JP6985909B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

The present invention relates to a water-in-oil emulsified cosmetic.

Conventionally, cosmetics that prevent makeup from collapsing, especially shine caused by sebum, have been studied. For example, Patent Document 1 and Patent Document 2 describe cosmetics containing an oil-absorbing powder capable of absorbing squalane having a weight of 1.5 times or more of its own weight.

Japanese Unexamined Patent Publication No. 4-117315 Japanese Unexamined Patent Publication No. 4-305511

In recent years, various products have been put on the market, and consumers are becoming more aware of cosmetics. In addition to demanding the effect of preventing makeup from collapsing, there are voices demanding various feelings of use in cosmetics. With the cosmetics described in Patent Documents 1 and 2, the feeling of a thin film could not be felt at the time of application, and the skin after application may appear white.

By using a specific spherical organic powder in combination with synthetic mica or glass flakes and volatile oil, the present inventors can feel a thin film feeling at the time of application, and the skin after application does not appear white. It has been found that a water-in-oil emulsified cosmetic can be obtained.

In the present invention, the following components (A), (B), (C) and (H):
(A) Spherical organic powder having an oil absorption of 1.0 g / g or more and a water absorption of 1.0 g / g or less of squalane 0.1 to 10% by mass,
(B) Synthetic mica or glass flakes 0.05-10% by mass,
(C) Volatile oil 5-60% by mass,
(H) Water 5 to 70% by mass
Containing water-in-oil emulsified cosmetics.

In the water-in-oil emulsified cosmetic of the present invention, a thin film feeling can be felt at the time of application, and the skin after application does not appear white. In addition, it spreads well when applied, is less sticky, and has a good feel.
The thin film feeling is the feeling that when the cosmetic is applied and spread with the fingertips, the fingertips are covered with a moist and thin film, and the water-in-oil emulsified cosmetic is spread smoothly and without resistance to the skin. Indicates that. In addition, the state is different from the feeling of being wet with liquid oily components and aqueous components attached.
Further, the whitening of the skin after application means that after applying the water-in-oil emulsified cosmetic to the entire face, the entire face appears to be whitened from the surroundings.

The component (A) used in the present invention is a spherical organic powder having a squalane oil absorption of 1.0 g / g or more and a water absorption of 1.0 g / g or less.
Here, the spherical shape may include a true sphere, a substantially spherical shape, and a spheroid, and may be a spherical powder having an uneven surface, a powder surface, a spherical powder having voids inside, or the like.
The oil absorption of the spherical organic powder is shown by the oil absorption of squalane because of its similarity to sebum. The oil absorption amount of squalane indicates the amount (g) of absorbing squalane per 1 g of powder, and the water absorption amount indicates the amount (g) of absorbing water per 1 g of powder.

The oil absorption of squalane is 1.0 g / g or more, preferably 1.0 to 4.0 g / g, and 1.5 to 3.5 g, from the viewpoint of improving the feeling of a thin film at the time of application and suppressing stickiness. / G is more preferable, 1.8 to 3.0 g / g is even more preferable, and 2.2 to 2.8 g / g is even more preferable.

The water absorption amount is 1.0 g / g or less, preferably 0.8 g / g or less, more preferably 0.5 g / g or less, and 0.2 g / g, from the viewpoint of improving the feeling of a thin film at the time of coating. The following is more preferable.
The amount of oil absorption and the amount of water absorption of squalane can be determined by the method of Examples described later.

As the spherical organic powder of the component (A), a porous spherical organic powder is preferable from the viewpoint of improving the thin film feeling and elongation at the time of coating. Porosity refers to a structure having a large number of small voids inside or on the surface of the powder.

The spherical organic powder of the component (A) preferably has a volume average particle size of 1 to 30 μm, more preferably 2 to 20 μm, and even more preferably 3 to 15 μm, from the viewpoint of improving elongation.
Here, the volume average particle size is measured by a laser diffraction scattering particle size distribution measuring device (LA-920, manufactured by HORIBA, Ltd.). In the present invention, the volume average particle diameter is a volume-based average particle diameter, and is 50% median diameter.

