Water-in-oil emulsion cosmetic

Abstract

To provide a water-in-oil emulsion cosmetic which is free from oil bleeding and exhibits superior storage stability.SOLUTION: A water-in-oil emulsion cosmetic comprises the following components (A), (B), (C), and (D). Component (A) is 0.2 to 10 mass% of a glycerin fatty acid ester that is solid at 25°C. Component (B) is a linear volatile oil. Component (C) is a sorbitan fatty acid ester. Component (D) is a coloring pigment treated with amino acids and free from silicone.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a water-in-oil emulsion cosmetic.

Background Art

[0002] Conventionally, water-in-oil emulsion cosmetics that give the skin a glossy feeling and have excellent color unevenness covering power have been studied. For example, Patent Document 1 describes that a water-in-oil emulsion composition containing a cation-modified clay mineral substituted with a quaternary ammonium ion, a liquid phenyl-modified silicone, a sorbitan fatty acid ester, and a polyether-modified silicone is excellent in elongation during application, adhesion to the skin, and finished covering power. Patent Document 2 describes that a water-in-oil emulsion cosmetic containing a hydrophobized colored pigment, a volatile oil, a cation-modified clay mineral substituted with a quaternary ammonium ion, and a spherical organic powder has a good affinity for the skin during application, does not become heavy in stretching, has a non-catching feeling in use, and effectively conceals color unevenness.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present inventor has found that in a water-in-oil emulsion cosmetic containing a volatile oil, a sorbitan fatty acid ester, and an amino acid-treated powder, in the conventional technology applying a chain-like volatile oil and a powder subjected to a composite treatment of an amino acid and silicone, the stability deteriorates and oil oozes out to the surface.

Means for Solving the Problems

[0005] The present inventors have found that by using, in combination, a glycerin fatty acid ester that is solid at 25°C, a sorbitan fatty acid ester, a chain volatile oil, and an amino acid-treated colored pigment that does not contain silicone, an oil-in-water type emulsified cosmetic can be obtained that has improved oil bleeding, excellent storage stability, maintains the gloss of the skin after application, and has excellent skin color unevenness covering power.

[0006] The present invention relates to an oil-in-water type emulsified cosmetic containing the following components (A), (B), (C) and (D): (A) 0.2 to 10% by mass of a glycerin fatty acid ester that is solid at 25°C, (B) A chain volatile oil, (C) A sorbitan fatty acid ester, (D) An amino acid-treated colored pigment that does not contain silicone

Effects of the Invention

[0007] The oil-in-water type emulsified cosmetic of the present invention has no oil bleeding and is excellent in storage stability. Further, it maintains the gloss of the skin after application and is excellent in skin color unevenness covering power.

Modes for Carrying Out the Invention

[0008] Component (A) used in the present invention is a glycerin fatty acid ester that is solid at 25°C. Being solid at 25°C means showing a semi-solid to solid property at 25°C. As the glycerin fatty acid ester that is solid at 25°C, a triester is preferable. From the viewpoints of maintaining the viscosity of the oil-in-water type emulsified cosmetic, suppressing oil bleeding, having excellent storage stability, and having excellent adhesion to the skin and excellent skin color unevenness covering power, triglycerides of fatty acids having 20 to 28 carbon atoms are more preferable, triglycerides of fatty acids having 20 to 24 carbon atoms are even more preferable, and it is even more preferable to contain at least tribehenin.

[0009] ​Component (A) can be used singly or in combination of two or more. From the viewpoints of maintaining the viscosity of the water-in-oil emulsion cosmetic, suppressing the bleeding of oil, excellent storage stability, excellent feeling of adhesion to the skin, and excellent skin color unevenness covering power, the content is 0.2% by mass or more, preferably 0.6% by mass or more, more preferably 1% by mass or more, 10% by mass or less, preferably 7% by mass or less, and more preferably 5% by mass or less in the total composition. Further, the content of component (A) is 0.2 to 10% by mass, preferably 0.6 to 7% by mass, and more preferably 1 to 5% by mass in the total composition.

