, the natural feeling is lost. In addition, when the complementary color principle is used, there is a problem that although the hue can be covered, the saturation is lowered and the skin color is dull. These are caused by hue control based on subtractive color mixing, and are caused by the fact that if the colors are overlapped, the saturation is lowered and the color approaches gray.
Therefore, in order to compensate for the decrease in saturation, a method has been adopted in which an appropriate amount of a pearl pigment having a strong luster such as titanium mica is blended to give gloss. However, the finish has a strong luster in the specular reflection direction unique to the pearl pigment, and therefore, it tends to have an appearance or an unnatural finish that is different from the actual gloss of the skin.

  On the other hand, a proposal has been made to suppress strong gloss by coating a flaky pearl pigment such as titanium mica with a spherical powder. For example, Patent Document 1 is a technique in which spherical fine particles of an acrylic resin are attached to the surface of a flaky pearl pigment such as titanium mica by spray drying a slurry in which fine particles of an acrylic resin are dispersed. Further, Patent Document 2 mechanically dry blends plate-like powder and organic spherical powder and coats the plate-like powder with organic spherical powder. However, in any case, since the spherical fine particles are simply attached to the surface of the flaky pearl pigment, there is a drawback that adhesion is weak.

Further, when a pearl pigment is usually blended in a cosmetic, it is not enough to change the hue sensation as a whole because the color saturation is low enough to feel a slight color change in the regular reflection direction. Therefore, it is necessary to increase the blending amount of the pearl pigment in order to increase the change in the hue sensation, but there is a problem that an unnatural feeling of glare appears.
Cosmetics with enhanced saturation of the pearl pigment itself include cosmetics containing a hollow metal oxide plate powder (see Patent Document 3), and mica matrix materials such as titanium oxide, silicon oxide, and titanium oxide. There is known a cosmetic (see Patent Document 4) containing a high-saturation powder and a light-scattering powder that are sequentially coated with the above. Certainly, the composite pigments used in Patent Documents 1 and 2 have higher chroma as compared with the conventional pearl pigments. However, makeup cosmetics generally contain powders with very high surface gloss such as mica and talc, so when these composite pigments are blended, the color development is canceled and the effect of changing the hue sensation is achieved. There was a problem that it could not be fully demonstrated.

Japanese Patent Laid-Open No. 9-48707 Japanese Patent Laid-Open No. 9-12430 JP 2001-172118 A JP 2001-288038 A

  The object of the present invention is to improve the coloring efficiency of the interference color of titanium mica and change the skin hue sensation. The goal is to provide makeup cosmetics that help.

As a result of investigations to solve the above problems, the inventors of the present invention include composite plate-like particles in which organic polymer fine particles are fixed on the surface of titanium mica and flaky composite powders of a specific form in makeup cosmetics. It was found that the above-mentioned purpose can be achieved.
That is, the present invention provides a makeup cosmetic containing the following (A) composite plate-like particles and (B) flaky composite powder.
(A) A composite plate-like particle comprising titanium mica and organic polymer fine particles and satisfying the following conditions (1) to (4): (1) The composite plate-like particle has a pressure higher than the critical temperature and 4 MPa or higher. Organic polymer fine particles fixed to the surface of titanium mica in the presence of carbon dioxide (2) The average particle size of the organic polymer fine particles is 0.01 to 30 μm
(3) Ratio (a / b) of average particle diameter (a) of organic polymer fine particles to average particle diameter (b) of titanium mica is 1/2000 to 1/5.
(4) The mass ratio of organic polymer fine particles to mica titanium is 0.001-1.
(B) A flaky composite powder in which a base material is coated with fine particles, wherein the base material has an average particle size of 0.1 to 1000 μm, and the fine particles have an average particle size with respect to the average particle size of the base material A flaky composite powder that is 1/5 or less and the content of the base material is 50 to 95% by mass

  The makeup cosmetic of the present invention comprises a composite plate-like particle (A) in which specific organic polymer fine particles are plasticized by carbon dioxide in a supercritical state and firmly fixed on the surface of titanium mica, and a flaky composite of a specific form Contains powder (B). Therefore, the makeup cosmetics of the present invention can produce a bright, natural finish with high transparency, an effect of reducing glare, a high skin color correction effect, and an effect of giving a finish with high covering power Can be expressed.

The makeup cosmetic of the present invention is characterized by containing (A) specific composite plate-like particles and (B) a flaky composite powder having a specific form.
The (A) composite plate-like particle used in the present invention is a composite plate-like particle comprising mica titanium and organic polymer fine particles. Here, titanium mica is an optically characteristic pearl pigment that gives a pearly luster and interference color by coating the surface of finely divided mica (plate-like particles) with titanium oxide. As the mica, which is a base material of titanium mica, muscovite, scale mica, phlogopite, biotite, artificial mica, sericite (sericite) and the like can be used. Of these, muscovite, scale mica, and phlogopite are particularly preferable.
Titanium oxide covering the surface of mica includes a rutile type, anatase type, and brookite type. Among these, a rutile type and an anatase type are preferable. Commercially available titanium mica can be used. Further, a mica titanium further coated with iron oxide, and a mica coated with a mixture of titanium oxide and iron oxide or tin oxide can also be used.