Spherical organic powder component (A), a thin film feeling during coating, from the viewpoint of improving the elongation, to suppress the stickiness, the specific surface area is preferably from 50~300m ² / g, 60~260m ² / g is more preferred, 70 to 230 m ² / g is even more preferred, and 80 to 220 m ² / g is even more preferred.
In the present invention, the specific surface area means the surface area per unit mass, and in the present invention, it means the specific surface area obtained by the _{BET method (N 2).} The specific surface area can be determined by the method of Examples described later.

As the spherical organic powder of the component (A), one or more vinyl monomers having a solubility parameter of 7 to 10 are polymerized from the viewpoint of improving the thin film feeling, elongation, and oil absorption of squalane during coating. The porous vinyl-based polymer thus obtained is preferable.

Here, the solubility parameter δ (SP value) is a substance constant given by ^{δ = (E / V) 1/2} (J / cm ³ ) from the molecular aggregation energy E and the molar molecular volume V of the liquid. SP value is determined by various methods, in the present invention, the method of Fedors (J. BRANDR UP al., "POLYMER HANDBOOK-4 ^th" JHON WILEY & SONS, INC 1999 Issued, the parameters given in Section VII685~686 It was calculated according to the one obtained by using).

Examples of the vinyl-based monomer having a solubility parameter of 7 to 10 include alkyl (meth) acrylate having a hydrocarbon group having a linear or branched chain having 1 to 24 carbon atoms, styrene, and a linear or linear monomer having 1 to 12 carbon atoms. Examples thereof include a styrene derivative having a hydrocarbon group of a branched chain, a vinyl ester of a saturated carboxylic acid having 8 to 20 carbon atoms, and a diolefin having 4 to 6 carbon atoms.
As the spherical organic powder of the component (A), among these monomers, a straight-chain or branched hydrocarbon group having 1 to 24 carbon atoms is used from the viewpoint of improving the thin film feeling at the time of coating and the oil absorption of styrene. A porous vinyl polymer obtained by polymerizing one or more selected from an alkyl (meth) acrylate, styrene, and a styrene derivative having a linear or branched hydrocarbon group having 1 to 12 carbon atoms. Preferably, a porous vinyl polymer obtained by polymerizing one or more selected from alkyl (meth) acrylates and styrene having a linear or branched hydrocarbon group having 1 to 24 carbon atoms is more preferable. A porous vinyl polymer obtained by polymerizing one or more selected from alkyl (meth) acrylates having a linear or branched hydrocarbon group having 1 to 24 carbon atoms is further preferable. Further, a crosslinked product is preferable.

As the component (A), cosmetics labeled as "Methyl Methacrylate Crosspolymer" (INCI name "Methyl Methacrylate Crosspolymer") in which methyl methacrylate is crosslinked with ethylene glycol dimethacrylate, and cosmetics in which stearyl methacrylate and styrene are crosslinked with divinylbenzene. Display names such as "(styrene / stearyl Methacrylate Crosspolymer") (INCI name "Styrene / Stearyl Methacrylate Crosspolymer") and the like can be mentioned. As the component (A), "methyl methacrylate crosspolymer" and "(styrene / stearyl methacrylate) cloth" are used from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing the whitening and stickiness of the skin after application. "Polymer" is preferable, and "(styrene / stearyl methacrylate) crosspolymer" is more preferable.
Examples of commercially available products of "methyl methacrylate crosspolymer" include MAKIBEADS 150 and MAKIBEADS 250 (all manufactured by Daito Kasei Kogyo Co., Ltd.), and "(styrene / stearyl methacrylate) crosspolymer" is described in JP-A-63-. It can be produced by the method described in 316715.

One or two or more kinds of the component (A) can be used, and the content is in the whole composition from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing the whitening and stickiness of the skin after application. It is 0.1 to 10% by mass, preferably 1 to 7% by mass, more preferably 2 to 5% by mass, still more preferably 2.4 to 4.3% by mass.

Component (B) is synthetic mica or glass flakes.
Of these, synthetic mica is preferably one or more selected from synthetic phlogopite and synthetic muscovite from the viewpoint of improving the thin film feeling at the time of application and suppressing whitening and stickiness of the skin after application. , Synthetic phlogopite is more preferred.
Examples of the synthetic phlogopite include those obtained by mixing and melting silicic acid anhydride, aluminum oxide, magnesium oxide, and potassium silicate, crystallizing crystals, pulverizing, and heat-treating. It may also contain iron. When iron is contained, the iron content is preferably 0.5 to 10% by mass in terms of iron oxide from the viewpoint of suppressing whitening of the skin after application.