[0010] Component (B) is a chain volatile oil. Volatile means having a flash point of 35 to 87 °C. Examples of the volatile oil of component (B) include chain volatile silicone oils and chain volatile hydrocarbon oils. Examples of the chain volatile silicone oils include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1 cs), dimethylpolysiloxane (1.5 cs), dimethylpolysiloxane (2 cs); and branched siloxanes such as methyltrimethicone, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane. It is preferably composed of one or more selected from dimethylpolysiloxane (1 cs), dimethylpolysiloxane (1.5 cs), dimethylpolysiloxane (2 cs), and methyltrimethicone.

[0011] Examples of the chain volatile hydrocarbon oils include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; and isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene. It preferably contains isododecane.

[0012] From the viewpoints of suppressing the bleeding of oil, excellent storage stability, maintaining the gloss of the skin after application, and excellent skin color unevenness covering power, the volatile oil of component (B) is preferably a chain volatile silicone oil, more preferably a branched silicone oil, and even more preferably contains at least methyltrimethicone.

[0013] Component (B) can be used singly or in combination of two or more. From the viewpoint of suppressing oil bleeding, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, the content is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 50% by mass or less, more preferably 25% by mass or less, and still more preferably 15% by mass or less in the whole composition. Further, the content of component (B) is preferably 1 to 50% by mass, more preferably 2 to 25% by mass, and still more preferably 3 to 15% by mass in the whole composition.

[0014] Component (C) used in the present invention is sorbitan fatty acid ester. From the viewpoint of storage stability, the HLB of sorbitan fatty acid ester is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 7 or less, and still more preferably 6 or less.

[0015] In the present invention, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant and is determined by the Griffin's formula. Further, when composed of two or more nonionic surfactants, the HLB of the mixed surfactant is determined as follows. The HLB of the mixed surfactant is the weighted average of the HLB values of each nonionic surfactant based on its blending ratio. Mixed HLB = Σ(HLBx × Wx) / ΣWx HLBx indicates the HLB value of nonionic surfactant X. Wx indicates the mass (g) of nonionic surfactant X having the value of HLBx.

[0016] Examples of sorbitan fatty acid esters include sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquistearate, sorbitan sesquioleate, etc. From the perspective of suppressing oil bleeding, excellent storage stability, and excellent gloss of the skin after application, it preferably contains one or more selected from sorbitan monoisostearate, sorbitan monooleate, and sorbitan sesquistearate, more preferably contains one or more selected from sorbitan monoisostearate and sorbitan sesquistearate, and even more preferably contains sorbitan monoisostearate. Examples of the sorbitan fatty acid ester as component (C) include, for example, as sorbitan monoisostearate, Span 120 (HLB 4.7) (manufactured by Croda), as sorbitan sesquistearate, NIKKOL SS-15V (HLB 4.2), as sorbitan monooleate, NIKKOL SO-10V (HLB 4.3) (above, manufactured by Nikko Chemicals Co., Ltd.), etc., and commercially available products can be used.

[0017] One or more kinds of component (C) can be used. From the perspective of suppressing oil bleeding, excellent storage stability, and excellent gloss of the skin after application, the content is preferably 0.001% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less in the total composition. Also, the content of component (C) is preferably 0.001 to 10% by mass, more preferably 0.1 to 7% by mass, and even more preferably 1 to 4% by mass in the total composition.

[0018] In the present invention, the mass ratio (C) / (A) of component (C) to component (A) is preferably 0.01 or more, more preferably 0.3 or more, still more preferably 0.6 or more, preferably 8 or less, more preferably 5 or less, and still more preferably 2.4 or less, from the viewpoint of suppressing the bleeding of oil, having excellent storage stability, maintaining the glossiness of the skin after application, and having excellent skin color unevenness covering power. Further, the mass ratio (C) / (A) of component (C) to component (A) is preferably 0.01 to 8, more preferably 0.3 to 5, and still more preferably 0.6 to 2.4.

