Water-in-oil type emulsion composition

Abstract

To provide water-in-oil type emulsion compositions excellent in make-up persistence, skin fitting feeling and emulsion stability.SOLUTION: Provided is a water-in-oil type emulsion composition for impregnation, which comprises: (A) a cation modified clay mineral substituted with quaternary ammonium ion; (B) one or more selected from alkyl-modified silicones and phenyl-modified silicones being liquid at 25°C; (C) a modified silicone having an alkyl group of C10 or more and a polyglyceryl group; and (D) an ester oil being liquid at 25°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a water-in-oil emulsion composition. [Background technology]

[0002] Conventionally, cosmetics have been developed in which a liquid cosmetic is impregnated into a holder such as a sponge contained in a compact container, and when used, the cosmetic is taken from the holder using a finger or an applicator and applied to the skin. For example, Patent Document 1 describes that a cosmetic product containing a polyether-based urethane foam impregnated with a cosmetic composition is excellent in stability, portability, and usability. Patent Document 2 describes that a cosmetic product in which a water-insoluble sponge is impregnated with a cosmetic composition containing a specific organic ultraviolet blocking agent has excellent ultraviolet blocking properties. Patent Document 3 describes that a water-in-oil emulsion cosmetic for impregnation, which contains a cross-linked polyether-modified silicone or a cross-linked polyglycerin-modified silicone and an acrylic polymer having a dendrimer-type siloxane structure in its side chain or a siliconized pullulan, is excellent in usability and pore correction effect while maintaining the suitability for filling and retention in an impregnated body. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2013-530252 A [Patent Document 2] JP 2017-088631 A [Patent Document 3] JP 2019-131489 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional cosmetics have problems such as poor adhesion to the skin, a tendency for the cosmetics to become shiny or come off, and poor makeup durability. [Means for solving the problem]

[0005] The present inventors have discovered that a water-in-oil emulsion composition combining a cation-modified clay mineral with one or more selected from phenyl-modified silicones and alkyl-modified silicones, an alkyl glyceryl ether-modified silicone, and a liquid ester oil has improved adhesion to the skin, a good fit to the skin, is less likely to cause makeup to run, has excellent makeup durability, and is also excellent in emulsion stability.

[0006] The present invention comprises the following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The present invention relates to a water-in-oil type emulsion composition for impregnation, comprising:

[0007] The present invention also relates to a cosmetic product in which a holder impregnated with the water-in-oil emulsion composition is incorporated in a compact container. The present invention also relates to a method for using the above cosmetic, which comprises taking the water-in-oil emulsion composition impregnated in the support with a finger or an applicator from the support and applying it to the skin. The present invention also relates to a composition comprising the following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The present invention relates to a cosmetic kit comprising a holder impregnated with a water-in-oil emulsion composition containing the above-mentioned compound and a compact container.

[0008] The present invention also relates to a composition comprising the following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The present invention relates to a water-in-oil emulsion composition comprising: Effect of the Invention

[0009] The water-in-oil emulsion composition of the present invention has improved adhesion to the skin, a good fit to the skin, no makeup deterioration even after a long time has passed, excellent makeup durability, and excellent emulsion stability. The water-in-oil emulsion composition is suitable for use as a cosmetic material impregnated in a support and contained in a compact container. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The cationically modified clay mineral of component (A) used in the present invention is substituted with a quaternary ammonium ion, and can be used without any limitation as long as it is one used in ordinary cosmetics. For example, cationically 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):

[0011] [ka]

[0012] (In the formula, R 1 represents an alkyl group having 10 to 22 carbon atoms or a benzyl group, R 2 represents a methyl group or an alkyl group having 10 to 22 carbon atoms; R3 and R 4 represents 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 expressed as follows.

[0013] Specifically, dodecyl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, myristyl dimethyl ethyl ammonium chloride, cetyl dimethyl ethyl ammonium chloride, stearyl dimethyl ethyl ammonium chloride, behenyl dimethyl ethyl ammonium chloride, myristyl diethyl methyl ammonium chloride, cetyl diethyl methyl ammonium chloride, stearyl diethyl methyl ammonium chloride, behenyl diethyl methyl ammonium chloride, Examples of the above-mentioned compounds include benzyl dimethyl myristyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, benzyl dimethyl behenyl ammonium chloride, benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dihydroxyethyl ammonium chloride, and compounds in which the chloride of each of the above-mentioned compounds is replaced with a bromide compound, and further examples thereof include dipalmityl propyl ethyl ammonium methyl sulfate. Among these, it is preferable to contain one or more selected from benzyl dimethylstearyl ammonium chloride and dimethyl distearyl ammonium chloride, and dimethyl distearyl ammonium chloride is more preferable.

[0014] The cationic modified clay mineral obtained by substituting the layered clay mineral with a quaternary ammonium salt type cationic surfactant preferably contains one or more selected from dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, and benzyl dimethyl stearyl ammonium hectorite, more preferably contains one or more selected from dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite, and even more preferably contains dimethyl distearyl ammonium hectorite. In addition, examples of commercially available products include Benton 38, Benton 38VCG, and Benton 27 (all manufactured by Elementis Japan Co., Ltd.).

[0015] The organically modified clay mineral can also be used as a dispersion diluted with a solvent, because it improves workability and has an excellent effect of thickening oil. Specifically, it is preferable to use a premix gel in which organic modified clay mineral is dispersed in a solvent in advance.The solvent is not limited as long as it can be thickened by organic modified clay mineral, but from the viewpoint of the thickening effect of oil, it is preferable to include one or more selected from C9-12 alkane, C13-15 alkane, hydrocarbon oil such as mineral oil, silicone oil such as phenyl trimethicone, tri(caprylic acid / capric acid) glyceryl, alkyl benzoate (C12-15), and more preferably to include one or more selected from tri(caprylic acid / capric acid) glyceryl, alkyl benzoate (C12-15). The content of the organically modified clay mineral in the premix gel is preferably 5 to 25 mass%, more preferably 10 to 20 mass%, and even more preferably 10 to 18 mass%, from the viewpoints of improving workability, thickening effect of oil, and suppressing oil separation from the thickened oily gel itself. As premix gels, commercially available products such as BENTONE GEL LC V, BENTONE GEL HS V, BENTONE LUXE XO, BENTONE GEL MIOV, BENTONE GEL VS-5 PC V, BENTONE GEL PTM V (all manufactured by Elementis Specialties), BENTONE GEL GTCC V, and BENTONE GEL TN V (all manufactured by Elementis Specialties) can be used.