The shape of these synthetic mica is preferably a plate-like shape, and the volume average particle size is preferably 5 to 100 μm from the viewpoint of improving the feeling of a thin film at the time of application and suppressing whitening and stickiness of the skin after application. , 5 to 50 μm is more preferable. The aspect ratio is preferably 15 to 100, more preferably 20 to 85.
Here, the volume average particle diameter is measured by the same method as that of the component (A). The thickness of the particles is obtained by averaging the thicknesses of 10 to 50 particles measured by observing with a scanning electron microscope or a transmission electron microscope.
The aspect ratio is calculated by the ratio of the volume average particle diameter to the average thickness, and is defined by the aspect ratio = (volume average particle diameter / average thickness).

Such synthetic mica can be manufactured and used by the above-mentioned production method, or a commercially available product can also be used. Examples of commercially available products include PDM-1000 (volume average particle diameter 12 μm, aspect ratio 20), PDM-10L (volume average particle diameter 12 μm, aspect ratio 60), and PDM-20L (volume average particle diameter) manufactured by Topy Industries, Ltd. 20 μm, aspect ratio 70), PDM-40L (volume average particle diameter 40 μm, aspect ratio 80), PDM-NFES (volume average particle diameter 5 μm, aspect ratio 40) and the like can be used.

Further, the glass flakes may be any glass flakes as long as they are used in ordinary cosmetics, and may be coated with one or more precious metals, metal oxides, and / or silica. Examples thereof include titanium oxide-coated glass flakes, silver-coated glass flakes, gold-coated glass flakes, iron oxide-coated glass flakes, and the like, with iron oxide-coated glass flakes being preferred.
The shape of the glass flakes is preferably plate-like, and the volume average particle size is preferably 1 to 50 μm from the viewpoint of improving the feeling of a thin film at the time of application and suppressing whitening and stickiness of the skin after application. 5 to 30 μm is more preferable. The aspect ratio is preferably 10 to 90, more preferably 15 to 80.
The volume average particle diameter and the particle thickness are measured by the same method as that of synthetic mica, and the aspect ratio is calculated by the same method as that of synthetic mica.

As such glass flakes, commercially available products can be used, for example, Metashine MT1040RG (volume average particle diameter 40 μm, aspect ratio 40), silky flakes FTD025FY-F02 (volume average particle diameter 25 μm, manufactured by Nippon Plate Glass Co., Ltd., Aspect ratio 62.5), silky flake FTD025FY-F12 (volume average particle diameter 25 μm, aspect ratio 62.5), silky flake FTD010FY-F01 (volume average particle diameter 10 μm, aspect ratio 25) and the like can be used.

The synthetic mica and glass flakes of the component (B) can be used as they are, or can be hydrophobized, if necessary.
Examples of the hydrophobizing treatment include silicone treatment, fluorine treatment, fatty acid treatment, N-acylamino acid treatment and the like. Examples of the silicone treatment include methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, alkylalkoxysilane treatment and the like, and examples of the fluorine treatment include perfluoroalkylphosphate ester treatment and perfluoroalkylalkoxysilane treatment. Examples of the fatty acid treatment include stearic acid treatment and myristic acid treatment, and examples of the N-acylamino acid treatment include lauroyl lysine treatment, dilauroyl glutamic acid lysine Na treatment, stearoyl glutamic acid 2Na treatment, lauroyl aspartate Na treatment and the like. ..
As the hydrophobic treatment, silicone treatment and fluorine treatment are preferable from the viewpoint of improving the feeling of thin film and suppressing whitening of the skin after application, and methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, alkylalkoxysilane treatment, etc. Perfluoroalkylalkoxysilane treatment is more preferred, and methylhydrogenpolysiloxane treatment and dimethylpolysiloxane treatment are even more preferred.
The hydrophobizing treatment can be carried out by a usual method.
When the component (B) is hydrophobized, the content, volume average particle size, and particle thickness of the component (B) are the content including the hydrophobized agent, the volume average particle diameter, and the particles. Means the thickness of.

As the component (B), one kind or two or more kinds can be used, and the content is added to the whole composition from the viewpoint of improving the feeling of a thin film at the time of application and suppressing whitening and stickiness of the skin after application. It is 0.05 to 10% by mass, preferably 0.10 to 8% by mass, and more preferably 0.5 to 6% by mass.