The average particle diameter of the mica titanium used is preferably 1 to 150 μm, and particularly preferably 5 to 100 μm, from the viewpoint that the organic polymer particles are not glazed and have an appropriate gloss. If the average particle size exceeds 150 μm, the gloss of titanium mica as the substrate becomes too strong, and it becomes difficult to control the gloss, and there is a risk of glare. On the other hand, when the thickness is less than 5 μm, the gloss of titanium mica as a substrate is lowered, and desired optical characteristics cannot be obtained, which is not preferable.
Said mica titanium can be used individually by 1 type or in mixture of 2 or more types.

Next, as the organic polymer fine particles, a polymer compound that swells and plasticizes with carbon dioxide at a critical temperature or higher and a pressure of 4 MPa or higher is used.
Examples of the polymer compound include a thermoplastic resin, a thermosetting resin, a fluorine polymer compound, and a silicone polymer compound.
Thermoplastic resins include acrylic resins such as polymethyl methacrylate (PMMA), polyolefin resins such as polyethylene and polypropylene, polystyrene resins, polyester resins, polyvinyl chloride resins, polyethylene terephthalate resins, polycarbonate resins, polyamide resins such as nylon, etc. Is mentioned. In these, an acrylic resin is preferable and especially polymethyl methacrylate (PMMA) is preferable.
Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, epoxy resin, and urethane resin.

  As the fluorine-based polymer compound, any polymer compound having a fluorine atom can be used without particular limitation. Among these, a homopolymer of (meth) acrylate having a perfluoroalkyl group having 4 or more carbon atoms, a polyfluoroalkyl group or a perfluoropolyether group, and an alkyl group having 8 to 22 carbon atoms with this compound A copolymer with (meth) acrylate is particularly preferred. Further, from the viewpoint of dispersibility and solubility in carbon dioxide, those having a weight average molecular weight of 3,000 to 500,000, particularly 5,000 to 300,000 are preferable.

As the silicone-based polymer compound, various polysiloxanes, modified silicones, silicone-modified acrylic resins and the like can be used without any particular limitation. Among these, poly (N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane copolymer is particularly preferable. Further, from the viewpoint of dispersibility and solubility in carbon dioxide, those having a weight average molecular weight of 500 to 500,000, particularly 1,000 to 300,000 are preferable.
Details of these fluorine-based polymer compounds and silicone-based polymer compounds are described in paragraphs [0035] to [0046] of JP-A No. 2002-210356.
The organic polymer fine particles may be used alone or in combination of two or more.

The shape of the organic polymer fine particles used in the present invention is not particularly limited, but is preferably spherical.
The average particle diameter of the organic polymer fine particles is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, and still more preferably 0.1 to 3 μm.
The relationship between the average particle diameter (a) of the organic polymer fine particles and the average particle diameter (b) of the mica titanium is such that the ratio of the average particle diameter (a / b) is 1 / It is 2000-1 / 5, Preferably it is 1 / 800-1 / 10, More preferably, it is 1 / 400-1 / 20. Here, the average particle size is calculated from a volume-based particle size distribution measured by a laser diffraction / scattering method using a laser diffraction / scattering particle size distribution analyzer (for example, Horiba, Ltd., LA-920). Mean median diameter.

Next, a production example of (A) composite plate-like particles will be described.
(A) The composite plate-like particles plasticize organic polymer fine particles in a container such as an autoclave having a stirring mechanism or a pressure cell in the presence of carbon dioxide having a pressure higher than the critical temperature and 4 MPa or higher. It can be obtained by fixing on the surface and compositing. There is no restriction | limiting in particular as an apparatus used for such operation, For example, the apparatus as described in Unexamined-Japanese-Patent No. 11-47681, Unexamined-Japanese-Patent No. 2000-210356, etc. can be used.

In the present invention, it is preferable to mix organic polymer fine particles with mica titanium before the contact treatment with carbon dioxide. As a mixing method, a general powder mixing method can be used. In particular, it is preferable to dry-blend titanium mica and organic polymer fine particles in a predetermined container using a high-speed fluid mixer or the like and perform physical adhesion by stirring force.
In dry blending, in order to prevent aggregation between the organic polymer fine particles and the resulting composite plate-like particles, inorganic fine particles can coexist within a range that does not impair the object of the present invention. Examples of inorganic fine particles that can be used include silica, magnesium silicate, talc, sericite, mica, kaolin, and the like.
The average particle diameter of these inorganic fine particles is preferably smaller than the average particle diameter of the organic polymer fine particles, and is usually 0.3 μm or less, preferably 0.1 μm or less.

Next, carbon dioxide having a pressure not lower than the critical temperature and not lower than 4 MPa is introduced into the container, and the organic polymer fine particles are plasticized by the carbon dioxide. The temperature at this time depends on the plasticity of the organic polymer fine particles, but from the viewpoint of efficiently performing plasticization, the temperature is set to the carbon dioxide critical temperature (304.2 K) or higher. A preferable temperature is 310 to 370 K, more preferably 320 to 360 K, from the viewpoint of efficiently removing carbon dioxide and reducing pressure.
Further, the pressure in plasticization depends on the plasticity of the organic polymer fine particles, but is 4 MPa or more. A preferable pressure is a critical pressure (7.37 MPa) or more, more preferably 10 MPa or more. Since the density of carbon dioxide increases as the pressure increases, the fluidity of the mica titanium and the composite plate-like particles is improved, and the cohesiveness of the particles is improved. Accordingly, the pressure is preferably higher, but is preferably 50 MPa or less, more preferably 40 MPa or less, from the viewpoint of efficiently performing the cost of equipment, removing carbon dioxide, or reducing the pressure. A particularly preferable pressure is 10 to 35 MPa.