[0019] Component (D) is an amino acid-treated coloring pigment that does not contain silicone. Examples of the coloring pigment include 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 iron oxide, ultramarine blue, cobalt blue, chromium oxide, chromium hydroxide; metal complexes such as manganese violet, cobalt titanate; and inorganic pigments such as carbon black; synthetic organic pigments, organic dyes and their lake pigments such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, 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, Yellow No. 5, Yellow No. 401, Blue No. 1, Blue No. 404; natural organic pigments such as β-carotene, caramel, paprika pigment, etc. Complexes of these coloring pigments, and mixed pigments obtained by diluting these coloring pigments with extender pigments such as barium sulfate and talc are also included. As the coloring pigment, from the viewpoint of improving the covering power of the finish and the clean makeup finish feeling of the whole face, it preferably contains a metal oxide, more preferably contains one or more selected from titanium oxide, zinc oxide, yellow iron oxide, black iron oxide, and red iron oxide, and still more preferably contains one or more selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide.

[0020] The coloring pigment of component (D) is treated with an amino acid, including amino acids and those treated with acylated amino acids, and those treated with acylated amino acids are preferred. Examples of the amino acid used to treat the coloring pigment include proline, hydroxyproline, alanine, glycine, sarcosine, lysine, aspartic acid, glutamic acid, etc., and salts thereof are included. Further, the fatty acid constituting the acyl group of the acylated amino acid preferably has 1 to 23 carbon atoms, more preferably 8 to 20 carbon atoms. Among them, stearoyl glutamate, cocooyl glutamate, lauroyl aspartic acid, dilauroyl glutamate lysine, and lauroyl lysine are even more preferred. Examples of these salts include Na, Ca, Al, Mg, Zn, Zr, and Ti salts. Specifically, from the viewpoints of suppressing oil bleeding, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, those treated with disodium stearoyl glutamate, sodium lauroyl aspartate, and disodium cocooyl glutamate are preferred, and those treated with sodium lauroyl aspartate and disodium cocooyl glutamate are more preferred. The amino acid treatment can be carried out according to a normal method. Note that the coloring pigment of component (D) may be hydrophobically treated together with a compound other than an amino acid, but from the viewpoint of suppressing oil bleeding, silicone treatment is not included.

[0021] The coloring pigment of component (D) can be used alone or in combination of two or more. From the viewpoints of suppressing oil bleeding, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less in the total composition. Further, the content of component (D) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and even more preferably 5 to 20% by mass in the total composition.

[0022] In the present invention, the mass ratio (D) / (A) of component (D) to component (A) is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, preferably 40 or less, more preferably 25 or less, and still more preferably 17 or less, from the viewpoints of suppressing the bleeding of oil, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power. Further, the mass ratio (D) / (A) of component (D) to component (A) is preferably from 1 to 40, more preferably from 3 to 25, and still more preferably from 4 to 17.

[0023] In the present invention, the mass ratio (D) / (B) of component (D) to component (B) is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less, from the viewpoints of suppressing the bleeding of oil, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power. Further, the mass ratio (D) / (B) of component (D) to component (B) is preferably from 0.5 to 8, more preferably from 1 to 6, and still more preferably from 1.5 to 4.

[0024] The water-in-oil emulsion cosmetic of the present invention may further contain (E) a cation-modified clay mineral substituted with a quaternary ammonium ion, which can improve the storage stability. The cation-modified clay mineral of component (E) is substituted with a quaternary ammonium ion and can be used without limitation as long as it is used in ordinary cosmetics. For example, cation-modified clay minerals obtained by substituting layered clay minerals such as bentonite, laponite, hectorite, montmorillonite, and magnesium aluminum silicate with a quaternary ammonium salt type cationic surfactant are preferred. Here, the quaternary ammonium salt type cationic surfactant is represented by the following formula (1):

[0025]

Chemical formula

[0026] (In the formula, R1 represents an alkyl group or a benzyl group having 10 to 22 carbon atoms, and R 2 represents a methyl group or an alkyl group having 10 to 22 carbon atoms, and R 3 and R 4 represent an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or a methyl sulfate residue). It is represented by