In the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing the whitening and stickiness of the skin after application. , 0.05 to 50, more preferably 0.1 to 40, still more preferably 0.2 to 30.

In the volatile oil of the component (C), the volatility is one having a flash point of 35 to 100 ° C.
The volatile oil may be any oil used in ordinary cosmetics, and examples thereof include silicone oil, hydrocarbon oil, and ether oil.
Examples of the silicone oil include chain dimethylpolysiloxane and cyclic dimethylpolysiloxane. The chain dimethylpolysiloxane may be either a straight chain or a branched chain, and examples of the linear dimethylpolysiloxane include dimethylpolysiloxane (1.5 cs) and dimethylpolysiloxane (2 cs). Examples thereof include methyltrimethicone, tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane and the like. Examples of the cyclic dimethylpolysiloxane include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
Examples of the hydrocarbon include isododecane, isotridecane, isohexadecane, liquid isoparaffin and the like, and examples of the ether oil include ethyl perfluorobutyl ether and the like.

Of these, one or more selected from silicone oil and hydrocarbon oil are preferable from the viewpoint of improving the feeling of a thin film at the time of coating and suppressing stickiness, and dimethylpolysiloxane (2cs) and decamethylcyclopentasiloxane are preferable. , Isododecane, one or more selected from light isoparaffin is more preferred, and one or more selected from dimethylpolysiloxane (2cs), decamethylcyclopentasiloxane is even more preferred.
The volatile oil of the component (C) preferably contains at least a silicone oil from the viewpoint of improving the feeling of a thin film at the time of coating and suppressing stickiness.

As the component (C), one kind or two or more kinds can be used, and the content is 5 to 60% by mass in the total composition from the viewpoint of improving the feeling of a thin film at the time of coating and suppressing stickiness. It is preferably 10 to 50% by mass, more preferably 15 to 30% by mass.

In the present invention, the mass ratio (B) / (C) of the component (B) to the component (C) is from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing the whitening and stickiness of the skin after application. , 0.001 to 0.6, more preferably 0.005 to 0.4, still more preferably 0.010 to 0.28.

The water-in-oil emulsified cosmetic of the present invention preferably further contains (D) a water-soluble polymer from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing stickiness.
The water-soluble polymer may be any one used in ordinary cosmetics, for example, a protein or polypeptide such as gelatin, collagen; hyaluronic acid or a salt thereof, tuberose polysaccharide, xanthan gum, chondroitin sulfate or a salt thereof, Polysaccharides such as dextrin, pectin, gellan gum, carrageenan, purulan, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, alginic acid or salts thereof; carboxyvinyl polymers which may be alkyl-modified, polyacrylamides, acrylamides and acrylics. Examples thereof include a copolymer with an acid, at least an acrylic acid salt or an acrylic acid-based polymer such as a copolymer obtained by copolymerizing at least hydroxyalkyl acrylate and an acryloyldimethyltaurine salt.
Of these, one or more selected from polysaccharides and acrylic acid-based polymers is preferable, and one selected from polysaccharides or one or more from the viewpoint of improving the thin film feeling and elongation at the time of application and suppressing stickiness. Two or more are more preferable, and one or more selected from hyaluronic acid or a salt thereof is further preferable.

The component (D) can be used alone or in combination of two or more, and the content is 0.0001 to 0.0001 in the entire composition from the viewpoint of improving the thin film feeling and elongation at the time of coating and suppressing stickiness. 0.1% by mass is preferable, 0.0003 to 0.05% by mass is more preferable, and 0.001 to 0.03% by mass is further preferable.

In the present invention, the mass ratio (A) / (D) of the component (A) to the component (D) is preferably 10 to 10000, preferably 80 to 5000, from the viewpoint of improving the feeling of a thin film at the time of coating and suppressing stickiness. Is more preferable, 150 to 1500 is further preferable, and 330 to 1000 is even more preferable.

The water-in-oil emulsified cosmetic of the present invention preferably further contains (E) a liquid polar oil at 25 ° C. from the viewpoint of improving the thin film feeling and elongation at the time of application. Here, the liquid has fluidity, and includes cream-like and paste-like ones.
The polar oil liquid at 25 ° C. may be any oil used in ordinary cosmetics, and is one or two selected from ester oils, alcohols having 12 to 24 carbon atoms and fatty acids having 12 to 24 carbon atoms. More than seeds can be mentioned.

