JP7650644B2 - Water-in-oil emulsion cosmetics - Google Patents

Description

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

Water-in-oil emulsion cosmetics such as foundations are required to have excellent cosmetic durability, be non-sticky, and have a good feel when used.
For example, Patent Literature 1 describes that a water-in-oil emulsion cosmetic containing a surface-treated pigment, a volatile oil, water, an organic silicone resin, and a nonionic surfactant provides a uniform finish without a sticky feeling while maintaining a fresh feel to the touch.

JP 2019-99468 A

The inventors have found that although emulsion cosmetics containing a silicone-based film-forming agent, a volatile oil, and an ester oil have excellent makeup durability, they have the problem that the makeup tends to come off over time.

The inventors have discovered that by using a specific non-volatile silicone oil and ester oil in a specific ratio in a water-in-oil emulsion cosmetic that contains a silicone-based film-forming agent and a volatile oil, the brightness of the skin immediately after application is sustained, a uniform finish is obtained, and the skin does not become shiny even over a long period of time, makeup wear is prevented, and the feel of makeup is sustained.

The present invention comprises the following components (A), (B), (C) and (D):
(A) 0.1 to 25% by mass of a non-volatile silicone oil that is incompatible with squalane,
(B) silicone-based film-forming agent: 2 to 20% by mass;
(C) a volatile oil,
(D) Ester oil 0.1 to 12 mass%
Contains
Component (A) has a viscosity at 25°C of 30 to 100,000 mPa·s,
The present invention relates to a water-in-oil emulsion cosmetic, in which the mass ratio of component (A) to the total content of components (A) and (D), (A)/[(A)+(D)], is 0.3 to 0.95.

The water-in-oil emulsion cosmetic of the present invention is characterized by its excellent durability of makeup feel, the brightness of the skin immediately after application and the uniform finish that are maintained even after a long period of time, the shine caused by sebum is suppressed, and the makeup does not come off even when the made-up skin is touched with a towel. Here, the makeup feel refers to a natural finish with sufficient covering power and a transparent feel.

The component (A) used in the present invention is a non-volatile silicone oil that is incompatible with squalane.
The term "non-volatile" refers to an oil agent that has a mass loss of 1% or less after 1 g of the oil agent is spread on a glass petri dish having a diameter of 48 mm and left for 24 hours at normal pressure at 25° C. The silicone oil may be a linear silicone oil such as dimethylpolysiloxane, or a modified silicone having a substituent such as phenyl-modified silicone or methylhydrogenpolysiloxane.
In addition, the term "not compatible with squalane" means that when silicone oil and squalane are mixed in a mass ratio of 1:1, and stirred and mixed by hand with a stroke count of 120 times/min and a stroke width of 30 cm for 30 seconds, then further stirred with a vortex mixer for 30 seconds, and then allowed to stand for 1 minute, and the state is observed, and the mixture becomes cloudy. Such silicone oil separates into two layers over time.

It is preferable that component (A) contains at least dimethylpolysiloxane, as this is incompatible with squalane, which allows the cosmetic feel to last, maintains the brightness of the skin immediately after application even after the passage of time, and provides a uniform finish without unevenness.

In addition, the viscosity of component (A) at 25° C. is preferably 30 to 100,000 mPa·s, more preferably 30 to 50,000 mPa·s, more preferably 50 to 10,000 mPa·s, even more preferably 100 to 5,000 mPa·s, and even more preferably 150 to 3,000 mPa·s, in order to suppress shine caused by sebum even over a long period of time and to prevent makeup from being removed even when a towel is brought into contact with the made-up skin. In addition, the viscosity of component (A) at 25° C. is preferably 100 to 50,000 mPa·s in order to maintain a feeling of makeup, maintain the brightness of the skin immediately after application even after the passage of time, provide a uniform finish without unevenness, and prevent makeup from being removed even when a towel is brought into contact with the made-up skin.
The viscosity here is measured at 25° C. using a B-type viscometer (TVB-10 model, manufactured by Toki Sangyo Co., Ltd., measurement conditions: rotors TM1 to TM4, 6 rpm, 1 minute). Viscosities of 30 to 1000 mPa·s are measured using TM1, those of 1000 to 5000 mPa·s using TM2, those of 5000 to 20000 mPa·s using TM3, and those of 20000 to 100000 mPa·s using TM4.

One or more types of component (A) can be used, and since it is incompatible with squalane, the cosmetic feel is sustained, the brightness of the skin immediately after application is sustained even after the passage of time, and a uniform finish is obtained without unevenness. Therefore, the content is 0.1% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, and is 25% by mass or less, preferably 20% by mass or less, and more preferably 13% by mass or less in the total composition. The content of component (A) is 0.1 to 25% by mass, preferably 1 to 20% by mass, and more preferably 2 to 13% by mass in the total composition.