[0027] Specifically, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyl dimethylethylammonium chloride, stearyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylethylammonium chloride, cetyl diethylethylammonium chloride, stearyldiethylethylammonium chloride, behenyldiethylethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, distearyldimethylammonium chloride, dibehenyldihydroxyethylammonium chloride, and those obtained by replacing the chlorides of the above compounds with bromide compounds, and further dipalmitoylpropylethylammonium methyl sulfate and the like can be mentioned. Among them, it preferably contains one or more selected from benzyldimethylstearylammonium chloride and dimethyldistearylammonium chloride, and dimethyldistearylammonium chloride is more preferable.

[0028] Examples of the cation-modified clay minerals obtained by substituting a layered clay mineral with a quaternary ammonium salt type cationic surfactant include one or more selected from dimethyldistearylammonium hectorite, dimethyldistearylammonium bentonite, and benzyldimethylstearylammonium hectorite. It is preferably one or more selected from dimethyldistearylammonium hectorite and benzyldimethylstearylammonium hectorite, more preferably one or more selected from dimethyldistearylammonium hectorite and benzyldimethylstearylammonium hectorite, and even more preferably containing dimethyldistearylammonium hectorite. Examples of commercially available products include Benton 38, Benton 38VCG, Benton 27 (manufactured by Elementis Japan Co., Ltd., etc.).

[0029] The organically modified clay mineral can also be used as a dispersion diluted with a solvent from the viewpoints of improving workability and excellent oil thickening effect. Specifically, it is preferable to use a premix gel in which the organically modified clay mineral is previously dispersed in a solvent. The solvent is not limited as long as it can be thickened by the organically modified clay mineral, but from the viewpoint of the oil thickening effect, it preferably contains one or more selected from octyldodecanol, mineral oil, volatile silicone oil, tri(caprylic acid / capric acid) glyceryl, and alkyl benzoate (C12-15), and more preferably contains one or more selected from tri(caprylic acid / capric acid) glyceryl and alkyl benzoate (C12-15). The content of the organically modified clay mineral in the premix gel is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, and even more preferably 10 to 18% by mass from the viewpoints of improving workability, the oil thickening effect, and suppressing oil separation of the thickened oily gel itself. As the premix gel, commercially available products such as benton gel EUGV containing 10% by mass of cation-modified clay mineral, benton gel MIOV, benton gel VS-5 PCV containing 18% by mass, benton gel PTM containing 15% by mass (all of the above are manufactured by Elementis Japan Co., Ltd.), BENTONE GEL GTCC V containing 12.5% by mass, BENTONE GEL TN V (all of the above are manufactured by Elementis Specialties Co., Ltd.) can be used.

[0030] As the component (E), one kind or two or more kinds can be used. From the viewpoint of suppressing the bleeding of oil, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, the content is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less in the total composition. Further, the content of the component (E) is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.2% by mass, and still more preferably 0.03 to 0.1% by mass in the total composition.

[0031] In the present invention, from the viewpoint of suppressing the bleeding of oil, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, the mass ratio (A) / (E) of the component (A) to the component (E) is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, preferably 200 or less, more preferably 100 or less, and still more preferably 80 or less. Further, the mass ratio (A) / (E) of the component (A) to the component (E) is preferably 10 to 200, more preferably 15 to 100, and still more preferably 20 to 80.