Specifically, the ester oils include, for example, monoester oils such as isotridecyl isononanoate, isostearyl myristate, 2-ethylhexyl paramethoxysilicate, and diglyceryl monoisostearate; diisostearyl malate and neodicaprate. Diester oils such as pentylglycol, diglyceryl diisostearate, and glyceryl monomyristate monoisostearate; and tryester oils of triisostea, glyceryl tri2-ethylhexanoate and the like.

Examples of the alcohol having 12 to 24 carbon atoms include octyldodecanol and oleyl alcohol.
Examples of the fatty acid having 12 to 24 carbon atoms include oleic acid, isostearic acid, isopalmitic acid, isomyristic acid, linolenic acid, linoleic acid, ricinoleic acid, and oxystearic acid.

The component (E) is preferably one or more selected from monoester oil, diester oil, and triester oil, and is selected from monoester oil and diester oil, from the viewpoint of improving the thin film feeling and elongation at the time of coating. One or more of them are more preferable, and one or more of them selected from monoester oils are even more preferable. Further, from the viewpoint of improving the thin film feeling and elongation at the time of application, it is preferable to contain at least 2-ethylhexyl paramethoxycinnamate.

The component (E) can be used alone or in combination of two or more, and the content is preferably 0.1 to 15% by mass in the entire composition from the viewpoint of improving the thin film feeling and elongation at the time of coating. , 0.4 to 12% by mass, more preferably 1.0 to 8.0% by mass, and even more preferably 1.5 to 6.5% by mass.

The water-in-oil emulsified cosmetic of the present invention further contains (F) a nonionic surfactant having a size of less than HLB8 from the viewpoint of improving the feeling of a thin film at the time of application and suppressing whitening of the skin after application. Is preferable.
From the same viewpoint, the HLB of the nonionic surfactant of the component (F) is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably less than 8, more preferably less than 7, and less than 6. Is even more preferable.

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lypophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and for nonionic surfactants, Griffin ( It is obtained by the formula of Griffin). The HLB of a mixed surfactant composed of two or more nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is a phase addition average of the HLB values of each nonionic surfactant based on the blending ratio.
Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X. Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

Such nonionic surfactants are those used in ordinary cosmetics, for example, alkanolamide, amine oxide, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid amide, poly. Examples thereof include oxyethylene alkylamine, alkyl saccharide, α-monoalkyl glyceryl ether, polyether-modified silicone and the like.

As the nonionic surfactant having less than HLB8 of the component (F), one or 2 selected from the polyether-modified silicone from the viewpoint of improving the thin film feeling at the time of application and suppressing the whitening of the skin after application. More than a seed is preferred. As the polyether-modified silicone, a commercially available product can be used. For example, as the polyoxyethylene / methylpolysiloxane copolymer, KF-6015 (HLB4.5), KF-6017 (HLB4.5), KF-6028 ( HLB4) (above, manufactured by Shin-Etsu Chemical Co., Ltd.), SH3775M (HLB5) (manufactured by Toray Dow Corning Co., Ltd.), etc .; as an alkyl-modified copolymer, KF-6038 (HLB3) (manufactured by Shin-Etsu Chemical Co., Ltd.); Poly Examples of the (oxyethylene / oxypropylene) methylpolysiloxane copolymer include KF-6012 (HLB7) (manufactured by Shin-Etsu Chemical Co., Ltd.).

As the component (F), one kind or two or more kinds can be used, and the content is 0. 1 to 8% by mass is preferable, 0.2 to 5% by mass is more preferable, and 0.3 to 2% by mass is further preferable.

The water-in-oil emulsified cosmetic of the present invention preferably further contains ^{(G) zinc oxide having a specific surface area of 10 to 100 m 2 / g from the viewpoint of suppressing stickiness.}
From the same viewpoint, the zinc oxide of the component (G) ^{preferably has a specific surface area of 15 to 95 m 2} / g.
Here, the specific surface area is measured by the same method as that of the component (A).

From the same viewpoint, the average particle size is preferably 5 to 50 nm, more preferably 10 to 40 nm.
The average particle size is a value obtained from a transmission electron micrograph as an arithmetic mean of the major axis and the minor axis of the particles.
The zinc oxide of the component (G) can be used as it is, or if necessary, a hydrophobized zinc oxide can be used as in the component (B).

