WO2021095712A1

WO2021095712A1 - Water-in-oil emulsified cosmetic

Info

Publication number: WO2021095712A1
Application number: PCT/JP2020/041851
Authority: WO
Inventors: 智典福地; 廉十川; 亮介藤井; 美香子渡邉; 舞斗為行
Original assignee: 花王株式会社
Priority date: 2019-11-14
Filing date: 2020-11-10
Publication date: 2021-05-20
Also published as: JP2021080247A; TW202122067A; CN114727942A; KR20220082875A

Abstract

Provided is a water-in-oil emulsified cosmetic containing the following components (A), (B), (C), and (D): (A) non-volatile silicone oil which is incompatible with squalane, in an amount of 0.1-25 mass%; (B) a silicone-based film forming agent in an amount of 2-20 mass%; (C) volatile oil; and (D) ester oil in an amount of 0.1-12 mass%, wherein the component (A) has a viscosity of 30-100000 mPa·s at 25ºC, and the mass ratio (A)/[(A)+(D)] of the component (A) content to the total of the component (A) content and the component (D) content is 0.3-0.95.

Description

Water-in-oil emulsified cosmetics

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

Water-in-oil emulsified cosmetics such as foundations are required to have excellent make-up durability, non-greasyness, and good usability.
For example, in Patent Document 1, a water-in-oil emulsified cosmetic containing a surface-treated pigment, volatile oil, water, organic silicone resin, and nonionic surfactant maintains a fresh feel without stickiness. However, it is described that a uniform finish can be obtained.

(Patent Document 1) Japanese Unexamined Patent Publication No. 2019-99468

In the present invention, the following components (A), (B), (C) and (D):
(A) Non-volatile silicone oil incompatible with squalane 0.1 to 25% by mass,
(B) Silicone-based film forming agent 2 to 20% by mass,
(C) Volatile oil,
(D) Ester oil 0.1-12% by mass
Contains,
The component (A) has a viscosity at 25 ° C. of 30 to 100,000 mPa · s.
Water-in-oil emulsified makeup in which the mass ratio (A) / [(A) + (D)] of the component (A) to the total content of the components (A) and (D) is 0.3 to 0.95. Regarding charges.

Detailed description of the invention

The present inventors have found that an emulsified cosmetic containing a silicone-based film-forming agent, a volatile oil, and an ester oil has excellent makeup durability, but has a problem that makeup can be easily removed over time.

By using a specific non-volatile silicone oil and an ester oil in a specific ratio in a water-in-oil emulsified cosmetic containing a silicone-based film-forming agent and a volatile oil, the present inventors have applied the skin immediately after application. It was found that the brightness of the oil is maintained, a uniform finish is obtained, and even after a long period of time, the makeup is not shiny, the makeup is suppressed, and the makeup feeling is maintained.

The water-in-oil emulsified cosmetic of the present invention has excellent long-lasting cosmetic feeling, maintains the brightness and uniform finish of the skin immediately after application even after a long period of time, suppresses the shine caused by sebum, and makes the makeup skin. The feature is that the makeup cannot be removed even if the towel is brought into contact with the skin. Here, the cosmetic feeling means a natural finish with sufficient covering power and a transparent feeling.

The component (A) used in the present invention is a non-volatile silicone oil that is incompatible with squalane.
Non-volatile means that 1 g of an oil agent is spread on a glass petri dish having a diameter of 48 mm and the mass loss rate is 1% or less after being left at 25 ° C. and normal pressure for 24 hours. 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, incompatible with squalane means that silicone oil and squalane are mixed at a mass ratio of 1: 1 and held by hand with a stroke count of 120 times / minute and a stroke width of 30 cm, stirred and mixed for 30 seconds, and then further vortex mixer. When the mixture is stirred for 30 seconds and allowed to stand for 1 minute and the state is observed, the state becomes cloudy. Such silicone oil separates into two layers over time.

As the component (A), since it is incompatible with squalane, the cosmetic feeling is maintained, the brightness of the skin immediately after application is maintained even after a lapse of time, and an even and uniform finish can be obtained. It preferably contains at least dimethylpolysiloxane.