As the silicone film-forming agent of component (B), any of those typically used in cosmetics can be used, and those that are solid at 25°C are preferred.
Examples of the film-forming agent of component (B) include trimethylsiloxysilicate, fluorine-modified silicone resin, and acrylic silicone resin.

Of the components (B), component (B-1) trimethylsiloxysilicate is not limited as long as it is one that is commonly used in cosmetics, and is preferably a compound having a crosslinked structure with a siloxane structure as the main skeleton and expressed as [( _CH3 ) _{3SiO1 / 2} ] _a [SiO2] _b (a is 1 to 3, b is 0.5 to 8).
From the viewpoint of cosmetic durability and finish, the component (B-1) trimethylsiloxysilicate is preferably one having a mass average molecular weight of 1000 to 10000, more preferably one having 2000 to 9000, and even more preferably one having 3000 to 6000. The state of the trimethylsiloxysilicate may be any of liquid, gum, paste, solid, etc. at 25°C, but from the viewpoint of cosmetic durability and finish, a solid state is preferable. From the viewpoint of blendability, the trimethylsiloxysilicate may be a solution or dispersion diluted with a solvent, or may be used in the form of a solution or dispersion obtained by mixing in advance. The solvent for dilution or dispersion is preferably one or more selected from dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and isododecane, and more preferably volatile dimethylpolysiloxane and decamethylcyclopentasiloxane. Volatile means that the flash point is 35 to 87°C.

As commercially available products of component (B-1), those that have been dissolved in a solvent in advance can be used, such as KF-7312J (50% solids solution in decamethylcyclopentasiloxane), KF-9021 (50% solution in decamethylcyclopentasiloxane), X21-5249 (50% solution in decamethylcyclopentasiloxane) (all manufactured by Shin-Etsu Chemical Co., Ltd.), SS4267 (35% solution in dimethylpolysiloxane), SR1000 (all manufactured by Momentive Performance Materials Japan, LLC), BY11-018 (30% solution in cyclopentasiloxane) (manufactured by Dow Corning Toray Silicone Co., Ltd.), and BELSIL TMS 803 (manufactured by Wacker Chemie AG).

Among the components (B), the component (B-2) fluorine-modified silicone resin is a silicone resin represented by the general formula (1):
R ¹ _a SiO _(4-a)/2 (1)
(wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a functional group having the general formula -R ² -Rf (R ² is a divalent alkylene group having 2 to 6 carbon atoms, and Rf is a perfluoroalkyl group having 1 to 8 carbon atoms), selected arbitrarily from a hydroxyl group and a functional group having the general formula -R ² -Rf as an essential component, and a is an average number satisfying 1.0≦a≦1.8.)
Preferably, the compound has a structure represented by the following formula:
From the viewpoint of adhesion to the skin, the fluorine-modified silicone resin has silanol groups in the molecule, and the proportion of OH groups in the silanol groups is preferably 0.1 to 5 mass %, more preferably 0.5 to 5 mass %, based on the mass of the resin.

Component (B-2) is preferably a solid at 25°C, and from the viewpoint of compatibility, it may be a solution or dispersion diluted with a solvent, or may be used in the form of a solution or dispersion obtained by mixing in advance. As a solvent for dilution or dispersion, it is preferable to dissolve in cyclic silicone, dimethylpolysiloxane, etc., and use it. As a cyclic silicone, it is preferable to dissolve in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).
As such a fluorine-modified silicone resin, commercially available products such as XS66-B8226, XS66-C1191, and XS66-B8636 (all manufactured by Momentive Performance Materials, Inc.), which have the INCI name "Trifluoropropyldimethyl/Trimethylsiloxysilicate", can be used.

Among the components (B), the component (B-3) acrylic silicone resin includes vinyl polymers having a carbosiloxane dendrimer structure in the side chain, and acrylic-silicone graft copolymers.
Examples of vinyl polymers having a carbosiloxane dendrimer structure in the side chain include silicone dendrimer-acrylic copolymers, which can be produced according to the production methods described in, for example, JP-A Nos. 11-1530 and 2000-63225.
The number average molecular weight of the vinyl polymer having a carbosiloxane dendrimer structure used in the present invention is preferably from 3,000 to 2,000,000, and more preferably from 5,000 to 800,000, from the standpoint of cosmetic durability and finish.
In terms of cosmetic durability and finish, the property is preferably a solid state. The vinyl polymer having a carbosiloxane dendrimer structure can be blended in a solid state, but can also be dissolved in a solvent before use. Examples of the solvent include silicone oil and hydrocarbon oil, and one or more selected from dimethylpolysiloxane, decamethylcyclopentasiloxane, and isododecane can be used.