[0016] Component (A) may be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, preferably 8% by mass or less, more preferably 4% by mass or less, and even more preferably 2% by mass or less, as a solid content, in the entire composition of the water-in-oil emulsion composition, from the viewpoint of excellent adhesion to the skin, covering power after application, and stability. The content of component (A) is preferably 0.1 to 8% by mass, more preferably 0.3 to 4% by mass, and even more preferably 0.5 to 2% by mass, as a solid content, in the entire composition of the water-in-oil emulsion composition.

[0017] The component (B) used in the present invention is one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C. Being liquid at 25°C means that the viscosity at 25°C is 10,000 mPa·s or less. The viscosity of component (B) at 25° C. is preferably 4000 mPa·s or less, more preferably 600 mPa·s or less, even more preferably 200 mPa·s or less, and even more preferably 50 mPa·s or less. Here, the viscosity is measured under the following conditions. Viscosity measurement conditions: B-type viscometer (TVB-10 model, manufactured by Toki Sangyo Co., Ltd.), rotor No. 4, 60 rpm, 60 seconds

[0018] Among component (B), examples of phenyl-modified silicones that are liquid at 25° C. include methylphenylpolysiloxane, phenyltrimethicone, diphenylsiloxyphenyltrimethicone, diphenyldimethicone, trimethylsiloxyphenyldimethicone, and trimethylpentaphenyltrisiloxiane. Among these, from the viewpoint of excellent adhesion of the coating film after application, it is preferable to contain one or more types selected from methylphenylpolysiloxane, phenyltrimethicone, and diphenylsiloxyphenyltrimethicone, and it is more preferable to contain at least methylphenylpolysiloxane.

[0019] Examples of phenyl-modified silicones that are liquid at 25°C include commercially available products such as SH556 Fluid (manufactured by Dow Corning Toray Co., Ltd.) as phenyl trimethicone; KF-56A (manufactured by Shin-Etsu Chemical Co., Ltd.) as diphenylsiloxyphenyl trimethicone; DOWSIL FZ-209 (manufactured by Dow Toray Co., Ltd.) as methylphenyl polysiloxane; KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-54P (manufactured by Shin-Etsu Chemical Co., Ltd.) as diphenyl dimethicone; PDM-1000 (manufactured by Wacker Asahi Kasei Silicone Co., Ltd.) as trimethylsiloxyphenyl dimethicone; and PH-1555 HRI Cosmetic Fluid (manufactured by Dow Corning Toray Co., Ltd.) as trimethylpentaphenyl trisiloxane.

[0020] Of the components (B), examples of the alkyl-modified silicone that is liquid at 25° C. include silicone oils to which an alkyl group having 8 to 28 carbon atoms has been added. From the viewpoint of excellent compatibility with the skin, the alkyl group preferably has 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, even more preferably 8 to 16 carbon atoms, and even more preferably 8 to 12 carbon atoms.

[0021] Alkyl-modified silicones that are liquid at 25°C include those commonly used in cosmetics, such as caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, behenoxy dimethicone, and (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer. Among these, it is preferable to contain at least one or more selected from caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, and behenoxy dimethicone, and it is more preferable to contain at least caprylyl methicone.

[0022] As component (B), it is preferable to use a combination of a phenyl-modified silicone and an alkyl-modified silicone that are liquid at 25° C., from the viewpoint of excellent adhesion of the coating film after application and compatibility with the skin.

[0023] One or more kinds of component (B) can be used, and the content is preferably 1% by mass or more, more preferably 6% by mass or more, even more preferably 11% by mass or more, preferably 30% by mass or less, more preferably 21% by mass or less, and even more preferably 16% by mass or less, based on the total composition of the water-in-oil emulsion composition, from the viewpoint of excellent adhesion of the coating film after application and excellent compatibility with the skin. The content of component (B) is preferably 1 to 30% by mass, more preferably 6 to 21% by mass, and even more preferably 11 to 16% by mass, based on the total composition of the water-in-oil emulsion composition.

[0024] Component (C) is a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, and has a siloxane skeleton, an alkyl group having 10 or more carbon atoms, and a polyoxyalkylene group or a polyglyceryl group. The siloxane skeleton refers to a so-called silicone chain, and examples thereof include dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc. The length of the silicone chain is not particularly limited, and may be any length that is normally used in cosmetics, etc. The modified silicone of component (C) may be a block copolymer type containing a silicone chain and a polyoxyalkylene group or polyglyceryl group chain within the main chain, or it may be a terminal-modified type, or it may be a side-chain-modified type in which a polyoxyalkylene group or a polyglyceryl group is bonded as a side chain of a siloxane skeleton. The oxyalkylene of the polyoxyalkylene group contained in the modified silicone has one or more of ethylene oxide and propylene oxide in one molecule, and preferably has ethylene oxide and propylene oxide. The number of moles of oxyalkylene added in the polyoxyalkylene group is preferably 4 to 12, more preferably 8 to 10. The number of moles of glycerin added in the polyglyceryl group contained in the modified silicone is preferably 1 to 10, more preferably 1 to 4.

[0025] The modified silicone of component (C) preferably has an HLB of 2 to 7, and more preferably 2 to 5, from the viewpoints of spreading with a uniform thickness when spread, suppressing the occurrence of makeup breakdown and shine due to sebum, and improving makeup durability. In the present invention, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of a surfactant, and is calculated by the following Griffin formula. HLB = 20 x (molecular weight of hydrophilic group / total molecular weight)

[0026] Specific examples of modified silicones of component (C) include lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone, cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG / PPG-18 / 18 methicone, and the like.

[0027] Furthermore, the modified silicone of component (C) may be an alkyl glyceryl ether modified silicone represented by the following general formula (2).

[0028] [ka]

[0029] (R 11 and R 19 R are each independently a linear or branched hydrocarbon group, which may be the same or different, and which has a carbon number of 1 to 32 as a mode; 12 ~R 18 are each independently the same or different, a straight-chain or branched hydrocarbon group having 1 to 5 carbon atoms; Q is a straight-chain or branched divalent hydrocarbon group having 3 to 20 carbon atoms; R 20 and R 21 are each independently a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 28 carbon atoms, at least one of which is a hydrogen atom; p represents the number of repeating units, the average being 5 to 60; q represents the number of repeating units, the average being 2.5 to 10; and the constituent units of the repeating numbers p and q may be either a block copolymer or a random copolymer, provided that in the formula, at least one alkyl group having 10 or more carbon atoms is present.

[0030] In the general formula (2), R 11 and R 19 each independently represents a linear or branched hydrocarbon group having a carbon number mode of 1 to 32. Here, the carbon number mode refers to the carbon number of the hydrocarbon group that is most abundant among the chain lengths of the hydrocarbon groups having a distribution, and the carbon number mode is preferably 8 to 32, more preferably 12 to 28, and even more preferably 16 to 18.