In addition, the component (A) has a viscosity at 25 ° C. of 30 to 100,000 mPa · s because the shine caused by sebum is suppressed even after a long period of time and the makeup cannot be removed even if the towel is brought into contact with the makeup skin. It is preferably 30,000 to 50,000 mPa · s, more preferably 50 to 10000 mPa · s, even more preferably 100 to 5000 mPa · s, and even more preferably 150 to 3000 mPa · s. In addition, the makeup feeling lasts, the brightness of the skin immediately after application is maintained even after a lapse of time, an even and uniform finish can be obtained, and even if the towel is brought into contact with the makeup skin, the makeup cannot be removed. , The viscosity at 25 ° C. is preferably 100 to 50,000 mPa · s.
The viscosity here is measured at 25 ° C. with a B-type viscometer (TVB-10 type, manufactured by Toki Sangyo Co., Ltd., measurement conditions: rotors TM1 to TM4, 6 rpm, 1 minute). The viscosity of 30 to 1000 mPa · s is measured by TM1, 1000 to 5000 mPa · s is measured by TM2, 5000 to 20000 mPa · s is measured by TM3, and 20000 to 100,000 mPa · s is measured by TM4.

As the component (A), one type or two or more types can be used, and by not being compatible with squalane, the cosmetic feeling is maintained, and the brightness of the skin immediately after application is maintained even after a lapse of time. From the viewpoint of obtaining an even and uniform finish, the content is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and 25% by mass or less in the entire composition. 20% by mass or less is preferable, and 13% by mass or less is more preferable. The content of the component (A) is 0.1 to 25% by mass in the total composition, preferably 1 to 20% by mass, and more preferably 2 to 13% by mass.

As the silicone-based film-forming agent of the component (B), any one usually used for cosmetics can be used, and a solid state at 25 ° C. is preferable.
Examples of the film-forming agent of the component (B) include trimethylsiloxysilicic acid, a fluorine-modified silicone resin, and an acrylic silicone resin.

Among the component (B), the component (B-1) trimethylsiloxysilicic acid is not limited as long as it is used in ordinary cosmetics, and is a compound having a crosslinked structure having a siloxane structure as a main skeleton. (CH ₃ ) ₃ SiO _1/2 ] _a [SiO ₂ ] _b (a is 1 to 3, b is 0.5 to 8) is preferable.
The component (B-1) trimethylsiloxysilicic acid preferably has a mass average molecular weight of 1000 to 10000, more preferably 2000 to 9000, and even more preferably 3000 to 6000, from the viewpoint of makeup retention and finish. Further, the properties may be liquid, gum-like, paste-like, solid-like or the like at 25 ° C., but solid-state ones are preferable from the viewpoint of the obtained makeup lasting and finish. Further, from the viewpoint of compoundability, it can be used as a solution or dispersion diluted with a solvent, or as a solution or dispersion obtained by mixing in advance. As the solvent to be diluted or dispersed, one or more selected from dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and isododecane are preferable, and volatile dimethylpolysiloxane and decamethylcyclopentasiloxane are used. More preferred. Volatile means having a flash point of 35 to 87 ° C.

Commercially available products of the component (B-1) are those previously dissolved in a solvent, and include KF-7312J (50% solid content decamethylcyclopentasiloxane solution) and KF-9021 (50% decamethylcyclopentasiloxane solution). , X21-5249 (50% decamethylcyclopentasiloxane solution) (above, manufactured by Shinetsu Chemical Industry Co., Ltd.), SS4267 (35% dimethylpolysiloxane solution), SR1000 (above, manufactured by Momentive Performance Materials Japan GK) , BY11-018 (30% cyclopentasiloxane solution) (manufactured by Toray Dow Corning Silicone), BEALSIL TMS 803 (manufactured by Wacker Chemie AG), and the like can be used.

Of the component (B), the component (B-2) fluorine-modified silicone resin has the general formula (1).
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group or a general formula-R ^2- Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf is a carbon. a showing a perfluoroalkyl group having 1 to 8), arbitrarily chosen a hydroxyl group and the general formula -R ² -Rf from the functional groups as an essential, 1.0 ≦ a ≦ 1 a is an average number. 8)
Those having a structure represented by are preferable.
The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to the skin, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass with respect to the resin mass. It is preferably 0.5 to 5% by mass, more preferably 0.5 to 5% by mass.