[0032] The water-in-oil type emulsified cosmetic of the present invention can further contain an oil component having a melting point of 30 to less than 61°C, and the bleeding of oil is suppressed. In the present invention, the melting point is measured by the third method of the general test method described in the cosmetic raw material standards. That is, while stirring the sample, it is gradually heated to 90 - 92°C until it melts, the heating is stopped, and the sample is cooled to a temperature 8 - 10°C higher than the melting point. Then, after cooling the thermometer (a thermometer for petroleum jelly melting point specified in Japanese Industrial Standard B7410) to 5°C, the moisture is wiped off with filter paper, half of the mercury bulb is inserted into the sample, immediately withdrawn, kept vertical and cooled. When the attached sample becomes turbid, it is immersed in water at a temperature of 16°C or lower for 5 minutes. Next, the examiner inserts the thermometer and fixes the thermometer using a cork so that the distance between the lower end of the thermometer and the bottom of the test tube is 15 mm. This test tube is fixed in a 500 mL beaker filled with water at about 16°C so that the distance between the bottom of the test tube and the bottom of the beaker is 15 mm, and it is heated so that the temperature of the bath rises by 2°C per minute until the bath temperature reaches 30°C. Then, the heating is continued so that the temperature rises by 1°C per minute, and the temperature when a drop of the sample separates from the thermometer is measured. This test is performed three times. When the difference in the measured values is less than 1°C, the average value is taken. When it is 1°C or more, it is measured five times and the average value is taken as the melting point.

[0033] The oil components with a melting point of less than 30 to 61 °C are not restricted as long as they are those commonly used in cosmetics. For example, petrolatum (57 °C), beeswax (60 °C), synthetic beeswax (53 °C), vinyl resin wax (54 °C), hexaglycerin pentaester (behenic acid / benzoic acid / ethylhexanoic acid) (52 °C), cholesteryl hydroxystearate (52 °C), pentaerythritol tetraester (hydroxystearic acid / isostearic acid) (50 °C), hydrogenated palm oil (47 °C), dipentaerythritol hexahydroxystearate (45 °C), glyceryl triester (caprylic acid / capric acid / myristic acid / stearic acid) (40 °C), dipentaerythritol hexaester (hydroxystearic acid / stearic acid / rosin acid) (37 °C), phytosteryl oleate (33 °C), glyceryl triester (ethylhexanoic acid / stearic acid / adipic acid) (31 °C), dilauroyl glutamate di (octyldodecyl / phytosteryl / behenyl) (33 °C), dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) (34 °C), dimer dilinoleic acid dimer dilinoleyl bis (behenyl / isostearyl / phytosteryl) (38 °C), anhydrous lanolin (49 °C), lanolin alcohol (45 °C), bis-diglyceryl polyacyl adipate-2 (39 °C), etc. can be mentioned. Among these, those with a melting point of 32 to 58 °C are preferred from the viewpoints of suppressing oil bleeding, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power. It is more preferable to contain one or more selected from petrolatum (57 °C), dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) (34 °C), and dilauroyl glutamate di (octyldodecyl / phytosteryl / behenyl) (33 °C), and it is even more preferable to contain at least petrolatum (57 °C).

[0034] The oil component(s) having a melting point of less than 30 to 61°C can be used singly or in combination of two or more, and the content is preferably 0.4% by mass or more, more preferably 0.7% by mass or more, still more preferably 1% by mass or more, preferably 8% by mass or less, more preferably 6% by mass or less, and still more preferably 4% by mass or less in the total composition from the viewpoint of suppressing the bleeding of the oil, having excellent storage stability, maintaining the glossiness of the skin after application, and having excellent skin color unevenness covering power. Further, the content of the oil component having a melting point of less than 30 to 61°C is preferably 0.4 to 8% by mass, more preferably 0.7 to 6% by mass, and still more preferably 1 to 4% by mass in the total composition.

[0035] The water-in-oil emulsion cosmetic of the present invention can further contain a liquid non-volatile oil at 25°C excluding the oil component having a melting point of less than 30 to 61°C, and has excellent storage stability. Being liquid at 25°C means having fluidity at 25°C, and includes cream-like and paste-like substances. Further, non-volatile means having no flash point or having a flash point of 89°C or higher.

[0036] As the liquid non-volatile oil at 25°C, any oil that can be used in ordinary cosmetics may be used, and examples include hydrocarbon oils, ester oils, ether oils, silicone oils, higher alcohols, and the like. Examples of the hydrocarbon oil include linear or branched hydrocarbon oils such as liquid paraffin, liquid isoparaffin, hydrogenated polyisobutene, squalane, and squalene.