As a vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain, a silicone dendrimer-acrylic copolymer is preferred, and the cosmetic display name "(Acrylates/Polytrimethylsiloxymethacrylate) Copolymer" (INCI name "Acrylates/Polytrimethylsiloxymethacrylate Copolymer") is preferred, and commercially available products such as FA4001CM (30% by weight decamethylcyclopentasiloxane solution) and FA4002ID (40% by weight isododecane solution) (both manufactured by Dow Corning Toray Co., Ltd.) that have been dissolved in a solvent in advance can be used.

The acrylic-silicone graft copolymer is a radical polymer of an organopolysiloxane compound having a radically polymerizable group at one end of the molecular chain and a radically polymerizable monomer mainly composed of acrylate and/or methacrylate. For example, those described in JP-A-2-25411 and JP-A-2-132141, and acrylic-silicone graft copolymers described in JP-A-3-162442 and JP-A-2003-104825 can be used.

The acrylic-silicone graft copolymer is preferably one with the cosmetic labeling name "Acrylates/Dimethicone Copolymer" (INCI name "Acrylates/Dimethicone Copolymer"), and commercially available products such as KP545 (30% by weight decamethylcyclopentasiloxane solution), KP549 (40% by weight methyltrimethicone solution), and KP550 (40% by weight isododecane solution) (all manufactured by Shin-Etsu Chemical Co., Ltd.) that have been dissolved in a solvent in advance can be used.

Component (B) preferably contains one or more selected from trimethylsiloxysilicate, fluorine-modified silicone resin, and vinyl polymer having a carbosiloxane dendrimer structure in the side chain, and more preferably contains one or more selected from trimethylsiloxysilicate and fluorine-modified silicone resin, in order to form a film on the skin and suppress shine caused by sebum even over a long period of time.

One or more types of component (B) can be used, and since shine caused by sebum is suppressed even over a long period of time and makeup is not removed even when a towel is brought into contact with the made-up skin, the content is preferably 0.5% by mass or more in the total composition, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 2.3% by mass or more, even more preferably 2.6% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. The content of component (B) in the total composition is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, even more preferably 2.3 to 8% by mass, and even more preferably 2.6 to 8% by mass.

In the present invention, the mass ratio (B)/(A) of component (B) to component (A) is preferably 0.06 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and preferably 10 or less, more preferably 4 or less, and even more preferably 2.4 or less, in order to form a coating that repels sebum. In addition, the mass ratio (B)/(A) of component (B) to component (A) is preferably 0.06 to 10, more preferably 0.2 to 4, and even more preferably 0.3 to 2.4.

In the volatile oil of component (C), volatile means that it has a flash point of 35 to 87°C.
Volatile oils include volatile silicone oils and volatile hydrocarbon oils.
Examples of volatile silicone oils include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1cs), dimethylpolysiloxane (1.5cs), and dimethylpolysiloxane (2cs); branched siloxanes such as methyltrimethicone, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
Of these, linear dimethylpolysiloxane and cyclic dimethylpolysiloxane are preferred, and linear dimethylpolysiloxane is more preferred, since they provide a uniform finish on the skin immediately after application.

Examples of volatile hydrocarbon oils include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; and cyclic paraffinic hydrocarbon oils such as cyclodecane and cyclododecane. Of these, hydrocarbon oils with 8 to 16 carbon atoms are preferred, hydrocarbon oils with 10 to 16 carbon atoms are more preferred, and hydrocarbon oils with 12 carbon atoms are even more preferred.

The volatile oil of component (C) preferably contains a volatile silicone oil, and more preferably contains linear dimethylpolysiloxane, in order to obtain a uniform finish on the skin immediately after application.

One or more types of component (C) can be used, and in order to obtain a uniform finish on the skin immediately after application, the content is preferably 5% by mass or more in the total composition, more preferably 15% by mass or more, even more preferably 25% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The content of component (C) is preferably 5 to 50% by mass in the total composition, more preferably 15 to 40% by mass, and even more preferably 25 to 35% by mass.

The ester oil of component (D) is not limited as long as it is one that is commonly used in cosmetics, but non-volatile ester oils are preferred. Here, "non-volatile" means that it does not have a flash point between 35 and 87°C, and is preferably liquid or pasty and fluid at 25°C.