[0031] In the general formula (2), R 12 ~R 18each independently represents a straight-chain or branched hydrocarbon group having 1 to 5 carbon atoms, and may be the same or different. By using a hydrocarbon group having a carbon number within this range, plasticization of the film caused by oils contained in food can be more effectively prevented. Specific examples include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, and pentyl; and branched-chain alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl. Of these, the methyl group is preferred from the viewpoint of availability.

[0032] In addition, in the general formula (2), Q represents a divalent linear or branched hydrocarbon group having 3 to 20 carbon atoms. Examples of the divalent hydrocarbon group having 3 to 20 carbon atoms represented by Q include linear alkylene groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, hexadecamethylene, and octadecamethylene; and branched alkylene groups such as propylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, and 2-ethyloctamethylene. Of these, nonamethylene, decamethylene, undecamethylene, dodecamethylene, and tridecamethylene are preferred.

[0033] Also, R 20 and R 21are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 28 carbon atoms, at least one of which is a hydrogen atom. Examples of linear or branched hydrocarbon groups having 1 to 28 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, doeicosyl, tetraeicosyl, hexaeicosyl, and octaeicosyl; and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, and 1-heptyldecyl. Of these, R 20 and R 21 and are preferably both hydrogen atoms.

[0034] In the general formula (2), p represents the number of repeating units, and is an average value of 5 to 60, preferably 20 to 30. Here, the average value of p is 1 H-NMR was used to determine the R 14 and R 15 It is calculated from the intensity ratio of the peaks assigned to Furthermore, q represents the number of repeating units, and is an average value of 2.5 to 10, and preferably 3.0 to 6.0. Here, the average value of q is 1 H-NMR was used to determine the OR ratio based on the terminal methyl groups of the hydrocarbon groups introduced at both ends of the polysiloxane. 20 and OR 21 It is calculated from the intensity ratio of the peaks assigned to the added methine and methylene hydrogen. The constituent units having repeating numbers p and q may be either block copolymers or random copolymers, but are preferably random copolymers. Also, it is preferable that p is greater than q.

[0035] The alkyl glyceryl ether-modified silicone represented by general formula (2) can be produced, for example, by subjecting an organohydrogenpolysiloxane having at least one silicon-hydrogen bond to a hydrosilylation reaction with the corresponding alkenyl glyceryl ether, according to the method described in JP-A-4-134013.

[0036] As the alkyl glyceryl ether-modified silicone represented by general formula (2), glyceryl undecyl dimethicone and bis alkyl (C16-18) glyceryl undecyl dimethicone are preferred from the viewpoints of improving storage stability at high temperatures, as the moisture present on the skin and the ester oil of component (D) form a network structure during and after application to form a coating film on the skin that is resistant to makeup smudging, thereby suppressing makeup smudging and the occurrence of shine caused by sebum, and improving makeup durability.

[0037] Component (C) may be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 12% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total composition of the water-in-oil emulsion composition, from the viewpoint of suppressing the occurrence of makeup breakdown and greasiness due to sebum, and improving makeup durability. The content of component (C) is preferably 0.1 to 12% by mass, more preferably 1 to 7% by mass, and even more preferably 2 to 5% by mass, based on the total composition of the water-in-oil emulsion composition.

[0038] In the present invention, the mass ratio (A) / (C) of component (A) to component (C) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, preferably 3 or less, more preferably 1 or less, and even more preferably 0.6 or less, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from coming off even after a long period of time has passed, providing excellent makeup durability, and providing excellent emulsion stability at high temperatures. The mass ratio (A) / (C) of component (A) to component (C) is preferably 0.05 to 3, more preferably 0.1 to 1, and even more preferably 0.2 to 0.6.

[0039] In the present invention, the mass ratio (B) / (C) of component (B) to component (C) is preferably 0.5 or more, more preferably 1 or more, even more preferably 2.5 or more, preferably 15 or less, more preferably 7 or less, and even more preferably 5.5 or less, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from coming off even after a long period of time has passed, providing excellent makeup durability, and providing excellent emulsion stability at high temperatures. The mass ratio (B) / (C) of component (B) to component (C) is preferably 0.5 to 15, more preferably 1 to 7, and even more preferably 2.5 to 5.5.

[0040] Component (D) is an ester oil that is liquid at 25°C. Here, liquid means that the viscosity at 25°C is 10,000 mPa·s or less, similar to component (B). The viscosity is measured in the same manner as for component (B). The ester oil of component (D) may be any oil that is commonly used in cosmetics, and examples thereof include monoester oils such as ethylhexyl paramethoxycinnamate, cetyl ethylhexanoate, octyldodecyl myristate, isotridecyl isononanoate, isononyl isononanoate, etc.; diester oils such as neopentyl glycol dicaprate, propylene glycol dicaprate, diisostearyl malate, etc.; triester oils such as glyceryl tri-2-ethylhexanoate, tri(caprylic acid / capric acid)glyceryl, etc.; and tetraester oils such as dipentaerythrityl tetraisostearate, etc.

[0041] Among these, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from coming off even after a long period of time, and providing excellent makeup durability, preferred are ester oils having a molecular weight of 300 or more.Moreover, it is preferred to contain one or more types selected from monoesters and diesters, more preferred to contain one or more types selected from diisostearyl malate, neopentyl glycol dicaprate, isotridecyl isononanoate, cetyl ethylhexanoate, and propylene glycol dicaprate, and even more preferred to contain at least one or two types selected from diisostearyl malate and neopentyl glycol dicaprate.

[0042] Component (D) may be used alone or in combination of two or more, and the content is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 25% by mass or less, and even more preferably 16% by mass or less, based on the viewpoints of improved adhesion to the skin, good fit to the skin, no makeup loss even after a long time has passed, and excellent makeup durability, based on the total composition of the water-in-oil emulsion composition. The content of component (D) is preferably 3 to 40% by mass, more preferably 6 to 25% by mass, and even more preferably 10 to 16% by mass, based on the total composition of the water-in-oil emulsion composition.

[0043] In the present invention, the mass ratio (B) / (D) of component (B) to component (D) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from coming off even after a long period of time has passed, providing excellent makeup durability, and providing excellent emulsion stability at high temperatures. The mass ratio (B) / (D) of component (B) to component (D) is preferably 0.2 to 5, more preferably 0.4 to 3, and even more preferably 0.6 to 1.5.