The component (B-2) is preferably a solid at 25 ° C., and from the viewpoint of compoundability, it may be a solution or dispersion diluted with a solvent, or a solution or dispersion obtained by mixing in advance. It can also be used in the state. As the solvent to be diluted or dispersed, it is preferable to use it by dissolving it in cyclic silicone, dimethylpolysiloxane or the like. As the cyclic silicone, it is preferable to dissolve it in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).
Examples of such a fluorine-modified silicone resin include XS66-B8226, XS66-C1191 and XS66-B8636 (hereinafter referred to as Momentive Performance Materials), which have INCI names of "Trifluoropropyldimethyl / Trimethylsiloxysilicate". Commercially available products such as (manufactured by the company) can be used.

Among the component (B), examples of the component (B-3) acrylic silicone resin include a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, an acrylic-silicone graft copolymer, and the like.
Examples of the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain include a silicone dendrimer / acrylic copolymer and the like, and are described in, for example, JP-A-11-1530 and JP-A-2000-63225. It can be manufactured according to a manufacturing method.
The number average molecular weight of the vinyl-based polymer having the carbosiloxane dendrimer structure used in the present invention is preferably 3,000 to 2,000,000, preferably 5,000 to 800, from the viewpoint of makeup retention and finish. 000 is more preferable.
Further, the property is preferably solid from the viewpoint of long-lasting makeup and finish. Further, the vinyl-based polymer having a carbosiloxane dendrimer structure can be blended in a solid state, but can also be used by dissolving it in a solvent. Examples of the solvent include silicone oil and hydrocarbon oil, and one or more selected from dimethylpolysiloxane, decamethylcyclopentasiloxane, and isododecane can be used.

As the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain, a silicone dendrimer / acrylic copolymer is preferable, and the cosmetic labeling name "(Acrylate / Polytrimethylsiloxymethacrylate) copolymer" (INCI name "Acrylates / Polytrimethylsiloxymethacrylate Copolymer") ) Is preferable, and commercially available products such as FA4001CM (30 mass% decamethylcyclopentasiloxane solution) and FA4002ID (40 mass% isododecane solution) (all manufactured by Toray Dow Corning Co., Ltd.) previously dissolved in a solvent 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. This is, for example, those described in JP-A-2-25411, JP-A-2-132141, etc., and acrylics described in JP-A-3-162442, JP-A-2003-104825, etc. A silicone-based graft copolymer can be used.

As the acrylic-silicone graft copolymer, the cosmetic labeling name "(Acrylates / Dimethicone) Copolymer" (INCI name "Acrylates / Dimethicone Copolymer") is preferable, and KP545 (30 mass% decamethylcyclopenta) previously dissolved in a solvent is preferable. Commercial products such as siloxane solution), KP549 (40% by mass methyltrimethicone solution), and KP550 (40% by mass isododecane solution) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) can be used.

As the component (B), trimethylsiloxysilicic acid, a fluorine-modified silicone resin, and a carbosiloxane dendrimer structure are side chains from the viewpoint that a film is formed on the skin and the shine due to sebum is suppressed even after a long period of time. It is preferable to contain one or more selected from the vinyl-based polymers contained in the above, and more preferably one or two or more selected from trimethylsiloxysilicic acid and a fluorine-modified silicone resin.

The component (B) can be used alone or in combination of two or more, and is contained because the shine due to sebum is suppressed even after a long period of time, and the makeup cannot be removed even if the makeup skin is brought into contact with a towel. The amount is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, still more preferably 2.3% by mass or more, and 2.6% by mass in the total composition. % Or more is more preferable, 20% by mass or less is preferable, 10% by mass or less is more preferable, and 8% by mass or less is further preferable. The content of the component (B) is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, further preferably 2 to 8% by mass, and 2.3 to 8% by mass in the total composition. Is even more preferable, and 2.6 to 8% by mass is even more preferable.