Examples of such ester oils include isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, tricyclodecane methyl isononanoate, hexyl laurate, octyldodecyl malate, cetyl 2-ethylhexanoate, 2-hexyldecyl 2-ethylhexanoate, isopropyl myristate, 2-hexyldecyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, ethyl isostearate, isopropyl isostearate, isostearate, Monoester oils such as isobutyl phosphate, 2-hexyldecyl isostearate, 2-ethylhexyl hydroxystearate, octyldodecyl oleate, oleyl oleate, octyldodecyl ricinoleate, octyl paramethoxycinnamate, and propylene carbonate; di-2-hexylhexyl succinate, bis-ethoxydiglycol succinate, di(caprylic/capric)propanediol, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, and diisostearic acid Diester oils such as polyglyceryl, propanediol diisostearate, diisostearyl malate, di(phytosteryl/octyldodecyl) lauroyl glutamate, di(cholesteryl/behenyl/octyldodecyl) lauroyl glutamate, di(octyldodecyl/phytosteryl/behenyl) lauroyl glutamate, neopentyl glycol di-2-ethylhexanoate, and neopentyl glycol dioctanoate; trimethylolpropane triisostearate, glyceryl triisostearate, triisostearyl Triester oils such as diglyceryl phosphate, jojoba oil, trimethylolpropane tri-2-hexylhexanoate, glyceryl tri-2-ethylhexanoate, tri(caprylic/capric acid)glyceryl, trioctanoate, tritridecyl trimellitate, macadamia nut oil, olive oil, castor oil, jojoba oil, avocado oil, and sunflower oil; pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, and pentaerythritol tetraisostearate.

Of these, in order to make component (B) into a coating that has excellent skin-fitting properties, monoester oil, diester oil, and triester oil are preferred, monoester oil is more preferred, octyl paramethoxycinnamate and isononyl isononanoate are even more preferred, and those containing at least octyl paramethoxycinnamate are even more preferred.

One or more types of component (D) can be used, and in order to make component (B) into a coating that has excellent skin conformability, the content is 0.1% by mass or more in the total composition, preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and 12% by mass or less, preferably 8% by mass or less, and more preferably 6% by mass or less. The content of component (D) is 0.1 to 12% by mass in the total composition, preferably 0.5 to 8% by mass, and more preferably 1.5 to 6% by mass.

In the present invention, the mass ratio (A)/[(A)+(D)] of component (A) to the total content of components (A) and (D) is 0.3 or more, preferably 0.36 or more, more preferably 0.42 or more, and 0.95 or less, preferably 0.8 or less, and more preferably 0.72 or less, in order to form a coating that repels sebum, thereby sustaining the feeling of makeup, sustaining the brightness of the skin immediately after application even after the passage of time, obtaining a uniform finish without unevenness, suppressing shine due to sebum even after a long period of time, and preventing makeup from coming off even when a towel is brought into contact with the skin with makeup. In addition, the mass ratio (A)/[(A)+(D)] of component (A) to the total content of components (A) and (D) is 0.3 to 0.95, preferably 0.36 to 0.8, and more preferably 0.42 to 0.72.

In the present invention, the mass ratio (B)/[(A)+(D)] of component (B) to the total content of components (A) and (D) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and preferably 5 or less, more preferably 3 or less, and even more preferably 1.6 or less, because the composition forms a coating that repels sebum, thereby maintaining the feeling of makeup, maintaining the brightness of the skin immediately after application even after the passage of time, providing a uniform finish without unevenness, suppressing shine caused by sebum even after a long period of time, and preventing makeup from coming off even when a towel is brought into contact with the makeup-covered skin. The mass ratio (B)/[(A)+(D)] of component (B) to the total content of components (A) and (D) is preferably 0.05 to 5, more preferably 0.1 to 3, and even more preferably 0.2 to 1.6.

The water-in-oil emulsion cosmetic of the present invention may further contain (E) a nonionic surfactant, which is preferable because it provides excellent cosmetic durability and an even finish after application to the skin.
The nonionic surfactant of component (E) is not limited as long as it is one that is used in ordinary cosmetics, and examples thereof include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, alkyl glyceryl ether-modified silicones, polyether-modified silicones, polyoxyalkylene-alkyl co-modified silicones, polyoxyalkylene-fluoroalkyl co-modified silicones, and the like.

Among these, it is preferable to use a polyether-modified silicone, since it provides excellent cosmetic durability and an even finish after application to the skin.
As the polyether-modified silicone, for example, commercially available products such as SH3771M, SH3772M, SH3773M, SH3775M, SH3749, and DC5200 manufactured by Dow Corning Toray Co., Ltd., and KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF6017, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

The nonionic surfactant preferably has an HLB value of 1 or more and 7 or less, more preferably an HLB value of 2 or more and 6 or less, in order to provide excellent cosmetic durability and an even finish after application to the skin.

Here, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of a surfactant, and for nonionic surfactants, it can be calculated by Griffin's formula.
The HLB of a mixed surfactant consisting of two or more nonionic surfactants can be calculated as follows: The HLB of the mixed surfactant is the arithmetic average of the HLB values of each nonionic surfactant based on their blending ratio.