[0037] Examples of the ester oil include monoester oils, diester oils, triester oils, and tetraester oils. Examples of the monoester oil include monoesters of aliphatic or aromatic monocarboxylic acids or dicarboxylic acids having 2 to 24 carbon atoms. Specific examples include cetyl 2-ethylhexanoate, cetyl octanoate, isononyl isononanoate, isotridecyl isononanoate, hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, octyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, isocetyl isostearate, decyl oleate, isodecyl benzoate, octyl methoxycinnamate, hexyl decyl dimethyl octanoate, cetyl lactate, myristyl lactate, octyldodecyl lactate, lanolin acetate, 2-ethylhexyl succinate, 2-hexyldecyl adipate, alkyl (C12 - C15) benzoate, octyldodecyl 12-stearoyl stearate, and the like.

[0038] Examples of the diester oil include diesters of dicarboxylic acids having 3 to 18 carbon atoms, di-fatty acid esters of polyhydric alcohols, and the like. Specific examples include propylene glycol dicaprylate, neopentyl glycol dicaprylate, glycol distearate, propylene glycol diisostearate, glyceryl diisostearate, glyceryl monoisostearate monomyristate, glycerin di-2-heptylundecanoate, di-2-ethylhexyl succinate, diisopropyl sebacate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, diisobutyl adipate, di-2-heptylundecyl adipate, di-2-ethylhexyl sebacate, and the like.

[0039] Examples of the triester oil include triglycerides of polyhydric alcohols having three or more hydroxyl groups, specifically, glyceryl trimyristate, glyceryl triisopalmitate, glyceryl tri(2-heptylundecanoate), trimethylolpropane triethylhexanoate, trimethylolpropane trioctanoate, glyceryl tri(caprylic / capric acid), glyceryl trioleate, glyceryl tri(2-ethylhexanoate), glyceryl triisostearate, olive oil, jojoba oil, and the like.

[0040] Examples of the tetraester oil include tetra-fatty acid esters of polyhydric alcohols having four or more hydroxyl groups, specifically, pentaerythritol tetra(behenic acid / benzoic acid / ethylhexanoic acid), pentaerythritol tetraethylhexanoate, pentaerythritol tetraoctanoate, pentaerythritol tetra(2-ethylhexanoate).

[0041] Examples of the ether oil include dialkyl ethers, specifically, dihexyl ether, dicaprylyl ether, cetyl-1,3-dimethylbutyl ether, and the like.

[0042] Examples of the silicone oil include crosslinked methylpolysiloxane, network methylpolysiloxane, dimethylpolysiloxane, methyltrimethicone, dimethylcyclopolysiloxane, higher alcohol-modified organopolysiloxane, phenyl-modified silicone, etc., and preferably includes phenyl-modified silicone.

[0043] Examples of the higher alcohol include those having a linear or branched alkyl or alkenyl group with 10 to 24 carbon atoms, such as lauryl alcohol, myristyl alcohol, isocetyl alcohol, isostearyl alcohol, 2-octyldodecanol, oleyl alcohol, and the like.

[0044] The non-volatile oil that is liquid at 25°C preferably contains silicone oil, and more preferably contains phenyl-modified silicone, from the viewpoint of suppressing the bleeding of the oil. Examples of phenyl-modified silicones that are liquid at 25°C include phenyltrimethicone, diphenylsiloxyphenyltrimethicone, diphenyldimethylsilicone, trimethylsiloxyphenyldimethylsilicone, trimethylpentaphenyltrisiloxane, methylphenylpolysiloxane, etc. Phenyltrimethicone and methylphenylpolysiloxane are preferred, and those containing at least methylphenylpolysiloxane are more preferred.

[0045] The non-volatile oil that is liquid at 25°C can be used singly or in combination of two or more. From the viewpoints of excellent storage stability and excellent maintenance of the gloss of the skin after application, the content is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 16% by mass or less in the total composition. Also, the content of the non-volatile oil that is liquid at 25°C is preferably 1 to 25% by mass, more preferably 5 to 20% by mass, and still more preferably 8 to 16% by mass in the total composition.