In the present invention, the mass ratio (B) / (A) of the component (B) to the component (A) is preferably 0.06 or more, preferably 0.2, from the viewpoint of forming a film that repels sebum. The above is more preferable, 0.3 or more is further preferable, 10 or less is preferable, 4 or less is more preferable, and 2.4 or less is further preferable. The mass ratio (B) / (A) of the component (B) to the 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 the component (C), the volatility is one having a flash point of 35 to 87 ° C.
Examples of the volatile oil include volatile silicone oil and volatile hydrocarbon oil.
Examples of the volatile silicone oil include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1cs), dimethylpolysiloxane (1.5cs), and dimethylpolysiloxane (2cs); methyltrimethicone, tris (trimethylsilyl) methylsilane, and the like. Branched siloxanes such as tetrakis (trimethylsilyl) silane; cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
Of these, linear dimethylpolysiloxane and cyclic dimethylpolysiloxane are preferable, and linear dimethylpolysiloxane is more preferable, from the viewpoint that the skin immediately after application can be obtained with an even and uniform finish.

Examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane and hydrogenated polyisobutene; cyclodecane, cyclododecane and the like. Cyclic paraffin hydrocarbon oil can be mentioned. Of these, a hydrocarbon oil having 8 to 16 carbon atoms is preferable, a hydrocarbon oil having 10 to 16 carbon atoms is more preferable, and a hydrocarbon oil having 12 carbon atoms is further preferable.

The volatile oil of the component (C) preferably contains a volatile silicone oil, and more preferably a linear dimethylpolysiloxane, from the viewpoint of obtaining an even and uniform finish on the skin immediately after application.

As the component (C), one type or two or more types can be used, and the content is 5% by mass or more in the total composition from the viewpoint that the skin immediately after application can be obtained evenly and uniformly. Preferably, 15% by mass or more is more preferable, 25% by mass or more is further preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 35% by mass or less is further preferable. The content of the component (C) is preferably 5 to 50% by mass, more preferably 15 to 40% by mass, and even more preferably 25 to 35% by mass in the total composition.

The ester oil of the component (D) is not limited as long as it is used in ordinary cosmetics, and a non-volatile ester oil is preferable. Here, the non-volatile means those having no flash point at 35 to 87 ° C., and those having fluidity in the form of liquid or paste at 25 ° C. are preferable.

Examples of such ester oils include isononyl isononanoate, isodecyl isononanoate, isotorideyl isononanoate, tricyclodecanemethyl isononanoate, hexyl laurate, octyldodecyl malate, cetyl 2-ethylhexanoate, and 2-ethylhexanoate 2-ethylhexanoate. Hexyldecyl, isopropyl myristate, 2-hexyldecyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, ethyl isostearate, isopropyl isostearate, isobutyl isostearate, 2-hexyldecyl isostearate, hydroxysteer Monoester oils such as 2-ethylhexyl acid, octyldodecyl oleate, oleyl oleate, octyldodecyl ricinoleate, octyl paramethoxysilicate, propylene carbonate; di2-hetylhexyl succinate, bisethoxydiglycol succinate, di (Caprylic acid / capric acid) Propanediol, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, polyglyceryl diisostearate, propanediol diisostearate, diisostearyl malate, di (phytosteryl / octyldodecyl) lauroyl glutamate , Diester oils such as di-lauroyl glutamate (cholesteryl / behenyl / octyldodecyl), di lauroyl glutamate (octyldodecyl / phytosteryl / behenyl), neopentyl glycol di2-ethylhexanoate, neopentyl glycol dioctanoate; trimethyl triisostearate Propane, glyceryl triisostearate, diglyceryl triisostearate, jojoba oil, trimethyl propane tri-2-hetylhexanoate, glyceryl tri2-ethylhexanoate, glyceryl tri (caprylic / capric acid), glyceryl trioctanoate, tridecyl trimeritoate , Macademia nut oil, olive oil, sunflower oil, jojoba oil, avocado oil, sunflower oil and other triester oils; pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, pentaerythrit tetraisostearate, etc. Be done.

Of these, monoester oil, diester oil, and triester oil are preferable, monoester oil is more preferable, and octyl paramethoxycinnamate and isononanoic acid are preferable, because the component (B) forms a film having excellent skin followability. Isononyl is even more preferred, even more preferably containing at least octyl paramethoxycinnamate.