Mixed HLB=Σ(HLBx×Wx)/ΣWx
HLBx indicates the HLB value of nonionic surfactant X.
Wx denotes the weight (g) of the nonionic surfactant X having a value of HLBx.

One or more types of nonionic surfactants may be used as component (E), and in order to provide excellent cosmetic durability and a uniform finish after application to the skin, the content is preferably 0.1% by mass or more in the total composition, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less. The content of component (E) is preferably 0.1 to 8% by mass in the total composition, more preferably 0.3 to 6% by mass, and even more preferably 1 to 4% by mass.

In the present invention, the content of (F) water is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 60% by mass or less, and more preferably 40% by mass or less, in terms of excellent usability. The content of (F) water is preferably 1 to 60% by mass, and more preferably 10 to 40% by mass, in the total composition.

The water-in-oil emulsion cosmetic of the present invention may further contain a coloring pigment.
The color pigments are those used in ordinary cosmetics, such as metal oxides such as titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red ocher, Prussian blue, ultramarine, chromium oxide, and chromium hydroxide, metal complexes such as manganese violet and cobalt titanate, and inorganic pigments such as carbon black; Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 22, and the like. synthetic organic pigments such as Red No. 0, Red 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 405, Red No. 505, Orange No. 203, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 401, Blue No. 1, and Blue No. 404; natural organic pigments such as β-carotene, caramel, and paprika color, and composites of these color pigments, composite pigments combining these color pigments with pearl pigments, etc. Examples of the pearl pigment to be treated include natural or synthetic inorganic powders such as mica, phlogopite, talc, silica, sericite, mica, glass, kaolin, bismuth oxychloride, cerium oxide, calcium sulfate, barium sulfate, magnesium sulfate, and plate-like alumina powder. Specific examples of composite pigments include titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated titanium mica, iron oxide-coated synthetic phlogopite, chromium oxide-coated titanium mica, titanium oxide-coated glass powder, iron oxide-coated glass powder, titanium oxide-containing glass powder, and iron oxide-containing glass powder.
The color pigment is preferably at least one or more selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide, and more preferably contains at least titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide.

These color pigments can be used as they are, or they can be used after being subjected to a hydrophobic treatment.
Examples of the hydrophobic treatment include surface treatments such as silicone treatment, alkyl treatment, alkylsilane treatment, metal soap treatment, water-soluble polymer treatment, amino acid treatment, acylated amino acid treatment, lecithin treatment, organic titanate treatment, polyol treatment, acrylic resin treatment, methacrylic resin treatment, urethane resin treatment, fluorine compound treatment, etc. Among these, from the viewpoint of good adhesion to the skin and suppression of secondary adhesion, it is preferable to include one or more of the silicone treatment, alkylsilane treatment, amino acid treatment, and acylated amino acid treatment, and it is more preferable to include at least a silicone treatment.
The color pigment can be subjected to a hydrophobic treatment by a conventional method.

As the coloring pigment, it is preferable to use one or more selected from hydrophobically treated yellow iron oxide, hydrophobically treated black iron oxide, and hydrophobically treated red iron oxide in combination with hydrophobically treated titanium oxide, and it is more preferable to use one or more selected from silicone-treated yellow iron oxide, silicone-treated black iron oxide, and silicone-treated red iron oxide in combination with silicone-treated titanium oxide.

One or more types of color pigments can be used, and in order to achieve a beautiful makeup effect on the skin, the content is preferably 1% by mass or more in the total composition, more preferably 3% by mass or more, even more preferably 4% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 18% by mass or less. The content of the color pigment is preferably 1 to 30% by mass in the total composition, more preferably 3 to 25% by mass, and even more preferably 4 to 18% by mass.

The water-in-oil emulsion cosmetic of the present invention may contain, in addition to the above-mentioned components, components that are usually used in cosmetics, such as oil components other than those mentioned above, powders, water-soluble polymers, antioxidants, fragrances, colorants, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, germicides, skin activators, moisturizers, and cooling agents.

The water-in-oil emulsion cosmetic of the present invention can be produced according to a conventional method.
The water-in-oil emulsion cosmetic of the present invention can be in the form of a liquid, emulsion, paste, cream, gel, or the like, with emulsion and cream being preferred.

The water-in-oil emulsion cosmetic of the present invention can be used as a makeup base, foundation, concealer, makeup cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc., UV protection cosmetics such as sunscreen lotion, sunscreen cream, etc., skin care cosmetics such as skin care lotion, skin care cream, BB cream, serum, etc. Of these, makeup cosmetics are preferred, and makeup base, liquid foundation, and cream foundation are more preferred.
The water-in-oil emulsion cosmetic of the present invention can be used alone or can be layered with a powder cosmetic such as a liquid foundation, powder foundation, or face powder.