  High-pressure carbon dioxide exhibits wide solubility in organic polymer fine particles. In the presence of high-pressure carbon dioxide, organic polymer fine particles swell due to dissolution (sorption) of carbon dioxide. As a result, the plasticity is greatly increased even at a temperature lower than the melting point or glass transition temperature of the organic polymer fine particles. For this reason, the organic polymer fine particles are brought into contact with high pressure, particularly carbon dioxide of 4 MPa or more, thereby plasticizing the organic polymer fine particles and increasing the contact area to the surface of the mica titanium, thereby realizing strong fixation. Is possible.

In the case where carbon dioxide and organic polymer fine particles having a pressure equal to or higher than the critical temperature and 4 MPa or higher are brought into contact with each other, the mass ratio of the organic polymer fine particles to titanium mica is 0.001 to 1, preferably 0.01 to 0.5, More preferably, it is the range of 0.01-0.2.
The time for fixing the organic polymer fine particles to the surface of titanium mica depends on the plasticity of the organic polymer fine particles, but is usually 1 minute to 20 hours, preferably 5 minutes to 5 hours.
Further, if the inside of the container is stirred during this time, the fluidity of the mica titanium and the composite plate-like particles becomes good, and the aggregation property of the particles can be improved.

As the fixing mode of the composite plate-like particle (A) of the present invention, the organic polymer fine particles maintain the basic shape as the particle, and the contact portion with the mica titanium surface is deformed and fixed. Is mentioned. As shown in FIG. 3, for example, when the organic polymer fine particle is a sphere before plasticization, the portion where the organic polymer fine particle is in contact with the mica titanium becomes flat and is in contact with the mica titanium on the surface. The mode is mentioned. Moreover, the aspect in which the organic polymer microparticles are not in contact with the mica titanium maintains a substantially spherical shape. In addition, when the organic polymer fine particles are adjacent to each other, a part of the organic polymer fine particles are fused to each other by plasticization, and in some cases, a network shape is obtained.
In the ordinary spray drying method or dry blending method, as shown in FIG. 4, when the organic polymer fine particles are true spheres, they are almost adhered to the surface of titanium mica as they are substantially true spheres. On the other hand, the composite plate-like particles used in the present invention have the above structural characteristics, and thus exhibit the unique effects of the present invention.

  Further, (A) the composite plate-like powder can be subjected to a fluorine-based or silicone-based coating treatment usually applied to cosmetic powders. For example, when supercritical processing is performed in the presence of carbon dioxide, a fluorine compound or silicone compound that can be used as a coating agent is allowed to coexist in the container, and a part or all of the resulting composite plate-like particles are coated. You can also In this case, a part or all of the surface of titanium mica and / or organic polymer fine particles used as a raw material for the composite plate-like particles may be coated with a fluorine compound and / or a silicone compound in advance. As the fluorine-based compound and the silicone-based polymer compound, a fluorine-based or silicone-based compound that is generally used as a surface coating agent can be used.

Further, in order to promote plasticization of the organic polymer fine particles, a plasticizer can coexist with carbon dioxide. The plasticizer is preferably one that can be dissolved or emulsified in carbon dioxide at a critical temperature or higher and a pressure of 4 MPa or higher.
Examples of the plasticizer that can be used include 2-ethylhexyl p-methoxycinnamate, phthalic acid ester, phosphoric acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, dihydric alcohol ester, and oxyacid ester. Etc.
In addition, in the case where the organic polymer fine particles are a substance that is not easily plasticized by carbon dioxide, a cosolvent may be added as an entrainer to promote plasticization. The cosolvent is preferably a polar solvent, and examples thereof include alcohol, acetone, ethyl acetate, methyl ethyl ketone, and water. The alcohol is preferably ethanol and 1-propanol, more preferably ethanol.

After the organic polymer fine particles are fixed to the surface of titanium mica, it can be subjected to a step of removing carbon dioxide. As a removal method, a method of reducing the pressure of carbon dioxide can be used. That is, by reducing the pressure of carbon dioxide, the solubility of carbon dioxide in the organic polymer fine particles is drastically reduced, so that the organic polymer fine particles and carbon dioxide can be separated only by a pressure reduction operation. For example, the composite plate-like particles in the container can be separated from the carbon dioxide by reducing the pressure in the container to atmospheric pressure. The time required for reducing the pressure to atmospheric pressure depends on the apparatus, but is usually 2 seconds to 5 hours, preferably 5 seconds to 2 hours.
As another method, the mixture in the container is discharged out of the container, carbon dioxide is separated and removed from the mixture at the time of discharge, and composite plate-like particles without aggregation can be obtained. The discharge conditions are not particularly limited, but it is desirable from the viewpoint of a supercritical fluid 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.