[0046] The water-in-oil emulsion cosmetic of the present invention can further contain plate-like powder. The plate-shaped powder is not limited as long as it can be used in ordinary cosmetics. For example, boron nitride, silicic acid, silicic anhydride, magnesium silicate, sericite, talc, mica, kaolin, clay, bentonite, synthetic phlogopite, bismuth oxychloride, zirconium oxide, magnesium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, etc. can be mentioned. Further, a composite pigment using these plate-shaped powders as a base can also be used. Examples of the composite pigment using these plate-shaped powders as a base include sericite coated with titanium oxide, mica coated with titanium oxide, bismuth oxychloride coated with titanium oxide, talc coated with titanium oxide, mica coated with titanium oxide and iron oxide, synthetic phlogopite coated with titanium oxide, mica coated with titanium oxide and barium sulfate, mica coated with titanium oxide and silica, talc coated with zinc oxide, mica coated with titanium oxide and tin oxide, mica coated with zinc oxide and titanium oxide, mica coated with titanium oxide and alumina, mica coated with titanium oxide, iron oxide and silica, mica coated with titanium oxide, silica and alumina, etc. Among these, from the viewpoint of the finished touch, it is preferable to contain talc.

[0047] These plate-shaped powders can be used as they are, or those subjected to a hydrophobization treatment by a usual method can also be used. Examples of the hydrophobization treatment include surface treatments such as fluorine compound treatment, 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, etc. As the hydrophobization treatment of the plate-shaped powder, amino acid treatment and acylated amino acid treatment are preferable, and among them, those treated with acylated amino acid are more preferable. From the viewpoint of suppressing oil bleeding, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, those treated with acylated amino acid without containing silicone are further preferable, and talc treated with acylated amino acid containing at least no silicone is even more preferable.

[0048] The plate-shaped powder can be used alone or in combination of two or more kinds. From the viewpoint of suppressing the bleeding of oil, having excellent storage stability, maintaining the gloss of the skin after application, and having excellent skin color unevenness covering power, the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less in the total composition. Further, the content of the plate-shaped powder is preferably 0.1 to 15% by mass, more preferably 0.5 to 7% by mass, and still more preferably 1 to 5% by mass in the total composition.

[0049] In the present invention, from the viewpoint of storage stability, the water content is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less in the total composition. Further, the water content is preferably 5 to 60, more preferably 20 to 55% by mass, and still more preferably 30 to 50% by mass in the total composition.

[0050] In addition to the above components, the water-in-oil type emulsified cosmetic of the present invention can contain components usually used in cosmetics, for example, oil components other than the above, surfactants other than the above, powders other than the above, water-soluble polymers, antioxidants, fragrances, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, moisturizers, cooling agents, etc.

[0051] The water-in-oil type emulsified cosmetic of the present invention can be produced according to a usual method. The water-in-oil type emulsified cosmetic of the present invention can be made into dosage forms such as liquid, emulsion, paste, cream, gel, etc. From the viewpoint of excellent storage stability, the viscosity of the water-in-oil type emulsified cosmetic of the present invention is preferably 30000 to 95000 mPa·s, more preferably 40000 to 93000 mPa·s at 25°C. In the present invention, the viscosity is measured at 25°C with a B-type viscometer (TVB-15 type, manufactured by Toki Sangyo Co., Ltd.), rotor TM-4, rotation speed 6, and measurement time 30 seconds.

[0052] The water-in-oil type emulsified cosmetic of the present invention is preferably a skin-use water-in-oil type emulsified cosmetic, more preferably an ultraviolet ray-protecting cosmetic or a makeup cosmetic, and even more preferably a makeup cosmetic. The water-in-oil type emulsified cosmetic of the present invention can be applied, for example, as makeup cosmetics such as makeup bases, foundations, concealers, blushes, eyeshadows, mascaras, eyeliners, eyebrows, overcoat agents, lipsticks; ultraviolet ray-protecting cosmetics such as sunscreen milks and sunscreen creams; and skin care cosmetics such as skin care milks, skin care creams, BB creams, and beauty liquids.