With respect to the above-mentioned embodiment, the present invention further discloses the following composition.

<1> The following components (A), (B), (C) and (D):
(A) 0.1 to 25% by mass of a non-volatile silicone oil that is incompatible with squalane,
(B) silicone-based film-forming agent: 2 to 20% by mass;
(C) a volatile oil,
(D) Ester oil 0.1 to 12 mass%
Contains
Component (A) has a viscosity at 25°C of 30 to 100,000 mPa·s,
A water-in-oil emulsion cosmetic, in which the mass ratio of component (A) to the total content of components (A) and (D), (A)/[(A)+(D)], is 0.3 to 0.95.

<2> The water-in-oil emulsion cosmetic according to the above <1>, wherein the component (A) preferably contains at least dimethylpolysiloxane.
<3> The water-in-oil emulsion cosmetic according to <1> or <2> above, wherein the component (A) has a viscosity at 25°C of preferably 30 to 100,000 mPa·s, more preferably 30 to 50,000 mPa·s, more preferably 50 to 10,000 mPa·s, even more preferably 100 to 5,000 mPa·s, and still more preferably 150 to 3,000 mPa·s.
<4> The water-in-oil emulsion cosmetic according to any one of <1> to <3> above, wherein the content of component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total composition, and is preferably 20% by mass or less, and more preferably 13% by mass or less.

<5> The water-in-oil emulsion cosmetic according to any one of <1> to <4> above, wherein the film-forming agent of component (B) is preferably in a solid state at 25°C.
<6> The water-in-oil emulsion cosmetic according to any one of <1> to <5> above, wherein the film-forming agent of component (B) is preferably trimethylsiloxysilicate, a fluorine-modified silicone resin, or an acrylic silicone resin, and more preferably one or more selected from trimethylsiloxysilicate and a fluorine-modified silicone resin.
<7> The water-in-oil emulsion cosmetic according to any one of <1> to <6>, wherein the component (B) is preferably (B-1) trimethylsiloxysilicate, more preferably represented by [( _CH3 ) _{3SiO1 / 2} ] _a [SiO2] _b (a is 1 to 3, b is 0.5 to 8).
<8> The water-in-oil emulsion cosmetic according to any one of the above <1> to <7>, wherein the component (B) is preferably (B-1) trimethylsiloxysilicate having a mass average molecular weight of 1,000 to 10,000, more preferably 2,000 to 9,000, and even more preferably 3,000 to 6,000.

<9> The component (B) is preferably a fluorine-modified silicone resin (B-2) represented by the general formula (1):
R ¹ _a SiO _(4-a)/2 (1)
(wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a functional group having the general formula -R ² -Rf (R ² is a divalent alkylene group having 2 to 6 carbon atoms, and Rf is a perfluoroalkyl group having 1 to 8 carbon atoms), selected arbitrarily from a hydroxyl group and a functional group having the general formula -R ² -Rf as an essential component, and a is an average number satisfying 1.0≦a≦1.8.)
The water-in-oil emulsion cosmetic according to any one of the above items <1> to <8>, wherein the compound having the structure represented by the following formula (I) is more preferable, and trifluoropropyldimethyl/trimethylsiloxysilicate is even more preferable.
<10> The water-in-oil emulsion cosmetic according to any one of the above <1> to <9>, wherein the component (B) is preferably (B-3) an acrylic silicone resin, more preferably a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, or an acrylic-silicone graft copolymer.

<11> The water-in-oil emulsion cosmetic according to any one of <1> to <10> above, wherein the content of component (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, still more preferably 2.3% by mass or more, even more preferably 2.6% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, based on the total composition.
<12> The water-in-oil emulsion cosmetic according to any one of the above <1> to <11>, wherein the mass ratio (B)/(A) of the component (B) to the component (A) is preferably 0.06 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and is preferably 10 or less, more preferably 4 or less, and even more preferably 2.4 or less.

<13> The water-in-oil emulsion cosmetic according to any one of the above <1> to <12>, wherein the volatile oil of component (C) is preferably a volatile silicone oil or a volatile hydrocarbon oil, more preferably contains a volatile silicone oil, and further preferably contains a linear dimethylpolysiloxane.
<14> The water-in-oil emulsion cosmetic according to any one of <1> to <13>, wherein the content of component (C) is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 25% by mass or more, of the total composition, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