In the composite plate-like particle (A) of the present invention obtained as described above, the organic polymer fine particles are plasticized with carbon dioxide at a critical temperature or higher and a pressure of 4 MPa or higher, and firmly adhered to the surface of titanium mica. The average particle diameter of the organic polymer fine particles is 0.01 to 30 μm, preferably 0.05 to 20 μm, more preferably 0.1 to 3 μm. The ratio (a / b) of the average particle diameter (a) of the organic polymer fine particles to the average particle diameter (b) of mica titanium is 1/2000 to 1/5, preferably 1/800 to 1/10. It is preferably 1/400 to 1/20. Further, the mass ratio of the organic polymer fine particles to titanium mica is 0.001-1, preferably 0.01-0.5, more preferably 0.01-0.2.
The composite plate-like particles (A) are useful as various powders for make-up cosmetics because they can provide a transparent feeling while having sufficient covering power on the coated surface.

The (A) composite plate-like particles of the present invention can be subjected to water repellency and / or oil repellency treatment in advance before blending into the makeup cosmetic. Water repellent and / or oil repellent treatment is carried out by treating the composite plate-like particle surface with a silicone compound such as dimethylpolysiloxane and methylhydrogenpolysiloxane, a fluorine compound such as perfluoroalkyl phosphate compound, lecithin, amino acid, polyethylene, It can be performed by treating with metal soap or the like.
In order to further improve the feeling of use, surface treatment with sphingosine analogs, sterols and fatty acids described in JP-A No. 11-49634 can be used to bring out the effect of making the skin feel smooth and smooth. It is possible to obtain a cosmetic that has good moisture and is excellent in moisture effect and has no skin irritation.

Next, (B) flaky composite powder used in the present invention will be described.
(B) The flaky composite powder is obtained by coating the surface of a powder serving as a base material with fine particles (hereinafter referred to as coated particles), and the average particle size of the base material is 0.1 to 1000 μm, and the coated particles The average particle size of the base material is 1/5 or less of the average particle size of the base material, and the content of the base material is 50 to 95% by mass. (B) As a covering form of the flaky composite powder, there are forms in which the covering particles are present in layers or scattered on the surface of the base material, or a part of the covering particles are embedded in the base material. By coating the surface of the base material in such a form, it is possible to control the amount of surface reflected light of (B) flaky composite powder.
Here, “flaky” is a term used from the viewpoint of excluding so-called granular materials, and usually has an aspect ratio (ratio of powder major axis to thickness) of 5 to 100, particularly 10 to 70. It means what is. If the aspect ratio is within this range, it is preferable from the viewpoint that the friction between the powders is reduced and the usability is improved.

(B) As a base material of flaky composite powder, talc, mica, sericite, kaolin, smectite clay mineral, synthetic mica, synthetic sericite, plate-like titanium oxide, plate-like silica, plate-like aluminum oxide, nitriding Examples thereof include plate-like or flaky inorganic powders such as boron, barium sulfate, and plate-like titania / silica composite oxide. Among these, talc is particularly preferable from the viewpoint of usability. These base materials can be used individually by 1 type or in mixture of 2 or more types.
The average particle diameter of the base material (the long diameter of the plate-like powder) is 0.1 to 1000 μm, preferably 0.5 to 500 μm, and particularly preferably 5 to 50 μm. Moreover, it is preferable that the thickness of a base material is 0.05-1 micrometer.
The content of the base material in the flaky composite powder is 50 to 95% by mass, preferably 60 to 80% by mass.

The coated particles for coating the surface of the base material are not particularly limited, but metal oxide particles are preferable. Examples of the metal oxide include alumina, silica, zirconia, titanium oxide, zinc oxide, iron oxide, magnesium oxide, calcium oxide, and cerium oxide. Among these, alumina, silica, and titanium oxide are particularly preferable in terms of refractive index. These metal oxides can be used individually by 1 type or in mixture of 2 or more types.
The average particle size of the coated particles is 1/5 or less, preferably 1/10 or less, with respect to the average particle size of the base material. Here, the average particle diameter is the same as described above, and means the median diameter by the laser diffraction / scattering method.

The (B) flaky composite powder used in the present invention has a low surface reflection light quantity. (B) The surface reflected light amount of the flaky composite powder is measured by the following method.
Polyurethane black artificial leather (Okamoto Corporation, OK-7) to 10 cm × 5 cm, the flaky composite powder 5 mg / 50 cm ² was uniformly applied, two-dimensional variable angle spectrophotometer (Murakami Color Technology Research In other words, the surface reflected light amount is measured using GCMS-3). The measurement is performed under the conditions of the incident light angle of 10 ° and the light receiving angle of 10 ° under the light receiving condition of 2 ° field of view with C light (x), and under the conditions of the incident light angle of −40 ° and the light receiving angle of 60 ° (Y) is measured. Here, the Y value of tristimulus values in the 2 ° visual field XYZ color system is used as the surface reflected light amount. The surface reflected light is light that is reflected when incident light is applied to a sample applied to artificial leather. The incident light angle is an angle formed by the normal line of the reflecting surface and the incident light beam, and the light receiving angle is an angle formed by the normal line of the reflecting surface and the reflected light beam.
(B) It is preferable that the difference (xy) of each surface reflected light amount measured on said conditions for flaky composite powder is 12 or less. The difference (xy) in the amount of surface reflection light is more preferably 11 or less, and even more preferably 10 or less.