As the component (D), one type or two or more types can be used, and the content of the component (B) is 0.1% by mass or more in the total composition from the viewpoint of forming a film having excellent skin followability. Yes, 0.5% by mass or more is preferable, 1.5% by mass or more is more preferable, 12% by mass or less, 8% by mass or less is preferable, and 6% by mass or less is more preferable. The content of the component (D) is 0.1 to 12% by mass, preferably 0.5 to 8% by mass, and more preferably 1.5 to 6% by mass in the total composition.

In the present invention, the mass ratio (A) / [(A) + (D)] of the component (A) to the total content of the components (A) and (D) is determined by forming a film that repels sebum. The makeup feeling lasts, the brightness of the skin immediately after application is maintained even after a lapse of time, an even and uniform finish is obtained, and even after a long period of time, the shine due to sebum is suppressed and the makeup is made. From the viewpoint that makeup cannot be removed even if the towel is brought into contact with the skin, it is 0.3 or more, preferably 0.36 or more, more preferably 0.42 or more, 0.95 or less, and preferably 0.8 or less. , 0.72 or less is more preferable. The mass ratio (A) / [(A) + (D)] of the component (A) to the total content of the components (A) and (D) is 0.3 to 0.95, which is 0.36. ~ 0.8 is preferable, and 0.42 to 0.72 is more preferable.

In the present invention, the mass ratio (B) / [(A) + (D)] of the component (B) to the total content of the components (A) and (D) is determined by forming a film that repels sebum. The makeup feeling lasts, the brightness of the skin immediately after application is maintained even after a lapse of time, an even and uniform finish is obtained, and even after a long period of time, the shine due to sebum is suppressed and the makeup is made. From the viewpoint that makeup cannot be removed even if the towel is brought into contact with the skin, it is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, preferably 5 or less, and more preferably 3 or less. It is preferable, and 1.6 or less is more preferable. The mass ratio (B) / [(A) + (D)] of the component (B) to the total content of the components (A) and (D) is preferably 0.05 to 5. 1 to 3 is more preferable, and 0.2 to 1.6 is further preferable.

The water-in-oil emulsified cosmetic of the present invention is preferable because it can further contain (E) a nonionic surfactant, has excellent makeup durability after being applied to the skin, and finishes evenly.
The nonionic surfactant of the component (E) is not limited as long as it is used in ordinary cosmetics, and for example, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol. Fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, poly Oxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, alkyl Examples thereof include glyceryl ether-modified silicone, polyethylene-modified silicone, polyoxyalkylene / alkyl co-modified silicone, and polyoxyalkylene / fluoroalkyl co-modified silicone.

Of these, it is preferable to contain a polyether-modified silicone from the viewpoint of excellent cosmetic durability and even finish after application to the skin.
Examples of the polyether-modified silicone include SH3771M, SH3772M, SH3773M, SH3775M, SH3749, DC5200 manufactured by Toray Dow Corning, and KF-6011, KF-6012, KF-6013, KF-6015 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-6016, KF6017, KF-6004 and other commercially available products can be used.

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

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lipophilic 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 types of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is a phase-added 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.

As the nonionic surfactant of the component (E), one type or two or more types can be used, and after application to the skin, the content is 0 in the entire composition from the viewpoint of excellent makeup durability and even finish. .1% by mass or more is preferable, 0.3% by mass or more is more preferable, 1% by mass or more is further preferable, 8% by mass or less is more preferable, 6% by mass or less is more preferable, and 4% by mass or less is further preferable. preferable. The content of the component (E) is preferably 0.1 to 8% by mass, more preferably 0.3 to 6% by mass, and even more preferably 1 to 4% by mass in the total composition.