As the component (G), one kind or two or more kinds can be used, and the content is preferably 0.1 to 20% by mass, more preferably 0.5 to 17% by mass in the total composition from the same viewpoint. It is preferably 1 to 15% by mass, more preferably 1 to 15% by mass.

In the water-in-oil emulsified cosmetic of the present invention, the content of water (H) is preferably 5 to 70% by mass, more preferably 8 to 65% by mass, still more preferably 10 to 60% by mass in the total composition. ..

The water-in-oil emulsified cosmetic of the present invention further preferably contains a coloring pigment from the viewpoint of finishing the skin with a clean make-up effect, and contains one or more selected from titanium oxide and iron oxide. It is more preferable to do so.
One or two or more kinds of coloring pigments can be used, and the content is preferably 0.001 to 20% by mass, preferably 0.005 to 15% by mass in the entire composition from the viewpoint of finishing the skin with a clean make-up effect. The mass% is more preferable, and 0.01 to 10% by mass is further preferable.

In addition to the above-mentioned components, the emulsified cosmetic of the present invention includes components used in ordinary cosmetics, for example, powders other than the components (A), (B), (G) and coloring pigments, the components (C) and ( Oily ingredients other than E), surfactants other than ingredient (F), ethanol, polyhydric alcohol, preservatives, antioxidants, pigments, thickeners other than ingredient (D), pH adjusters, fragrances, UV absorption It can contain an agent, a moisturizer, a blood circulation promoter, a cooling sensation agent, an antiperspirant, a bactericidal agent and the like.

The water-in-oil emulsified cosmetic of the present invention can be produced by a usual method. Specifically, at a predetermined temperature of about 25 ° C., the powder component containing the components (A) and (B) is added to the oil phase component containing the component (C) and dispersed. Then, the aqueous phase component containing the component (H) is added and stirred to obtain a water-in-oil emulsified cosmetic.
The water-in-oil emulsified cosmetic of the present invention can be in the form of a liquid, milky liquid, paste, cream, gel or the like, and is preferably milky or creamy.

The water-in-oil emulsified cosmetic of the present invention is a makeup base, foundation, concealer; make-up cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as an ultraviolet protective cosmetic such as sunscreen cream. Of these, makeup bases, liquid foundations, concealers, sunscreen emulsions, and sunscreen creams are more preferred, and makeup bases and liquid foundations are even more preferred.
The water-in-oil emulsified cosmetic of the present invention can be used not only as a single item but also as a layer of powdered cosmetics such as liquid foundation, powder foundation and white powder.
The water-in-oil emulsified cosmetic of the present invention can be used by applying it to any of the skin, especially the skin excluding hair, preferably the face, body, limbs and the like.

Production Example 1 ((A) Production of organic spherical powder)
To a beaker, 500 g of water and 1.5 g of polyvinyl alcohol were added, and the mixture was stirred and mixed under the condition of 20 ° C. to obtain an aqueous polyvinyl alcohol solution. Then, a solution obtained by mixing and stirring 25 g of stearyl methacrylate, 40 g of styrene, 35 g of divinylbenzene, 150 g of n-heptane, and 3 g of lauroyl peroxide was added to the aqueous polyvinyl alcohol solution and stirred with a homomixer to obtain an emulsion. .. The prepared emulsion was added to a 2 L separable flask equipped with a stirrer, a reflux tube and a nitrogen introduction tube, the temperature was raised to 70 ° C. while stirring, and polymerization was carried out in a nitrogen atmosphere for 10 hours. After completion of the polymerization, n-heptane was distilled off by an evaporator, filtered off, washed with water, and dried. The obtained solid material was crushed by a mill to obtain a porous vinyl-based polymer ((styrene / stearyl methacrylate) crosspolymer) having a volume average particle diameter of 8 μm.

Hereinafter, in the present invention, the oil absorption amount, the water absorption amount and the specific surface area of the powdered squalane are measured according to the following methods. The measurement results of the powder used in the examples are shown in Table 1.