Next, a production example of (B) flaky composite powder will be described.
(B) The flaky composite powder, for example, by selecting 1 to 3 types having different refractive indexes from the metal oxide as coated particles, and coating the surface of the base material in order from the higher refractive index, Can be manufactured. The selection of the metal oxide is performed using as an index the covering force required when blending the flaky composite powder into the cosmetic. For example, when increasing the covering power of the flaky composite powder, it is preferable to use a metal oxide having a high refractive index, such as titanium oxide, for the first layer. On the other hand, when it is desired to set the covering force to be low, it is preferable to use a metal oxide having a medium refractive index, such as aluminum oxide, for the first layer. Next, the second and subsequent layers are coated, but in order to suppress the reflection of light and give a transparent feeling, the second and subsequent layers are made of a metal having a refractive index smaller than the refractive index of the first layer. It is desirable to use an oxide.

As a method for coating the base material with the coated particles, (i) a method of compounding in the presence of supercritical carbon dioxide, (ii) a method of coating by hydrolysis, and the like can be employed.
The method (i) of compounding in the presence of supercritical carbon dioxide is a base material and coated particles in the presence of supercritical carbon dioxide by the same operation as in the production example of the composite plate-like particle (A). In this method, a metal oxide and a polymer compound are brought into contact with each other to form a composite. In this method, the flaky composite powder usually has a structure covered with a polymer compound. More specifically, a composite form in which coated particles are present on the base material in a state where both the base material and the coated particles are coated with the polymer compound. Alternatively, coated particles may be present on the surface of the base material, and the whole may be coated with a polymer compound.
The polymer compound used preferably has a property that the intermolecular force is small and it is easily dissolved or dispersed in supercritical carbon dioxide. Specifically, at least one polymer compound selected from a fluorine-based polymer compound and a silicone-based polymer compound can be used. As these fluorine polymer compounds and silicone polymer compounds, those described above can be used.

As a method of coating by hydrolysis (ii), a metal salt or organometallic compound which is a precursor of a metal oxide is hydrolyzed, and the hydrolyzate is deposited on a base material on which a base material or a coating layer is formed. There is a way.
In this case, for example, by dispersing a base material in water, adding a predetermined amount of a metal salt such as titanyl sulfate, hydrolyzing in an alkaline atmosphere, and then depositing a metal salt hydrolyzate on the surface of the base material, A metal oxide coating layer such as titanium oxide having a predetermined thickness can be formed. When silica is coated as the outermost layer, a predetermined amount of an alkali metal silicate aqueous solution or an organic silicon compound is added to the dispersion of the base material on which a coating layer having a higher refractive index than silica is formed. Accordingly, a method of adding an acid or an alkali and further attaching a silicic acid polymer (hydrolytic condensation polymer) to the coated base material surface can be employed.

  The total coating film thickness of the coated particles is preferably 50 nm or less, and more preferably 20 nm to 50 nm, in order to give an excellent transparency to the cosmetic according to the present invention. The coating film thickness of the coated particle is determined by the geometric surface area of the matrix or the specific surface area measured by the nitrogen adsorption method, etc. It can be obtained more.

When the base material is sequentially coated with titanium oxide and aluminum oxide, the coating amount of titanium oxide and aluminum oxide is 0.42 or less in terms of the mass ratio of TiO ₂ / Al ₂ O _3. The difference (x−y) is not large, and it is preferable from the point that glare can be reduced. Furthermore, the total coating amount of titanium oxide and aluminum oxide is 1 to 50 in the flaky composite powder from the viewpoint that the feeling of use is good while maintaining transparency and the effect of making pores and the like inconspicuous. It is preferable that it is mass%, especially 5-40 mass%.
Further, when the base material is coated with titanium oxide, aluminum oxide, and silica sequentially, the coating amount of titanium oxide and aluminum oxide is 0.62 or less in terms of the weight ratio of TiO ₂ / Al ₂ O ₃ . It is 42 or less, and it is preferable that the total coating amount is 1 to 50% by mass, particularly 5 to 40% by mass. Furthermore, it is preferable that the coating amount of silica with respect to the powder is 0.1 to 30% by mass, particularly 0.2 to 20% by mass from the viewpoint of feeling of use (reducing squeaky feeling).

The (B) flaky composite powder obtained as described above preferably has a difference (xy) in the amount of surface reflection light of 12 or less, more preferably 11 or less, and even more preferably 10 or less. Further, the average particle diameter (major diameter of the plate-like powder) is preferably 0.1 to 1000 μm, more preferably 0.5 to 500 μm, particularly 5 to 50 μm from the viewpoint of handling as cosmetic particles. Is preferred.
The (B) flaky composite powder of the present invention can be subjected to a water repellency and / or oil repellency treatment in advance before blending into the makeup cosmetic. The conditions for the water and / or oil repellency treatment are the same as the conditions for the water and / or oil repellency treatment of the composite plate-like particles described above.

The make-up cosmetics of the present invention include powdered white powder, solid white powder, face powder, solid powdery foundation, oily foundation, creamy foundation, liquid foundation, concealer, blusher, eye shadow and the like.
The content of the (A) composite plate-like particles in these make-up cosmetics is 1 to 50% by mass from the viewpoint of avoiding unnaturalness due to a strong gloss while sufficiently exerting the content effect. Preferably it is the range of 2-30 mass%.
More specifically, in the case of powdered white powder, solid white powder and face powder, 0.1 to 30% by mass, particularly 0/5 to 30% by mass, in the case of solid powdery foundation and oily foundation, 0.1 to 30% by mass. %, Especially 0.5-30% by weight, 0.1-30% by weight for creamy foundations, liquid foundations and concealers, especially 0.5-25% by weight, 0.1% for blushers and eyeshadows. It is preferable to make it contain 30 mass%, especially 0.5-25 mass%.