[0044] The water-in-oil emulsion composition of the present invention may further contain a hydrophobically treated color pigment from the viewpoint of improving the covering power of the finished makeup and the feeling of a clean makeup finish on the entire face. 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. 220, Red No. 226, Red No. 227, Red No. 229, Red No. 230, Red No. 231, Red No. 232, Red No. 233, Red No. 234, Red No. 235, Red No. 236, Red No. 237, Red No. 238, Red No. 239, Red No. 240, Red No. 241, Red No. 242, Red No. 243, Red No. 244, Red No. 245, Red No. 246, Red No. 247, Red No. 248, Red No. 249 ...9, Red No. 240, Red No. 241, Red No. 242, Red No. 243, Red No. 244, Red No. 245, Red No. 246, Red No. 247, Red No Examples of the pigments include synthetic organic pigments, organic dyes and their lake pigments, such as Color 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 404; and natural organic dyes, such as β-carotene, caramel, and paprika dye. Examples of the pigments include composites of these color pigments and mixed pigments in which these color pigments are diluted with extender pigments such as barium sulfate and talc. From the viewpoint of covering the skin and imparting an aesthetic makeup effect, the color pigment preferably contains a metal oxide, more preferably contains one or more types selected from titanium oxide, zinc oxide, yellow iron oxide, black iron oxide, and red iron oxide, and further preferably contains one or more types selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide.

[0045] The hydrophobic treatment of these color pigments is not limited as long as it is a treatment that is performed on ordinary cosmetic powders, and dry treatment, wet treatment, etc. may be performed using a surface treatment agent such as a silicone compound, a metal soap, an amino acid compound, lecithin, an oil agent, or an organic titanate. Specific examples of surface treatment agents include alkylalkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and triethoxycaprylylsilane, silicone compounds such as dimethylpolysiloxane, methylhydrogenpolysiloxane, cyclic silicone, crosslinked silicone, silicone resin, and acrylic modified silicone; metal soaps such as aluminum stearate, aluminum myristate, zinc stearate, and magnesium stearate; amino acids such as proline, hydroxyproline, alanine, glycine, sarcosine, glutamic acid, aspartic acid, lysine, and derivatives thereof; acylated amino acids such as stearoyl glutamic acid, lauroyl aspartic acid, dilauroyl glutamic acid lysine, and lauroyl lysine; lecithin and hydrogenated lecithin; oils such as polyisobutylene, wax, oils and fats, and fatty acids; and organic titanates such as isopropyl triisostearoyl titanate. The acylated amino acid includes salts of acylated amino acids, and examples of the salts of acylated amino acids include Na, Ca, Al, Mg, Zn, Zr, and Ti salts, and preferably includes one or more selected from Na and Ca salts, and more preferably includes Na salts. Also, the acylated amino acid salts preferably include one or more selected from disodium stearoyl glutamate and sodium lauroyl aspartate, and more preferably includes disodium stearoyl glutamate, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, excellent cosmetic durability, and excellent stability at high temperatures. From the viewpoints of improving adhesion to the skin, providing a good fit to the skin, excellent cosmetic durability, and excellent stability at high temperatures, the surface treatment agent preferably contains one or more selected from silicone compounds, acylated amino acids, and organic titanates, more preferably contains one or more selected from dimethylpolysiloxane, methylhydrogenpolysiloxane, alkylalkoxysilane, disodium stearoyl glutamate, sodium lauroyl aspartate, and isopropyl triisostearoyl titanate, even more preferably contains one or more selected from dimethylpolysiloxane, alkylalkoxysilane, disodium stearoyl glutamate, and isopropyl triisostearoyl titanate, and even more preferably contains disodium stearoyl glutamate.

[0046] The hydrophobization treatment can be carried out according to a conventional method. The amount of the hydrophobization treatment is preferably 0.1 to 15 mass %, and more preferably 1 to 12 mass %, based on the amount of the coated powder, from the viewpoint of improving dispersibility in a solvent.

[0047] The hydrophobized color pigment may be one or more, and the content is preferably 1% by mass or more, more preferably 3% 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, based on the viewpoints of improved skin adhesion, good skin fit, excellent cosmetic durability, and excellent stability at high temperatures. The content of the hydrophobized color pigment is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total composition of the water-in-oil emulsion composition.

[0048] The water-in-oil emulsion composition of the present invention may further contain a volatile oil. Volatile means that it has a flash point of −4 to 88° C. Examples of volatile oils include volatile silicone oils and volatile hydrocarbon oils. Examples of volatile silicone oils include linear dimethylpolysiloxanes such as hexamethyldisiloxane, octamethyltrisiloxane (1cs), decamethyltetrasiloxane (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. 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. Among these, hydrocarbon oils having 8 to 16 carbon atoms are preferred, hydrocarbon oils having 10 to 16 carbon atoms are more preferred, and hydrocarbon oils having 12 carbon atoms are even more preferred.

[0049] From the viewpoints of forming a uniform coating film on the skin, improving adhesion, and improving the fit to the skin, the volatile oil is at least one oil selected from hydrocarbon oils and silicone oils, and preferably includes at least one oil selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxane having a kinetic viscosity of 2 cSt or less at 25° C. The kinetic viscosity can be measured, for example, using an Ubbelohde viscometer.

[0050] Commercially available products of hexamethyldisiloxane and dimethylpolysiloxane with a kinematic viscosity of 2 cSt or less at 25°C include "KF-96L-0.65cs" (hexamethyldisiloxane), "TMF1.5", "KF-96L-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs", and "KF-96L-2cs" manufactured by Shin-Etsu Chemical Co., Ltd., "SH200C Fluid 1cs" and "SH200C Fluid 1.5cs" manufactured by Dow Corning Toray Co., Ltd., "TSF451-0.65" manufactured by Momentive Performance Materials Japan, LLC, "BELSIL DM0.65" manufactured by Wacker Asahi Kasei Silicone Co., Ltd., and "XIAMETER PMX-200 SILICONE FLUID 0.65CS" manufactured by Dow Toray Co., Ltd., and the like.

[0051] The volatile oil may be used alone or in combination of two or more, and the content is preferably 1% by mass or more, more preferably 4% by mass or more, even more preferably 8% by mass or more, preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less, based on the total composition of the water-in-oil emulsion composition, from the viewpoint of forming a uniform coating film on the skin, improving adhesion, and improving the fit to the skin. The content of the volatile oil is preferably 1 to 50% by mass, more preferably 4 to 35% by mass, and even more preferably 8 to 25% by mass, based on the total composition of the water-in-oil emulsion composition.

[0052] From the viewpoints of being environmentally friendly, having excellent usability, and being excellent in stability at high temperatures, the water-in-oil emulsion composition of the present invention preferably contains no more than 1% by mass of organic resin powder such as microplastics in the total composition, more preferably no more than 0.1% by mass, and even more preferably is substantially free of such powder. Specifically, it refers to organic resin powder other than cellulose powder that has excellent biodegradability. Examples of the organic resin powder include crosslinked or non-crosslinked organic resin powders such as powders of one or more polymers or copolymers selected from polyamide resin, nylon resin, polyester resin, polyethylene resin, polytetrafluoroethylene resin, polypropylene resin, polystyrene resin, benzoguanamine resin, polymethylbenzoguanamine resin, polyurethane resin, vinyl resin, fluororesin, acrylic resin, and melamine resin; butyl acrylate-vinyl acetate copolymer, styrene-acrylic acid copolymer, silicone resin, and divinylbenzene-styrene copolymer.