(1) Method for measuring the oil absorption of powdered squalane:
The measurement was carried out with reference to the method for measuring the oil absorption of the pigment specified in JIS K5101-13-2: 2004. First, 1 g of powder was taken on a glass plate, squalane was dropped little by little using a pipette, and the powder and squalane were kneaded using a palette knife each time. When the powder and squalane changed into a hard paste, the squalane was kneaded drop by drop, and the paste was rapidly softened by the last drop of squalane, and the point at which the paste started to flow was defined as the end point of the oil absorption. The amount of squalane (g) when the end point was reached was defined as the amount of oil absorbed per 1 g of powder. In the JIS method, oil is used for boiled flax as oil, but in this method, squalane was used because of its similarity to sebum.
At the end point, the paste suddenly softens due to the dropping of the last drop of squalane, place more than half of the paste on the palette knife, tilt the flat surface of the palette knife 90 ° to the ground, and paste within 10 seconds. (If it does not fall within 10 seconds, it is not considered as a paste-like end point).
Further, the squalane was dropped onto the powder, and the work of pressing the squalane against the powder with a palette knife was performed twice. When the squalane and the powder were clearly not mixed, the oil absorption amount was set to 0 g / g.

(2) Method for measuring water absorption of powder:
In the method for measuring the oil absorption of squalane, squalane was changed to water and the same method was used.

(3) Method for measuring the specific surface area of powder:
For the specific surface area of the powder, for the sample dried under reduced pressure at 80 ° C. for 15 hours, about 0.1 g of the measurement sample was concentrated in the measurement cell to 4 digits after the decimal point, and immediately before the measurement of the specific surface area, the measurement was performed in an atmosphere of 120 ° C. After drying for 10 minutes, the measurement was carried out by the nitrogen adsorption method (BET method) using a specific surface area measuring device (single-point BET specific surface area measuring device Flowsorb III 2305, manufactured by Shimadzu Corporation).

Examples 1 to 15 and Comparative Examples 1 to 3
A water-in-oil emulsified cosmetic having the composition shown in Table 2 was produced, and the thin film feeling, the finish without whitening, the ease of spreading, and the non-stickiness were evaluated. The results are also shown in Table 2.

(Manufacturing method)
At 25 ° C., a powder component containing the components (A), (B) and (G) was added to the oil phase component containing the components (C), (E) and (F) and dispersed. Then, the aqueous phase component containing the components (D) and (H) was added and stirred with a homomixer to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
(1) Thin film feeling:
Five expert evaluators applied the water-in-oil cosmetics to the skin and evaluated the feeling of thin film between the fingers and the skin while stretching it on the following five stages. The evaluation results in the table are shown by the total score of 5 professional evaluators. The thin film feeling means that when the cosmetic is applied and spread with the fingertips, the fingertips are covered with a moist and thin film, and the cosmetic is spread smoothly and without resistance to the skin. In addition, the state is different from the feeling of being wet with liquid oily components and aqueous components attached.
5; I feel a very thin film while stretching.
4; I feel a little thin film while stretching.
3; I feel a little thin film while stretching.
2; I hardly feel a thin film while stretching.
1; I do not feel a thin film feeling at all while stretching.

(2) Finish that does not appear white:
When five expert evaluators applied each of the water-in-oil emulsified cosmetics to the face, the feeling of the finish in which the entire face was white and invisible from the surroundings was evaluated according to the following criteria. The evaluation results in the table are shown by the total score of 5 professional evaluators.
5; Whitening is not noticeable at all.
4; Whitening is hardly noticeable.
3; Whitening is not so noticeable.
2; Whitening is a little noticeable.
1; Whitening is very noticeable.

(3) Ease of stretching:
When five expert evaluators applied the water-in-oil cosmetic to the skin, the elongation during application was evaluated on the following five stages. The evaluation results in the table are shown by the total score of 5 professional evaluators.
5; Very good spread on the skin.
4; Good spread on the skin.
3; Slightly stretches on the skin.
2; Slightly poor growth on the skin.
1; Poor growth on the skin.

(4) Non-sticky:
Five expert evaluators evaluated the non-stickiness when touching the skin while applying the water-in-oil cosmetic to the skin on the following five stages. The evaluation results in the table are shown by the total score of 5 professional evaluators.
5; There is no stickiness on the skin during application.
4; There is almost no stickiness on the skin during application.
3; There is a little stickiness on the skin during application.
2; The skin is sticky during application.
1; The skin is very sticky during application.