Examples

[0053] Examples 1 to 5 and Comparative Examples 1 to 3 A water-in-oil type emulsified cosmetic (liquid foundation) having the composition shown in Table 1 was produced, and its viscosity immediately after production at 25°C, storage stability at 25°C, storage stability at 40°C, skin color unevenness covering power immediately after application, and glossiness immediately after application were evaluated. The results are shown together in Table 1.

[0054] (Production method) To the oil phase containing components (A), (B), (C) and (D), the powder phase containing component (D) was added and dispersed, and then the aqueous phase component was added and stirred with a homomixer to obtain a water-in-oil type emulsified cosmetic (liquid foundation).

[0055] (Evaluation method) (1) Viscosity immediately after production at 25°C: For each water-in-oil type emulsified cosmetic, the viscosity at 25°C immediately after production was measured at 25°C using a B-type viscometer (TVB-15 type, manufactured by Toki Sangyo Co., Ltd.), rotor TM-4, rotation speed 6, and measurement time 30 seconds.

[0056] (2) Storage stability at 25°C: 50 g of each water-in-oil type emulsified cosmetic was filled into a glass bottle, and the properties (oil bleeding) after storage at 25°C for 7 days were visually evaluated according to the following criteria. ○: No oil seepage. ×: Oil seeps out and separation is observed.

[0057] (3) Storage stability at 40°C: 50 g of each water-in-oil emulsion cosmetic was filled into a glass bottle and stored at 40°C for 7 days. The properties (oil seepage) after storage were visually evaluated according to the following criteria. ○: No oil seepage. ×: Oil seeps out and separation is observed.

[0058] (4) Skin color unevenness coverage immediately after application: Five professional evaluators evaluated the skin color unevenness coverage immediately after applying each water-in-oil emulsion cosmetic to the skin according to the following criteria. The results are shown as the total score of the five evaluators. 5: Can firmly cover skin color unevenness. 4: Can cover skin color unevenness. 3: Can slightly cover skin color unevenness. 2: Can hardly cover skin color unevenness. 1: Cannot cover skin color unevenness.

[0059] (5) Gloss immediately after application: Five professional evaluators evaluated the gloss immediately after applying each water-in-oil emulsion cosmetic to the skin according to the following criteria. The results are shown as the total score of the five evaluators. 5: A prominent gloss can be obtained over the entire skin. 4: A gloss can be obtained over the entire skin. 3: A slightly gloss can be obtained over the entire skin. 2: Hardly any gloss can be obtained over the entire skin. 1: No gloss can be obtained over the entire skin.

[0060]

Table 1

[0061] Example 6 The water-in-oil type emulsified cosmetic (liquid foundation) having the composition shown in Table 2 was produced in the same manner as in Examples 1 to 5, has no seepage of oil, is excellent in storage stability, and has good skin color unevenness covering power immediately after application and good glossiness immediately after application.

[0062]

Table 2

Claims

**Claim 1** The following components (A), (B), (C) and (D): (A) 0.2 to 10% by mass of a glycerin fatty acid ester that is solid at 25°C, (B) a linear volatile oil, (C) a sorbitan fatty acid ester, (D) an amino acid-treated coloring pigment that does not contain silicone A water-in-oil emulsion cosmetic containing them. **Claim 2** The water-in-oil emulsion cosmetic according to claim 1, wherein the content of component (B) is 1 to 50% by mass, the content of component (C) is 0.001 to 10% by mass, and the content of component (D) is 0.1 to 30% by mass. **Claim 3** The water-in-oil emulsion cosmetic according to claim 1 or 2, wherein component (B) is one or more selected from linear volatile silicone oils and linear volatile hydrocarbon oils. **Claim 4** The water-in-oil emulsion cosmetic according to any one of claims 1 to 3, wherein the mass ratio (C) / (A) of component (C) to component (A) is 0.01 to 8. **Claim 5** The water-in-oil emulsion cosmetic according to any one of claims 1 to 4, wherein the mass ratio (D) / (A) of component (D) to component (A) is 1 to 40.

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