[0053] In the water-in-oil emulsion composition of the present invention, the water content is preferably 3 to 50 mass % of the total composition, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, from the viewpoint of forming a stable emulsion composition.

[0054] In addition to the above-mentioned components, the water-in-oil emulsion composition of the present invention can optionally contain various components that are commonly used in cosmetics. Examples of these components include oily components other than those mentioned above, surfactants, water-soluble polymers, antioxidants, UV absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, disinfectants, skin activators, etc.

[0055] The water-in-oil emulsion composition of the present invention can be produced according to a conventional method, and can be made into a dosage form such as a liquid, emulsion, paste, cream, gel, or solid. Furthermore, the water-in-oil emulsion composition of the present invention can be made into a water-in-oil emulsion cosmetic, and can be used, for example, as makeup cosmetics such as a makeup base, foundation, concealer, blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc.; UV protection cosmetics such as a sunscreen lotion, a sunscreen cream, etc.; skin care cosmetics such as a skin care lotion, a skin care cream, a BB cream, a beauty serum, etc. In particular, it is suitable as a liquid water-in-oil emulsion cosmetic.

[0056] From the viewpoints of forming a uniform coating film on the skin, improving adhesion, and improving the fit to the skin, the water-in-oil emulsion composition of the present invention preferably has a viscosity at 30°C of 3,000 to 30,000 mPa s, and more preferably 5,000 to 25,000 mPa s. The viscosity was measured using a B-type viscometer (TVB-10 model, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 12 rpm, a measurement time of 30 seconds, and a temperature of 30° C. The following rotors were used depending on the viscosity of the composition. Viscosity 2,500 mPa·s or more but less than 10,000 mPa·s: Rotor No. 3, Viscosity 10,000 mPa·s or more: Rotor No. 4 In addition, in Table 1, the viscosity of the water-in-oil emulsion composition of Example 1 was 12000 mPa·s at 30°C.

[0057] The water-in-oil emulsion composition of the present invention can be used as a water-in-oil emulsion composition for impregnation by impregnating a support, taking it from the support with a finger or an applicator, and applying it to the skin. The support is one that is impregnated with and supports the water-in-oil emulsion composition having fluidity, and examples thereof include nonwoven fabrics made of a single or mixed material such as resin, pulp, cotton, etc., resin-treated fibrous bodies, foams such as sponges, porous bodies with a continuous mechanism, and aggregates of fibers. Examples of the material include NBR (acrylonitrile butadiene rubber), SBR (styrene butadiene rubber), NR (natural rubber), urethane, nylon, polyolefin, polyester, EVA (ethylene vinyl acetate), PVA (polyvinyl alcohol), silicone elastomer, etc., but are not limited to these materials as long as the support can contain the contents. Among them, an aggregate of polyester fibers is preferable, and an aggregate of polyester fibers having a layered structure in which the front layer and the back layer are connected by crosslinked yarns may be used. A fibrous body molded using polyester fibers, which preferably has a hardness of 40 to 60 (measured by an F hardness scale) and an apparent density (based on JIS K 6400-1) of 0.006 to 0.1 g / cm3, is preferable. 3 Preferably, the density is 0.02 to 0.1 g / cm 3 It is more preferable to use one of the following:

[0058] Among these, the fiber aggregate includes an aggregate of fibers having a core-sheath structure. The core-sheath structure fiber is composed of fibers in which the periphery of the core part is surrounded by the sheath part, and the fibers are preferably composed of a thermoplastic resin, and the core part is preferably composed of a thermoplastic resin having a higher melting point than the sheath part. In addition, the material of the core part and the sheath part in the core-sheath structure fiber is not particularly limited, but polyolefin resin is preferable because it is not deteriorated over time by the components of the emulsion composition.

[0059] Among polyolefin resins, those in which the core portion is made of polypropylene (melting point 165° C.) and the sheath portion is made of polyethylene (melting point 130° C.), or those in which the core portion is made of polypropylene (melting point 165° C.) and the sheath portion is made of polybutene (melting point 127° C.) can be used. From the viewpoint of impregnation and retention of the emulsion composition, the core-sheath fiber preferably has a thickness of 2.0 to 15 dtex, more preferably 2.0 to 13 dtex.

[0060] Furthermore, eccentric sheath-core composite fibers are preferred in terms of three-dimensional crimping. The shape of the core of the eccentric sheath-core composite fiber may be circular or irregular, such as elliptical, Y-shaped, or X-shaped, and the cross-sectional shape of the eccentric sheath-core composite fiber may be circular or irregular, such as elliptical, Y-shaped, X-shaped, well-shaped, polygonal, or star-shaped, or hollow.

[0061] The core-sheath fiber aggregate can be manufactured by a known method. Examples include a thermal bonding method, a needle punch method, and a hydroentanglement method. A fiber having a core-sheath structure in which a part of the sheath portion is fused is more preferable as the core-sheath fiber aggregate. The manufacturing method is not limited, and can be, for example, a hot air conveyor furnace type, a mold forming type, or a method using a mesh belt (the method described in Japanese Patent No. 4195043), and then cut into a size suitable for the holder by a press or other cutting process.

[0062] The aggregate of fibers having a core-sheath structure has an apparent density (based on JIS K 6400-1) of 0.02 to 0.1 g / cm 3 is more preferred from the viewpoint of impregnation and retention of the emulsion composition. The size of the aggregate of core-sheath fibers is not particularly limited, and can be determined according to ease of use or the size of the container in which it is stored.

[0063] The support may be in a state where it is wholly or partially impregnated with the water-in-oil emulsion composition, or may be disposed as a screen net on the surface of the water-in-oil emulsion composition. In the weaving form of the screen net, the method of constructing the yarn weave, the shape of the yarn, the number of twists of the yarn, the thickness, the material, etc. are not limited, and for example, any of plain weave, 1 / 2 twill weave, 2 / 1 twill weave, twill weave, georgette weave, half georgette weave, and satin weave are acceptable. The screen net may be made of, for example, polyurethane, TPE (thermoplastic elastomer), polyester, polyether, acrylic, olefin, etc. The thickness of the fibers constituting the screen net is preferably 0.01 to 1.0 mm.

[0064] It is preferable that the screen net is completely attached to the support impregnated with the emulsion composition by being in close contact with it, or that the absorbent and the screen net are not attached to each other and are positioned at a distance of 0.1 to 3.0 mm from the screen net.