* 1: Spherical organic powder: Production Example 1 (volume average particle diameter 8 μm),
* 2: Methyl methacrylate crosspolymer: manufactured by Daito Kasei Kogyo Co., Ltd., MAKIBEADS 150 (volume average particle diameter 8 μm),
* 3: Methyl methacrylate crosspolymer: manufactured by Daito Kasei Kogyo Co., Ltd., MAKIBEADS 250 (volume average particle diameter 8 μm),
* 4: (Vinyl dimethicone / methicone silsesquioxane) Cross polymer: KSP-100 (volume average particle diameter 5 μm) manufactured by Shin-Etsu Chemical Co., Ltd.,
* 5: Methyl methacrylate crosspolymer: Matsumoto Yushi Pharmaceutical Co., Ltd., Matsumoto Microsphere M-305 (volume average particle diameter 13 μm),
* 6: Silicone 2% by mass treatment Synthetic phlogopite: Topy Industries, Ltd., PDM-10L treated with 2% by mass methylhydrogenpolysiloxane (average particle size 12 μm, aspect ratio 60),
* 7: Silicone 3% by mass treatment Synthetic phlogopite: Topy Industries, Ltd., synthetic mica PDM-40L treated with 3% by mass dimethylpolysiloxane (average particle size 40 μm, aspect ratio 80),
* 8: Glass flakes: Silky flakes FTD025FY-F12 (average particle diameter 25 μm, aspect ratio 62.5), manufactured by Nippon Sheet Glass Co., Ltd.,
* 9: Didimethylpolysiloxane: Shin-Etsu Chemical Co., Ltd., Silicone KF-96L-2CS,
* 10: Sodium hyaluronate (1% by mass aqueous solution): Kewpie Co., Ltd., hyaluronic acid solution HA-Q1,
* 11: Fluorine-modified silicone: the compound described in JP-A-2016-22259, Synthesis Example 1.
* 12: Polyoxyethylene / methylpolysiloxane copolymer: manufactured by Dow Corning, Silicon SH 3775 M (HLB 5),
* 13: Fluorine-modified silicone resin (50% by mass decamethylcyclopentasiloxane solution): Silicone XS66-B8226, manufactured by Momentive Performance Materials Japan LLC,
* 14: Poly (N-propionyl polyethyleneimine-modified silicone: JP-A-2016-22259, compound described in Synthesis Example 3,
* 15: Silicone 6% by mass treated Zinc oxide: Made by Sakai Chemical Industry Co., Ltd., FINEX-50 treated with 6% by mass methylhydrogenpolysiloxane (specific surface area 50 m ² / g, average particle size 20 nm),
* 16: Silicone 2% by mass treated Titanium oxide: Titanium oxide treated with 2% by mass methylhydrogenpolysiloxane,
* 17: Silicone 2% by mass treated Red iron oxide: Red iron oxide treated with 2% by mass methylhydrogenpolysiloxane,
* 18: Silicone 2% by mass treatment Yellow iron oxide: Yellow iron oxide treated with 2% by mass methylhydrogenpolysiloxane

Claims (5)

The following components (A), (B), (C) , (E), (F) and (H):
(A) Organic spherical powder selected from methyl methacrylate crosspolymer and (styrene / stearyl methacrylate) crosspolymer having an oil absorption of 1.0 g / g or more and a water absorption of 1.0 g / g or less of squalane. 1-10% by mass,
(B) Synthetic mica or glass flakes 0.5 to 10% by mass,
(C) Volatile oil 5-60% by mass,
(E) Polar oil liquid at 25 ° C,
(F) Nonionic surfactant less than HLB8,
(H) Water 5 to 70% by mass
A water-in-oil emulsified cosmetic having a mass ratio (A) / (B) of the component (A) to the component (B) of 0.05 to 30. Further, (D) in oil according to claim 1, containing a water-soluble polymer type emulsion cosmetic. The water-in-oil emulsified cosmetic according to claim 2 , wherein the component (D) is hyaluronic acid or a salt thereof. The water-in-oil emulsified cosmetic according to claim 2 or 3, wherein the mass ratio (A) / (D) of the component (A) to the component (D) is 10 to 10,000. (G) The water-in-oil emulsified cosmetic according to any one of claims 1 to 4 , which contains zinc oxide having a specific surface area of 10 to 100 m ^{2 / g.}