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

The water-in-oil emulsified cosmetic of the present invention can further contain a coloring pigment.
Color pigments are those used in ordinary cosmetics, such as titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red iron oxide, dark blue, ultramarine blue, chromium oxide, chromium hydroxide, etc. Metal oxides, manganese violet, metal complexes such as 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 205 No., Red No. 220, Red No. 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, Synthetic organic pigments such as Yellow No. 5, Yellow No. 401, Blue No. 1, Blue No. 404; Natural organic pigments such as β-carotene, caramel, paprika pigment, etc. Examples thereof include composite pigments in which pigments and pearl pigments are combined. Examples of the pearl pigment to be treated include mica, phlogopite, talc, silica, sericite, mica, glass, kaolin, bismuth oxychloride, cerium oxide, calcium sulfate, barium sulfate, magnesium sulfate, plate-shaped alumina powder and the like. Examples include natural or synthetic inorganic powders. Specific examples of the composite pigment include titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, iron oxide-coated synthetic gold mica, chromium oxide-coated mica titanium, titanium oxide-coated glass powder, iron oxide-coated glass powder, and oxidation. Examples include titanium-encapsulating glass powder and iron oxide-encapsulating glass powder.
As the coloring pigment, at least one or more selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide is preferable, and at least titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide are more preferable.

These coloring pigments can be used as they are, or hydrophobized coloring pigments can also be used.
Examples of the hydrophobizing treatment include 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, and the like. Surface treatments such as methacrylic resin treatment, urethane resin treatment, and fluorine compound treatment can be mentioned. Among them, from the viewpoint of good adhesion to the skin and suppressing secondary adhesion, it is preferable to include one or more types of silicone treatment, alkylsilane treatment, amino acid treatment, and acylated amino acid treatment, and at least silicone treatment is performed. It is more preferable to include it.
The hydrophobizing treatment of the coloring pigment can be carried out by a usual method.

As the coloring pigment, one or more selected from hydrophobized yellow iron oxide, hydrophobized black iron oxide, and hydrophobized red iron oxide and hydrophobized titanium oxide are used in combination. It is 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.

As the coloring pigment, one type or two or more types can be used, and the content is preferably 1% by mass or more in the total composition, and 3% by mass or more, from the viewpoint of finishing the skin with a beautiful make-up effect. Is more preferable, 4% by mass or more is further preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 18% by mass or less is further preferable. The content of the coloring pigment is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 4 to 18% by mass in the total composition.

In addition to the above-mentioned components, the water-in-oil emulsified cosmetic of the present invention includes components usually used in cosmetics, such as oil components other than the above, powders, water-soluble polymers, antioxidants, fragrances, pigments, and preservatives. It can contain agents, thickeners, pH regulators, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, moisturizers, refreshing agents and the like.

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method.
The water-in-oil emulsified cosmetic of the present invention can be in the form of liquid, emulsion, paste, cream, gel or the like, and is preferably emulsion or cream.

The water-in-oil emulsified cosmetic of the present invention is a makeup base, foundation, concealer; makeup cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, UV protection cosmetics such as sunscreen cream; can be applied as skin care cosmetics such as skin care milky lotion, skin care cream, BB cream, and beauty liquid. Of these, make-up cosmetics are preferable, and makeup bases, liquid foundations, and cream foundations are more preferable.
The water-in-oil emulsified cosmetic of the present invention can be used alone or in layers of powder cosmetics such as liquid foundation, powder foundation and white powder.

Regarding the above-described embodiment, the present invention further discloses the following composition.

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

<2> The water-in-oil emulsified cosmetic according to <1>, wherein the component (A) preferably contains at least dimethylpolysiloxane.
<3> The component (A) preferably has a viscosity at 25 ° C. of 30 to 100,000 mPa · s, more preferably 30,000 to 50,000 mPa · s, more preferably 50 to 10,000 mPa · s, and 100 to 5,000 mPa · s. The water-in-oil emulsified cosmetic according to <1> or <2>, more preferably 150 to 3000 mPa · s.
<4> The content of the component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 20% by mass or less, and more preferably 13% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <3>.

<5> The water-in-oil emulsified cosmetic according to any one of <1> to <4>, wherein the film-forming agent of the component (B) is preferably in the form of a solid at 25 ° C.
<6> The film-forming agent of the component (B) is preferably trimethylsiloxysilicic acid, a fluorine-modified silicone resin, or an acrylic silicone resin, and one or two selected from trimethylsiloxysilicic acid and a fluorine-modified silicone resin. The water-in-oil emulsified cosmetic according to any one of <1> to <5>, wherein the above is more preferable.
<7> The component (B) is preferably (B-1) trimethylsiloxysilicic acid, and [(CH ₃ ) ₃ SiO _1/2 ] _a [SiO ₂ ] _b (a is 1 to 3, b). The water-in-oil emulsified cosmetic according to any one of <1> to <6>, more preferably represented by 0.5 to 8).
<8> The component (B) is preferably (B-1) trimethylsiloxysilicic acid, more preferably 1000 to 10000 by mass average molecular weight, further preferably 2000 to 9000, and 3000 to 6000. The water-in-oil emulsified cosmetic according to any one of <1> to <7>, wherein the one according to any one of <1> to <7> is more preferable.