[0065] The water-in-oil emulsion composition of the present invention can be used by impregnating such a support, taking it from the support with a finger or an applicator, and applying it to the skin. The water-in-oil emulsion composition of the present invention can be used by impregnating such a support, placing a screen net adjacent to it, and then taking the composition from the screen net with a finger or an applicator and applying it to the skin. Applicators for applying to the skin typically include sponges, puffs, tips, etc., which are used when applying liquid cosmetics to the skin.

[0066] The water-in-oil emulsion composition of the present invention can be used as a cosmetic product by incorporating a support impregnated with the composition into a compact container. The water-in-oil emulsion composition of the present invention can be used as a cosmetic product contained in a compact container by placing a support impregnated with the composition adjacent to a screen net. Furthermore, a cosmetic kit can be made by combining a holder impregnated with the water-in-oil emulsion composition of the present invention with a compact container.

[0067] The water-in-oil emulsion composition of the present invention can be used by impregnating a support, but can also be suitably used as a normal liquid water-in-oil emulsion cosmetic, particularly a liquid foundation, without being impregnated into a support.

[0068] In relation to the above-mentioned embodiment, the present invention further discloses the following compositions, etc.

[0069] <1> The following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C A water-in-oil type emulsion composition for impregnation comprising:

[0070] <2> The following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The cosmetic product comprises a holder impregnated with a water-in-oil emulsion composition containing the above-mentioned and housed in a compact container.

[0071] <3> The component (A) is preferably a cationically modified clay mineral obtained by substituting a layered clay mineral with a quaternary ammonium salt type cationic surfactant, and the layered clay mineral is represented by the following formula (1):

[0072] [ka]

[0073] (In the formula, R 1 represents an alkyl group having 10 to 22 carbon atoms or a benzyl group, R 2 represents a methyl group or an alkyl group having 10 to 22 carbon atoms; R 3 and R 4 represents an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or a methyl sulfate residue. More preferred is a cationic modified clay mineral obtained by substituting with a quaternary ammonium salt type cationic surfactant represented by the formula: and more preferred is one or more selected from dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, and benzyl dimethyl stearyl ammonium hectorite. Even more preferred is one or more selected from dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite. Even more preferred is dimethyl distearyl ammonium hectorite. <2> The cosmetic product described. <4> The content of component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, preferably 8% by mass or less, more preferably 4% by mass or less, and even more preferably 2% by mass or less, as a solid content, in the total composition of the water-in-oil emulsion composition. <2> or <3> The cosmetic product described.

[0074] <5> The phenyl-modified silicone of component (B) which is liquid at 25°C is preferably methylphenyl polysiloxane, phenyl trimethicone, diphenyl siloxy phenyl trimethicone, diphenyl dimethicone, trimethyl siloxy phenyl dimethicone, or trimethyl pentaphenyl trisiloxane, more preferably containing one or more selected from methylphenyl polysiloxane, phenyl trimethicone, and diphenyl siloxy phenyl trimethicone, and even more preferably containing at least methylphenyl polysiloxane. <2> ~ <4> 10. A cosmetic composition according to any one of the preceding claims. <6> The alkyl-modified silicone of component (B) which is liquid at 25°C is preferably caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, behenoxy dimethicone, (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer, more preferably containing at least one or more selected from caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, and behenoxy dimethicone, and further preferably containing at least caprylyl methicone. <2> ~ <4> 10. A cosmetic composition according to any one of the preceding claims.

[0075] <7> The component (B) is preferably a combination of a phenyl-modified silicone and an alkyl-modified silicone that are liquid at 25°C. <2> ~ <6> 10. A cosmetic composition according to any one of the preceding claims. <8> The content of component (B) is preferably 1% by mass or more, more preferably 6% by mass or more, and even more preferably 11% by mass or more, and is preferably 30% by mass or less, more preferably 21% by mass or less, and even more preferably 16% by mass or less, based on the total composition of the water-in-oil emulsion composition. <2> ~ <7> 10. A cosmetic composition according to any one of the preceding claims.

[0076] <9> The component (C) preferably has an HLB value of 2 to 7, more preferably an HLB value of 2 to 5. <2> ~ <8> 10. A cosmetic composition according to any one of the preceding claims. <10> The component (C) preferably contains a glyceryl ether silicone modified with alkyl groups at both ends. <2> ~ <9> 10. A cosmetic composition according to any one of the preceding claims. <11> The component (C) preferably contains at least one or more selected from lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone, cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl PEG / PPG-18 / 18 methicone. <2> ~ <10> 10. A cosmetic composition according to any one of the preceding claims.

[0077] <12> Component (C) is preferably a compound represented by the general formula (2):

[0078] [ka]

[0079] (R 11 and R 19 R are each independently a linear or branched hydrocarbon group, which may be the same or different, and which has a carbon number of 1 to 32 as a mode; 12 ~R 18 are each independently the same or different, a straight-chain or branched hydrocarbon group having 1 to 5 carbon atoms; Q is a straight-chain or branched divalent hydrocarbon group having 3 to 20 carbon atoms; R 20 and R 21 are each independently a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 28 carbon atoms, at least one of which is a hydrogen atom; p represents the number of repeating units, the average being 5 to 60; q represents the number of repeating units, the average being 2.5 to 10; and the constituent units of the repeating numbers p and q may be either a block copolymer or a random copolymer, provided that in the formula, at least one alkyl group having 10 or more carbon atoms is present. The alkyl glyceryl ether modified silicone represented by the formula (I) is preferably glyceryl undecyl dimethicone or bisalkyl (C16-18) glyceryl undecyl dimethicone. <2> ~ <9> 10. A cosmetic composition according to any one of the preceding claims.

[0080] <13> The content of component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, and is preferably 12% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total composition of the water-in-oil emulsion composition. <2> ~ <12> 10. A cosmetic composition according to any one of the preceding claims.

[0081] <14> The mass ratio (A) / (C) of the component (A) to the component (C) is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and is preferably 3 or less, more preferably 1 or less, and even more preferably 0.6 or less. <2> ~ <13> 10. A cosmetic composition according to any one of the preceding claims. <15> The mass ratio (B) / (C) of the component (B) to the component (C) is preferably 0.5 or more, more preferably 1 or more, even more preferably 2.5 or more, and is preferably 15 or less, more preferably 7 or less, and even more preferably 5.5 or less. <2> ~ <14> 10. A cosmetic composition according to any one of the preceding claims.