  The content of the (B) flaky composite powder in the makeup cosmetic varies depending on the cosmetic dosage form and the like, and is not generally limited, but is usually preferably 1 to 90% by mass, and more preferably 1 It is preferable to set it as -50 mass%, especially 5-30 mass%. If the content of the flaky composite powder is within the above range, it is preferable from the viewpoints of feeling of use (such as spreading and adhesion) and finishing (such as transparency and pore concealing properties).

In addition to (A) the composite plate-like particles and (B) the flaky composite powder, the makeup cosmetic of the present invention includes components that are usually used in cosmetics, such as pigments, water-soluble high Molecules, oils, surfactants, antioxidants, fragrances, pigments, preservatives, ultraviolet absorbers, humectants, refreshing agents, and the like can be included.
Among these, in particular, when a pigment is used, it is preferable from the viewpoint of makeup sustainability to perform a water repellency and / or oil repellency treatment in advance. As the water and / or oil repellent treatment agent, the same compounds as those used for the water and / or oil repellent treatment agent of the composite plate-like particles can be used.
The make-up cosmetic of the present invention can be produced by uniformly mixing the above-mentioned components by a conventional method.
For example, when producing powdered white powder, solid white powder, face powder, solid powdered foundation, blusher, eye shadow, etc., it is produced according to a conventional method using a Henschel mixer, retro mixer, Hobart mixer, planetary mixer, kneader, etc. be able to.

Production Example 1 (Production of (A) composite plate-like particles)
Titanium mica (average particle size: 45μm, ECKART Gmbh & Co. KG) 21.90g and spherical PMMA (average particle size 0.3μm, Soken Chemical Co., Ltd.) 1.10g high-speed fluidized mixer super mixer (product) Name: Piccolo SMP-2, inner volume 0.3 L, Kawata Co., Ltd.) and mixed at 3000 rpm for 5 minutes to obtain a premixed powder. A scanning electron micrograph of the obtained premixed powder is shown in FIG. 4 (magnification: 30,000 times).
Next, after filling the autoclave (internal volume 500 mL: AKIKO Co., Ltd.) with 23.00 g of the pre-mixed powder, carbon dioxide gas or liquefied carbon dioxide is supplied, and a condenser at which a refrigerant at −5 ° C. is passed. The carbon dioxide was condensed and the pressure was increased with a pressure pump.
The stirrer was turned, carbon dioxide was preheated and introduced into the autoclave, and the temperature was adjusted to 296 K and the pressure was 6.2 MPa. Thereafter, the temperature was adjusted to 353 K and the pressure was adjusted to 25.0 MPa, and the mixture was kept under these conditions for 0.5 hours, then evacuated and decompressed for 10 minutes. At this time, the temperature inside the container was adjusted so as not to become 313K or lower, and the temperature inside the container at the end of the decompression was 326K. The internal pressure of the autoclave was reduced to atmospheric pressure to obtain composite plate-like particles. In this composite plate-like particle, the average particle size of PMMA particles is 0.3 to 0.5 μm, the ratio of the average particle size of PMMA fine particles / titanium mica is 1/150, and PMMA fine particles contain 1 mass of mica titanium. It is fixed to the part in an amount of 0.05 part by mass.
Scanning electron micrographs of the obtained composite plate-like particles are shown in FIG. 1 (magnification: 1,000 times), FIG. 2 (magnification: 10,000 times), and FIG. 3 (magnification: 30,000 times). 1 to 3, it can be seen that the PMMA particles are swollen and plasticized, the contact surface with titanium mica is flattened, and dispersed and fixed on the titanium mica surface in a wide range. Moreover, it can be seen that for some PMMA particles, adjacent particles are fused.

Production Example 2 ((A) Production of composite plate-like particles)
In Production Example 1, composite plate-like particles were obtained in the same manner as in Production Example 1, except that the amount of titanium mica was changed to 20.90 g and the amount of PMMA was changed to 2.10 g. The obtained composite plate-like particles have an average particle diameter of PMMA particles of 0.3 to 0.5 μm, an average particle diameter ratio of PMMA fine particles / titanium mica of 1/150, and PMMA fine particles are mica titanium. It is fixed in an amount of 0.1 part by mass with respect to 1 part by mass. The composite plate-like particles were fixed in a larger area on the surface of the mica titanium as compared with the composite plate-like particles obtained in Production Example 1, but the fixed state was the same.