<15> The water-in-oil emulsion cosmetic according to any one of <1> to <14> above, wherein the ester oil of component (D) is preferably a non-volatile ester oil, more preferably a monoester oil, a diester oil, or a triester oil, still more preferably a monoester oil, still more preferably octyl paramethoxycinnamate or isononyl isononanoate, and still more preferably contains at least octyl paramethoxycinnamate.
<16> The water-in-oil emulsion cosmetic according to any one of <1> to <15>, wherein the content of component (D) is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, based on the total composition, and is preferably 8% by mass or less, and more preferably 6% by mass or less.
<17> The water-in-oil emulsion cosmetic according to any one of the above <1> to <16>, wherein the mass ratio (A)/[(A)+(D)] of the component (A) to the total content of the components (A) and (D) is preferably 0.36 or more, more preferably 0.42 or more, and is preferably 0.8 or less, and more preferably 0.72 or less.
<18> The water-in-oil emulsion cosmetic according to any one of the above <1> to <17>, wherein the mass ratio (B)/[(A)+(D)] of the component (B) to the total content of the components (A) and (D) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 1.6 or less.

<19> The water-in-oil emulsion cosmetic according to any one of the above <1> to <18>, further comprising (E) a nonionic surfactant.
<20> The water-in-oil emulsion cosmetic according to the above item <19>, wherein the nonionic surfactant of the component (E) preferably contains a polyether-modified silicone.
<21> The water-in-oil emulsion cosmetic according to the above item <19> or <20>, wherein the nonionic surfactant of component (E) preferably has an HLB value of 1 or more and 7 or less, more preferably an HLB value of 2 or more and 6 or less.
<22> The water-in-oil emulsion cosmetic according to any one of <19> to <21>, wherein the content of component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 1% by mass or more, of the total composition, and is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less.
<23> The water-in-oil emulsion cosmetic according to any one of <1> to <22>, wherein the content of (F) water is preferably 1% by mass or more, more preferably 10% by mass or more, based on the total composition, and is preferably 60% by mass or less, and more preferably 40% by mass or less.

<24> The water-in-oil emulsion cosmetic according to any one of the above <1> to <23>, wherein the component (A) preferably has a viscosity at 25° C. of 100 to 50,000 mPa·s.
<25> The water-in-oil emulsion cosmetic according to any one of the above <1> to <24>, further comprising preferably a coloring pigment, and more preferably a coloring pigment that has been subjected to a hydrophobic treatment.

<26> The water-in-oil emulsion cosmetic according to any one of the above <1> to <25>, wherein the content of component (A) is 1 to 20 mass% of the total composition, the content of component (B) is 2 to 20 mass% of the total composition, the content of component (D) is 0.5 to 8 mass% of the total composition, and the mass ratio of component (A) to the total content of components (A) and (D), (A)/[(A)+(D)], is 0.36 to 0.8.
<27> The water-in-oil emulsion cosmetic according to any one of the above <1> to <26>, wherein the content of component (A) is 2 to 13 mass% of the total composition, the content of component (B) is 2 to 8 mass% of the total composition, the content of component (D) is 1.5 to 6 mass% of the total composition, and the mass ratio of component (A) to the total content of components (A) and (D), (A)/[(A)+(D)], is 0.42 to 0.72.

<28> The water-in-oil emulsion cosmetic according to any one of the above <1> to <25>, wherein the content of component (A) is 0.1 to 25% by mass in the total composition, the content of component (B) is 2 to 20% by mass in the total composition, the content of component (D) is 0.1 to 12% by mass in the total composition, and the mass ratio of component (B) to the total content of components (A) and (D), (B)/[(A)+(D)], is 0.05 to 5.
<29> The water-in-oil emulsion cosmetic according to any one of the above <1> to <28>, wherein the content of component (A) is 2 to 13 mass% of the total composition, the content of component (B) is 2 to 8 mass% of the total composition, the content of component (D) is 1.5 to 6 mass% of the total composition, and the mass ratio of component (B) to the total content of components (A) and (D), (B)/[(A)+(D)], is 0.2 to 1.6.

<30> The following components (A), (B), (C) and (D):
(A) 0.1 to 25% by mass of a non-volatile silicone oil having a viscosity at 25° C. of 30 to 100,000 mPa s and incompatible with squalane,
(B) silicone-based film-forming agent: 2 to 20% by mass;
(C) a volatile oil,
(D) Ester oil 0.1 to 12 mass%
and (D) so that the mass ratio of component (A) to the total content of components (A) and (D) is 0.3 to 0.95 (A/[(A)+(D)]).

Examples 1 to 10, Comparative Examples 1 to 3
Water-in-oil emulsion cosmetics having the compositions shown in Table 1 were prepared and applied to the skin, and after 8 hours, the absence of shine due to sebum, the absence of secondary adhesion to a towel, the brightness of the skin, and the evenness of the skin were evaluated. The results are also shown in Table 1.
The dimethylpolysiloxane used in the examples was mixed with squalane in a mass ratio of 1:1, stirred by hand at a stroke frequency of 120 strokes/min and a stroke width of 30 cm for 30 seconds, and then further stirred in a vortex mixer for an additional 30 seconds. The state (whether the mixture was compatible with squalane) of the mixture after being allowed to stand for 1 minute is shown in Table 2.