[0082] <16> Component (D) is preferably an ester oil having a molecular weight of 300 or more, more preferably containing one or more selected from monoesters and diesters, even more preferably containing one or more selected from diisostearyl malate, neopentyl glycol dicaprate, isotridecyl isononanoate, cetyl ethylhexanoate, and propylene glycol dicaprate, and even more preferably containing at least one or two selected from diisostearyl malate and neopentyl glycol dicaprate. <2> ~ <15> 10. A cosmetic composition according to any one of the preceding claims. <17> The content of component (D) is preferably 3% by mass or more, more preferably 6% by mass or more, and even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 25% by mass or less, and even more preferably 16% by mass or less, based on the total composition of the water-in-oil emulsion composition. <2> ~ <16> 10. A cosmetic composition according to any one of the preceding claims.

[0083] <18> The mass ratio (B) / (D) of the component (B) to the component (D) is preferably 0.2 or more, more preferably 0.4 or more, and even more preferably 0.6 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less. <2> ~ <17> 10. A cosmetic composition according to any one of the preceding claims. <19> Preferably, the content of component (A) is 0.1 to 8 mass%, the content of component (B) is 1 to 30 mass%, the content of component (C) is 0.1 to 12 mass%, and the content of component (D) is 3 to 40 mass%. <2> ~ <18> 10. A cosmetic composition according to any one of the preceding claims.

[0084] <20> It is preferable that the water-in-oil emulsion composition further contains a hydrophobized color pigment, and it is more preferable that the hydrophobized color pigment is contained in an amount of 1 to 30 mass % based on the total composition of the water-in-oil emulsion composition. <2> ~ <19> 10. A cosmetic composition according to any one of the preceding claims. <21> The color pigment 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 further preferably contains one or more selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide. <20> The cosmetic product described.

[0085] <22> The surface treatment agent for hydrophobization preferably contains one or more selected from silicone compounds, acylated amino acids, and organic titanates, more preferably contains one or more selected from dimethylpolysiloxane, methylhydrogenpolysiloxane, alkylalkoxysilane, disodium stearoyl glutamate, sodium lauroyl aspartate, and isopropyl triisostearoyl titanate, further preferably contains one or more selected from dimethylpolysiloxane, alkylalkoxysilane, disodium stearoyl glutamate, and isopropyl triisostearoyl titanate, and even further preferably contains disodium stearoyl glutamate. <20> or <21> The cosmetic product described. <23> The content of the hydrophobized color pigment is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total composition of the water-in-oil emulsion composition. <20> ~ <22> 10. A cosmetic composition according to any one of the preceding claims.

[0086] <24> The water-in-oil emulsion composition preferably further contains a volatile oil, and more preferably contains the volatile oil in an amount of 1 to 50% by mass based on the total composition of the water-in-oil emulsion composition. <2> ~ <23> 10. A cosmetic composition according to any one of the preceding claims. <25> The volatile oil is preferably one or more selected from volatile hydrocarbon oils and volatile silicone oils, and more preferably one or more selected from isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxane having a kinetic viscosity of 2 cSt or less at 25° C. <24> The cosmetic product described. <26> The content of the volatile oil is preferably 1% by mass or more, more preferably 4% by mass or more, and even more preferably 8% by mass or more, and is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less, based on the total composition of the water-in-oil emulsion composition. <24> or <25> The cosmetic product described.

[0087] <27> The water-in-oil emulsion composition preferably contains no more than 1% by mass, more preferably no more than 0.1% by mass, and even more preferably is substantially free of organic resin powder. <2> ~ <26> 10. A cosmetic composition according to any one of the preceding claims. <28> The water-in-oil emulsion composition preferably has a water content of 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass, based on the total composition. <2> ~ <27> 10. A cosmetic composition according to any one of the preceding claims.

[0088] <29> The water-in-oil emulsion composition is preferably a liquid water-in-oil emulsion cosmetic. <2> ~ <28> 10. A cosmetic composition according to any one of the preceding claims. <30> The viscosity of the water-in-oil emulsion composition at 30° C. is preferably 3,000 to 30,000 mPa·s, and more preferably 5,000 to 25,000 mPa·s. <2> ~ <29> 10. A cosmetic composition according to any one of the preceding claims.

[0089] <31> The support is preferably a foam, a porous body, or an aggregate of fibers, and more preferably an aggregate of polyester fibers. <2> ~ <30> 10. A cosmetic composition according to any one of the preceding claims. <32> The water-in-oil emulsion composition impregnated in the support is taken from the support with a finger or an applicator and applied to the skin. <2> ~ <31> A method for using the cosmetic composition according to any one of the preceding claims.

[0090] <33> The following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The cosmetic kit comprises a holder impregnated with a water-in-oil emulsion composition containing the above and a compact container.

[0091] <34> The following components (A), (B), (C) and (D): (A) Cation-modified clay minerals substituted with quaternary ammonium ions; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C A water-in-oil emulsion composition comprising: EXAMPLES

[0092] Production Example 1 (Production of both terminal alkyl (C16-18) modified dimethylsiloxane-methyl (undecyl glyceryl ether) siloxane copolymer): (1) STEP-1 (synthesis of tetramethyldisiloxane having alkyl groups at both ends of the silicone chain that are different from the other alkyl groups in the silicone chain): 44.8 g of 1,1,3,3-tetramethyldisiloxane and 1.0 g of Spires catalyst (a 2% by mass solution of chloroplatinic acid in 2-propanol) were added to a three-neck flask and heated to 70°C. 174.2 g of α-olefin (Idemitsu Kosan's "Linealene 168", a 57 / 43 (mass ratio) mixture of carbon numbers 16 and 18) was added dropwise at 70°C under a nitrogen atmosphere, and the mixture was stirred for 2 hours. After cooling, the reaction system was neutralized with an aqueous sodium hydroxide solution and purified by distillation under reduced pressure. The resulting product 1 H-NMR spectrum (400 MHz) confirmed that the product obtained was a 1,1,3,3-tetramethyldisiloxane derivative having alkyl groups with 16 and 18 carbon atoms at both ends (22.1 g, yield: 85%).

[0093] (2) STEP-2 (synthesis of organohydrogenpolysiloxane having alkyl groups at both ends of the silicone chain that are different from the other alkyl groups in the silicone chain and having silicon-hydrogen bonds in the silicone chain): 44.8 g of the 1,1,3,3-tetramethyldisiloxane derivative with alkyl groups of 16 and 18 carbon atoms at both ends synthesized in (1), 78.6 g of decamethylcyclopentasiloxane, 19.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 50 g of n-heptane, and 5 g of activated clay were added to a three-neck flask and refluxed for 12 hours. After cooling, the mixture was purified by distillation under reduced pressure. 1 H-NMR spectrum confirmed that the product obtained was a dimethylsiloxane / methylsiloxane copolymer (p=23, q=4) having alkyl groups with 16 and 18 carbon atoms at both ends (132.8 g, yield: 95%).