Production Example 3 (Manufacture of (B) flaky composite powder)
340 g of talc was added to 3160 g of pure water and sufficiently dispersed. To this was added 200 g of a 20% strength titanyl sulfate aqueous solution as titanium dioxide, heated with stirring and boiled for 5 hours. This was cooled to room temperature, filtered, washed with water, and dried at 110 ° C. to obtain talc coated with a hydrate of titanium dioxide. Of these, 320 g was well dispersed in 2680 g of pure water, and 800 g of 10% strength aluminum chloride aqueous solution and 500 g of urea dissolved in 1800 g of water as aluminum oxide were added and mixed well, followed by heating at 90 ° C. for 10 hours. And then cooled to room temperature. This was filtered, washed with water, dried at 110 ° C., and then calcined at 600 ° C. for 5 hours to obtain talc coated sequentially with titanium oxide and aluminum oxide. Furthermore, 100 g of this was weighed and added to 1 L of a mixed solvent of ethanol and water (volume ratio of 7: 3) and well dispersed. To this was added 278 g of a 4% concentration ethyl silicate ethanol solution as silica, heated to 50 ° C. with stirring, and maintained for about 10 hours. Next, this was cooled, filtered, sufficiently washed with ethanol and pure water, and then dried at 110 ° C. to obtain talc coated sequentially with titanium oxide, aluminum oxide, and silica. The obtained flaky composite powder had a difference (xy) in the amount of surface reflection light of 10 and an average particle size of 20 μm.

Comparative production example 1
In the same manner as in Production Example 1, mica titanium and spherical PMMA were mixed to obtain a premixed powder. A scanning electron micrograph of the obtained composite plate-like particle is shown in FIG. 4 (magnification: 30,000 times). From FIG. 4, it can be seen that the PMMA particles that were almost spherical were only adhered on the surface of the mica titanium while remaining almost spherical.

Examples 1-2 and Comparative Examples 1-4 (Preparation of solid powdery foundation)
Components (1) to (13) shown in Table 1 ((A) composite plate-like particles of the present invention, (B) spherical powder, pigment, thickener, etc.) are mixed and ground. This is transferred to a high-speed blender, and components (14) and (15) mixed and dissolved at 80 ° C. are added and mixed uniformly. Ingredient (16) is added to the mixture, mixed and then ground again and passed through a sieve. This was compressed into a metal pan (solid powder foundation container) and molded.
(Evaluation methods)
Each of the products of the present invention and comparative products shown in Table 1 were used by 20 panelists specializing in cosmetics. According to the following evaluation criteria, “transparent finish”, “bright finish”, “natural skin color”, “glare” “Noness”, “Skin color correction effect”, and “Cover power” were evaluated. The average value of the evaluation results is shown in Table 1.
Evaluation criteria 5 points: very good 4 points: good 3 points: normal 2 points: slightly bad 1 point: bad

  The solid powdered foundations of Examples 1 and 2 had a clear natural skin color with a bright finish, very little glare, a high skin color correction effect, and a high covering power. On the other hand, the solid powder foundations of Comparative Examples 1 to 4 were inferior in “skin color correction effect”, “covering power” and the like.

Example 3 (Preparation of creamy foundation)
The following components (11) to (14) ((A) composite plate-like particles of the present invention, (B) flaky composite powder, pigment) are mixed and ground. Separately, a solution in which the aqueous phase components (7) to (10) are mixed is prepared, and the pulverized pigment is added and dispersed, followed by heating to 75 ° C. The oil phase components (1) to (6) heated and dissolved at 80 ° C. are added to the previously prepared aqueous phase with stirring and emulsified. This was cooled with stirring, the component (15) was added at 50 ° C., and the mixture was cooled with stirring to obtain a creamy foundation.
The obtained creamy foundation had high transparency, bright and natural, no unnatural glare, high skin color correction effect, and high covering power.
(Ingredient) (mass%)
(1) Stearic acid 5.5
(2) Glycerol monostearate 2.5
(3) Cetostearyl alcohol 1
(4) Monolauryl propylene glycol 3
(5) Squalane 7
(6) Olive oil 8
(7) Purified water Balance (8) Preservative appropriate amount (9) Triethanolamine 1.2
(10) Sorbit 3
(11) Titanium oxide 10
(12) Flaky composite powder of Production Example 6
(13) Colored pigment (Bengara, yellow iron oxide, black iron oxide) Appropriate amount (14) Composite plate-like particle of Production Example 1 5
(15) Fragrance Amount Trace Total 100

Example 4 (Preparation of white powder)
All the following components ((A) composite plate-like particles of the present invention, (B) flaky composite powder, pigment and the like) were mixed, pulverized through a pulverizer, and passed through a sieve to prepare a powdered white powder.
The obtained powdery white powder was transparent, bright and natural, had no unnatural glare, had a high skin color correction effect, and had high covering power.
(Ingredient) (mass%)
(1) Mica balance (2) Composite plate-like particle of Production Example 2 15
(3) Flaky composite powder of Production Example 3 20
(4) Spherical nylon 15
(Toray Industries, Inc. SP-500, average particle size: 6μm)
(5) Titanium oxide 0.5
(6) Bengala 0.3
(7) Yellow iron oxide 0.1
(8) Black iron oxide 0.01
(9) Magnesium stearate 10
(10) Preservative appropriate amount (11) Perfume Trace Total 100

Example 5 (Preparation of solid white powder)
The following components (1) to (7) ((A) composite plate-like particles of the present invention, (B) flaky composite powder, pigment) are mixed and ground, transferred to a high-speed blender, and further components (8) to (8) (10) mixed and dissolved at 80 ° C. is added and mixed uniformly. Component (11) is added to the mixture and mixed, then ground again and passed through a sieve. This was compressed and molded into a metal pan (white powder container).
The obtained solid white powder was high in transparency, bright and natural, free from unnatural glare, high in skin color correction effect, and high in covering power.
(Ingredient) (mass%)
(1) Mica balance (2) Composite plate-like particles of Production Example 1 (treated with dimethylpolysiloxane) 15
(3) Compounded plate-like particles (treated with dimethylpolysiloxane) of Production Example 2 10
(4) Flaky composite powder 20 of Production Example 20
(5) Zinc oxide 5
(6) Titanium oxide 0.5
(7) Black iron oxide 0.01
(8) Liquid paraffin 8
(9) Beeswax 2
(10) Preservative appropriate amount (11) Perfume Trace Total 100