<9> The component (B) is preferably (B-2) a fluorine-modified silicone resin, and has a general formula (1).
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group or a general formula-R ^2- Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf is a carbon. a showing a perfluoroalkyl group having 1 to 8), arbitrarily chosen a hydroxyl group and the general formula -R ² -Rf from the functional groups as an essential, 1.0 ≦ a ≦ 1 a is an average number. 8)
The water-in-oil emulsified cosmetic according to any one of <1> to <8>, wherein the one having the structure represented by (3) is more preferable, and trifluoropropyldimethyl / Trimethylsiloxysilicate is more preferable.
<10> The component (B) is preferably (B-3) an acrylic silicone resin, and a vinyl polymer having a carbosiloxane dendrimer structure in a side chain and an acrylic-silicone graft copolymer are more preferable. The water-in-oil emulsified cosmetic according to any one of <1> to <9>.

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

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

<15> The ester oil of the component (D) is preferably a non-volatile ester oil, more preferably a monoester oil, a diester oil, or a triester oil, further preferably a monoester oil, and paramethoxysilicate skin acid. The water-in-oil emulsified cosmetic according to any one of <1> to <14>, wherein octyl and isononyl isononanoate are more preferable, and at least octyl paramethoxysilicate is more preferable.
<16> The content of the component (D) is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, preferably 8% by mass or less, and 6% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <15>, which is more preferable.
<17> 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 and 0. The water-in-oil emulsified cosmetic according to any one of <1> to <16>, wherein .42 or more is more preferable, 0.8 or less is preferable, and 0.72 or less is more preferable.
<18> 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 and 0. .1 or more is more preferable, 0.2 or more is further preferable, 5 or less is preferable, 3 or less is more preferable, and 1.6 or less is further preferable. Mold emulsified cosmetics.

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

<24> The water-in-oil emulsified cosmetic according to any one of <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 emulsified cosmetic according to any one of <1> to <24>, further preferably containing a coloring pigment, and more preferably containing a hydrophobized coloring pigment.

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

<28> The content of the component (A) is 0.1 to 25% by mass in the total composition, the content of the component (B) is 2 to 20% by mass in the total composition, and the content of the component (D). However, the mass ratio (B) / [(A) + (D)] of the component (B) to the total content of the components (A) and (D) is 0, which is 0.1 to 12% by mass in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <25>, preferably .05 to 5.
<29> The content of the component (A) is 2 to 13% by mass in the total composition, the content of the component (B) is 2 to 8% by mass in the total composition, and the content of the component (D) is. 1.5 to 6% by mass in the total composition, the mass ratio (B) / [(A) + (D)] of the component (B) to the total content of the components (A) and (D) is 0.2. The water-in-oil emulsified cosmetic according to any one of <1> to <28>, preferably in the amount of ~ 1.6.

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

Examples 1 to 10, Comparative Examples 1 to 3
A water-in-oil emulsified cosmetic having the composition shown in Table 1 was manufactured, applied to the skin, and after 8 hours, there was no shine due to sebum, no secondary adhesion to towels, skin brightness, and skin. Uniformity was evaluated. The results are also shown in Table 1.
The dimethylpolysiloxane used in the examples was mixed with squalane at a mass ratio of 1: 1 and held by hand with a stroke number of 120 times / minute and a stroke width of 30 cm, and the mixture was stirred and mixed for 30 seconds, and then further with a vortex mixer. Table 2 shows the state (whether it is compatible with squalane) when the mixture is stirred for 30 seconds and allowed to stand for 1 minute.

(Production method)
The powder phase components were mixed and pulverized, added to the separately mixed oil phase components, and dispersed with a disper. Then, the aqueous phase component was added, dispersed with a disper, and then stirred with a homomixer to obtain a water-in-oil emulsified cosmetic (foundation).