[0094] (3) STEP-3 (Synthesis of polysiloxane in which both ends are substituted with alkyl groups and the side chains are graft-modified with alkyl glyceryl ether groups): 50.0 g of the dimethylsiloxane / methylsiloxane copolymer having alkyl groups with 16 and 18 carbon atoms at both ends, synthesized in (2), 61.0 g of 10-undecenyl glyceryl ether, and 0.25 g of 5% by mass platinum-supported carbon catalyst were added to a three-neck flask and stirred at 70°C for 3 hours. After cooling, the mixture was purified by distillation under reduced pressure. 1 H-NMR spectrum confirmed that the product was a dimethylsiloxane-methyl(undecylglyceryl ether)siloxane copolymer (p=23, q=4) bearing alkyl groups with carbon numbers of 16 and 18 at both ends (63.0 g, yield: 95%). The resulting copolymer is a random copolymer represented by the general formula (2) as shown below. R 11 and R 19 = an alkyl group having a mode of 18 carbon atoms; R 12 ~R 18 = methyl group, Q=an alkylene group having 11 carbon atoms; R 20 and R 21 = Hydrogen atom p(mean)=23, q(average value)=4.0

[0095] Examples 1 to 8, Comparative Example 1 Water-in-oil emulsion cosmetics (liquid foundations) having the compositions shown in Tables 1 and 2 were produced. The obtained water-in-oil emulsion cosmetic was impregnated into a support, and after 6 hours, the cosmetic was evaluated for its staying power, fit to the skin, and emulsion stability. The results are shown in Tables 1 and 2.

[0096] (Manufacturing method) A water-in-oil emulsion cosmetic (liquid foundation) was produced by adding and dispersing the powder components to the oil phase components containing the components (A), (B), (C), and (D), and then adding the water phase components and stirring with a homomixer. The obtained water-in-oil emulsion cosmetic was impregnated into a support (an assembly of polyester fibers).

[0097] (Evaluation method) (1) How well your makeup stays in place after 6 hours: Three expert panelists took each water-in-oil emulsion composition (support-impregnated foundation) with a puff, applied it to the skin, and evaluated the makeup retention after 6 hours according to the following criteria. The results were shown as the total score of the three panelists. 5;My makeup doesn't come off at all. 4; Makeup does not come off. 3; My makeup doesn't come off easily. 2: Makeup is slightly worn. 1: Makeup has come off.

[0098] (2) Fit to the skin: Three expert panelists took each water-in-oil emulsion composition (support-impregnated foundation) with a puff and applied it to the skin, and sensory evaluation was performed according to the following criteria. The results were shown as the total score of the three panelists. 5. Very good adhesion to the skin. 4;Good adhesion to the skin. 3; Fairly good adhesion to skin. 2;It doesn't adhere well to the skin. 1: It doesn't adhere well to the skin.

[0099] (3) Emulsion stability: Each water-in-oil emulsion composition (support-impregnated foundation) was stored in an environment of 40° C. for one month, and then the appearance and properties were visually evaluated according to the following criteria. A: No decrease in viscosity or separation was observed. B: Viscosity decreases slightly. C: Viscosity is slightly decreased and oily bleeding is observed. D: Separation is observed.

[0100] [Table 1]

[0101] [Table 2]

[0102] The water-in-oil emulsion cosmetics (liquid foundations) of Examples 1 to 8 can be filled in containers such as bottles and tubes without being impregnated into a support, and can be taken directly from the container with a finger or an applicator and applied to the skin. Even in this case, the cosmetics have excellent makeup durability, fit to the skin, and emulsion stability.

Claims

1. The following components (A), (B), (C) and (D): (A) a cationically modified clay mineral substituted with a quaternary ammonium ion; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C A water-in-oil type emulsion composition for impregnation comprising:

2. A cosmetic product comprising a holder impregnated with the water-in-oil emulsion composition according to claim 1 and housed in a compact container.

3. The cosmetic preparation according to claim 2, wherein component (C) comprises a glyceryl ether-modified silicone modified at both ends with alkyl groups.

4. Component (C) is represented by general formula (2): 【Chemistry 1】 (R 11 and R 19 are each independently a linear or branched hydrocarbon group, which may be the same or different, and which has a carbon number of 1 to 32 as a mode; R 12 ~R 18 are each independently the same or different, a straight-chain or branched hydrocarbon group having 1 to 5 carbon atoms; Q is a divalent straight-chain or branched hydrocarbon group having 3 to 20 carbon atoms; R 20 and R 21 are each independently a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 28 carbon atoms, at least one of which is a hydrogen atom; p represents the number of repeating units, the average being 5 to 60; q represents the number of repeating units, the average being 2.5 to 10; and the constituent units of the repeating numbers p and q may be either a block copolymer or a random copolymer, provided that in the formula, at least one alkyl group having 10 or more carbon atoms is present.

3. The cosmetic according to claim 2, comprising an alkyl glyceryl ether-modified silicone represented by the formula:

5. 4. The cosmetic preparation according to claim 2 or 3, wherein the content of component (A) is 0.1 to 8 mass%, the content of component (B) is 1 to 30 mass%, the content of component (C) is 0.1 to 12 mass%, and the content of component (D) is 3 to 40 mass%.

6. 4. The cosmetic preparation according to claim 2 or 3, wherein the mass ratio (B) / (C) of component (B) to component (C) is 0.5 to 15.

7. 4. The cosmetic preparation according to claim 2 or 3, wherein the water-in-oil emulsion composition further contains 1 to 30% by mass of a hydrophobically treated color pigment.

8. The cosmetic preparation according to claim 2 or 3, wherein the water-in-oil emulsion composition further contains 1 to 50% by mass of a volatile oil.

9. 4. The cosmetic according to claim 2 or 3, wherein the water-in-oil emulsion composition has a viscosity at 30° C. of 3,000 to 30,000 mPa·s.

10. 4. The cosmetic preparation according to claim 2 or 3, wherein the support is a foam, a porous body, or an aggregate of fibers.

11. 4. The cosmetic according to claim 2 or 3, wherein the support is an assembly of polyester fibers.

12. 4. A method for using the cosmetic preparation according to claim 2 or 3, characterized in that the water-in-oil emulsion composition impregnated in the support is taken from the support with a finger or an applicator and applied to the skin.

13. The following components (A), (B), (C) and (D): (A) a cationically modified clay mineral substituted with a quaternary ammonium ion; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C The cosmetic kit comprises a holder impregnated with a water-in-oil emulsion composition containing the above and a compact container.

14. The following components (A), (B), (C) and (D): (A) a cationically modified clay mineral substituted with a quaternary ammonium ion; (B) one or more selected from phenyl-modified silicones and alkyl-modified silicones that are liquid at 25°C; (C) a modified silicone having an alkyl group having 10 or more carbon atoms and a polyglyceryl group, (D) Ester oil that is liquid at 25°C A water-in-oil emulsion composition comprising:

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