Example 6 (Preparation of blusher)
The following components (1) to (7) ((A) composite plate-like particles of the present invention, (B) flaky composite powder, pigment, softener, etc.) were mixed and pulverized. Next, components (8) to (10) were sprayed and added in a mixer, mixed uniformly, passed through a sieve, and then compressed into a metal pan (blusher container) using a press to solidify.
The resulting blusher was transparent, bright and natural, free from unnatural glare, high skin color correction effect, and high covering power.
(Ingredient) (mass%)
(1) Mica balance (2) Composite plate-like particle of Production Example 2 20
(3) Flaky composite powder of Production Example 15 15
(4) Titanium oxide 4
(5) Zinc stearate 5
(6) Rice starch 5
(7) Color material 3
(8) Liquid paraffin 3
(9) Preservative appropriate amount (10) Fragrance Amount Trace Total 100

Example 7 (Preparation of liquid foundation)
After dissolving the following components (4) to (6) at room temperature, components (1) to (3) ((A) composite plate-like particles of the present invention, (B) flaky composite powder, pigment, etc.) Was added, dispersed with a disper, components (7) and (8) were added with stirring, and emulsified to prepare a liquid foundation.
The obtained liquid foundation was transparent, bright and natural, had no unnatural glare, had a high skin color correction effect, and had high covering power.
(Ingredient) (mass%)
(1) Hydrophobized pigment Titanium oxide (treated with methylhydrogenpolysiloxane) 1.0
Iron oxide (red, yellow, black) appropriate amount (treated with methyl hydrogen polysiloxane)
(2) Flaky composite powder of Production Example 3 6.0
(3) Composite plate-like particle of Production Example 1 5.0
(Methyl hydrogen polysiloxane treatment)
(4) Octamethylcyclotetrasiloxane 20.0
(5) Dimethylpolysiloxane 10.0
(KF-96A, Shin-Etsu Chemical Co., Ltd.)
(6) Dimethylpolysiloxane / polyoxyalkylene copolymer 1.0
("SH3775C", Toray Dow Corning Silicone Co., Ltd.)
(7) Glycerin 2.0
(8) Purified water balance Total 100

2 is a scanning electron micrograph (magnification: 1,000 times) showing the appearance of the composite plate-like particles obtained in Production Example 1. FIG. 2 is a scanning electron micrograph (magnification: 10,000 times) showing the appearance of the composite plate-like particles obtained in Production Example 1. FIG. 2 is a scanning electron micrograph (magnification: 30,000 times) showing the appearance of the composite plate-like particles obtained in Production Example 1. FIG. It is a scanning electron micrograph (magnification: 30,000 times) showing the appearance of the premixed powder obtained by the dry blend method.

Claims (8)

A makeup cosmetic containing the following (A) composite plate-like particles and (B) flaky composite powder.
(A) A composite plate-like particle comprising titanium mica and organic polymer fine particles and satisfying the following conditions (1) to (4): (1) The composite plate-like particle has a pressure higher than the critical temperature and 4 MPa or higher. Organic polymer fine particles fixed to the surface of titanium mica in the presence of carbon dioxide (2) The average particle size of the organic polymer fine particles is 0.01 to 30 μm
(3) Ratio (a / b) of average particle diameter (a) of organic polymer fine particles to average particle diameter (b) of titanium mica is 1/2000 to 1/5.
(4) The mass ratio of organic polymer fine particles to mica titanium is 0.001-1.
(B) A flaky composite powder in which a base material is coated with fine particles, wherein the base material has an average particle size of 0.1 to 1000 μm, and the fine particles have an average particle size with respect to the average particle size of the base material A flaky composite powder that is 1/5 or less and the content of the base material is 50 to 95% by mass   The makeup cosmetic according to claim 1, wherein the ratio (a / b) of the average particle size (a) of the organic polymer fine particles to the average particle size (b) of titanium mica is 1/800 to 1/10.   The makeup cosmetic according to claim 1 or 2, wherein the organic polymer fine particles are fine particles of polymethyl methacrylate.   (B) The makeup cosmetic according to any one of claims 1 to 3, wherein the flaky composite powder is based on talc.   (B) The makeup cosmetic according to any one of claims 1 to 4, wherein the flaky composite powder is obtained by coating a base material with at least one selected from titanium oxide, aluminum oxide, and silica.   (B) The makeup cosmetic according to any one of claims 1 to 5, wherein the flaky composite powder is obtained by sequentially coating a base material with titanium oxide and aluminum oxide.   The makeup cosmetic according to any one of claims 1 to 6, wherein (B) the flaky composite powder is obtained by sequentially coating a base material with titanium oxide, aluminum oxide, and silica.   The makeup cosmetic according to any one of claims 1 to 7, comprising (A) 1 to 50% by mass of composite plate-like particles and (B) 1 to 90% by mass of flaky composite powder.

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