(Evaluation method)
(1) No shine due to sebum after 8 hours of application to the skin:
Each foundation was applied to the skin by five specialized panelists, and the resistance to shine due to sebum 8 hours after application was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; There is no shine due to sebum.
4; There is no shine due to sebum.
3; There is not much shine due to sebum.
2; There is some shine due to sebum.
1; There is shine due to sebum.

(2) No secondary adhesion to towels after 8 hours of application to the skin:
Each foundation was applied to the skin by five specialized panelists, and 8 hours after the application, the color transfer of the foundation when a cotton towel was pressed against the skin was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; Even if the towel is pressed against the skin after application, the foundation does not adhere at all.
4; Even if the towel is pressed against the skin after application, the foundation does not come on.
3; Even if the towel is pressed against the skin after application, the foundation does not adhere much.
2; When you press the towel against the skin after application, the foundation will come a little.
1; When you press the towel against the skin after application, the foundation will be attached.

(3) Brightness of the skin after 8 hours of application to the skin:
Each foundation was applied to the skin by five specialized panelists, and the brightness of the makeup skin 8 hours after the application was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; Makeup skin looks bright.
4; Makeup skin looks a little bright.
3; Makeup skin does not look very bright.
2; Makeup skin does not look bright.
1; Makeup skin does not look bright at all.

(4) Skin uniformity after 8 hours of application to the skin:
Each foundation was applied to the skin by five specialized panelists, and the uniformity of the makeup skin 8 hours after the application was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; Makeup skin looks uniform.
4; Makeup skin looks a little uniform.
3; Makeup skin does not look very uniform.
2; Makeup skin does not look uniform.
1; Makeup skin does not look even at all.

Examples 11-14
In the same manner as in Examples 1 to 10, water-in-oil emulsified cosmetics (foundations) having the compositions shown in Table 3 were produced.
All of the obtained foundations are applied to the skin, and even after 8 hours have passed, there is no shine due to sebum, and even when a towel is pressed against the skin, the foundation does not adhere, and the skin looks bright and uniform.

Claims

The following components (A), (B), (C) and (D):
(A) Non-volatile silicone oil incompatible with squalane 0.1 to 25% by mass,
(B) Silicone-based film forming agent 2 to 20% by mass,
(C) Volatile oil,
(D) Ester oil 0.1-12% by mass
Contains,
The component (A) has a viscosity at 25 ° C. of 30 to 100,000 mPa · s.
Water-in-oil emulsified makeup in which the mass ratio (A) / [(A) + (D)] of the component (A) to the total content of the components (A) and (D) is 0.3 to 0.95. Fee.
The water-in-oil emulsified cosmetic according to claim 1, wherein the component (A) has a viscosity of 100 to 50,000 mPa · s at 25 ° C.
The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the component (A) contains at least dimethylpolysiloxane.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the component (B) is one or more selected from trimethylsiloxysilicic acid and fluorosilicone resin.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, wherein the content of the component (B) is 0.5 to 20% by mass.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, wherein the component (C) contains at least linear dimethylpolysiloxane.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, wherein the content of the component (C) is 5 to 50% by mass.
Any of claims 1 to 7, wherein the mass ratio (B) / [(A) + (D)] of the component (B) to the total content of the components (A) and (D) is 0.05 to 5. The water-in-oil emulsified cosmetic according to item 1.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 8, wherein the component (D) contains at least octyl paramethoxycinnamate.
Further, the water-in-oil emulsified cosmetic according to any one of claims 1 to 9, which contains (E) a nonionic surfactant.
The following components (A), (B), (C) and (D):
(A) Non-volatile silicone oil having a viscosity at 25 ° C. of 30 to 100,000 mPa · s and incompatible with squalane, 0.1 to 25% by mass,
(B) Silicone-based film forming agent 2 to 20% by mass,
(C) Volatile oil,
(D) Ester oil 0.1-12% by mass
Is blended so that the mass ratio (A) / [(A) + (D)] of the component (A) to the total content of the components (A) and (D) is 0.3 to 0.95. Water-in-oil emulsified cosmetics.