(Production method)
The powder phase components were mixed and ground, added to a separately mixed oil phase component, and dispersed using a disperser. The aqueous phase components were then added, dispersed using a disperser, and stirred using a homomixer to obtain a water-in-oil emulsion cosmetic (foundation).

(Evaluation Method)
(1) Absence of greasiness caused by sebum after 8 hours of application to skin:
Each foundation was applied to the skin by five expert panelists, and after 8 hours, the resistance to greasiness caused by sebum was evaluated according to the following criteria. The results were expressed as the total score of the five panelists.
5: No greasiness due to sebum at all.
4: No shine caused by sebum.
3: Not much shine caused by sebum.
2: There is some shine due to sebum.
1: There is greasiness due to sebum.

(2) Lack of secondary adhesion to a towel after 8 hours from application to the skin:
Each foundation was applied to the skin by five expert panelists, and eight hours after application, the absence of color transfer of the foundation when a cotton towel was pressed against the skin was evaluated according to the following criteria. The results were expressed as the total score of the five panelists.
5: After applying the foundation, when I press a towel against my skin, none of the foundation comes off.
4: Even when I press a towel against my skin after applying the foundation, no foundation comes off.
3: Even when I press a towel against my skin after applying the foundation, not much of it comes off.
2: When you press a towel against your skin after applying the foundation, some of it sticks to it.
1: After applying the foundation, press a towel against your skin and the foundation will stick to it.

(3) Skin brightness after 8 hours of application:
Each foundation was applied to the skin by five expert panelists, and the brightness of the made-up skin 8 hours after application was evaluated according to the following criteria. The results were shown as the total score given by the five panelists.
5: Make-up skin looks brighter.
4: The made-up skin looks slightly brighter.
3: The made-up skin doesn't look very bright.
2: The made-up skin does not look bright.
1: My made-up skin doesn't look bright at all.

(4) Evenness of skin after 8 hours of application:
Each foundation was applied to the skin by five expert panelists, and the evenness of the made-up skin 8 hours after application was evaluated according to the following criteria. The results were expressed as the total score of the five panelists.
5: The made-up skin looks even.
4: The makeup looks somewhat uniform.
3: The makeup doesn't look very even.
2: The makeup doesn't look even.
1: The made-up skin does not look uniform at all.

Examples 11 to 14
In the same manner as in Examples 1 to 10, water-in-oil emulsion cosmetics (foundations) having the compositions shown in Table 3 were produced.
All of the obtained foundations were applied to the skin, and even after 8 hours, there was no shine due to sebum, and the foundation did not stick to the skin even when a towel was pressed against the skin, leaving the skin looking bright and even.

Claims (9)

The following components (A), (B), (C) and (D):
(A) 0.1 to 25% by mass of a non-volatile silicone oil that is incompatible with squalane,
(B) silicone-based film-forming agent: 2 to 20% by mass;
(C) a volatile oil containing at least a linear dimethylpolysiloxane ;
(D) Ester oil 0.1 to 12 mass%
Contains
Component (A) has a viscosity at 25°C of 30 to 100,000 mPa·s,
A water-in-oil emulsion cosmetic, in which the mass ratio of component (A) to the total content of components (A) and (D), (A)/[(A)+(D)], is 0.3 to 0.95. The water-in-oil emulsion cosmetic according to claim 1, wherein component (A) has a viscosity of 100 to 50,000 mPa·s at 25°C. The water-in-oil emulsion cosmetic according to claim 1 or 2, wherein component (A) contains at least dimethylpolysiloxane. The water-in-oil emulsion cosmetic according to any one of claims 1 to 3, wherein component (B) is one or more selected from trimethylsiloxysilicate and fluorosilicone resins. The water-in-oil emulsion cosmetic according to any one of claims 1 to 4, wherein the content of component (B) is 0.5 to 20 mass%. The water-in-oil emulsion cosmetic according to any one of claims 1 to 5 , wherein the content of component (C) is 5 to 50 mass %. 7. The water-in-oil emulsion cosmetic according to any one of claims 1 to 6 , wherein the mass ratio of component (B) to the total content of components (A) and (D), (B)/[(A)+(D)], is 0.05 to 5. The water-in-oil emulsion cosmetic according to any one of claims 1 to 7 , wherein component (D) contains at least octyl paramethoxycinnamate. The water-in-oil emulsion cosmetic according to any one of claims 1 to 8 , further comprising (E) a nonionic surfactant.