Water-in-oil emulsion composition

Abstract

This water-in-oil emulsion composition for impregnation contains the following components: (A) a cation-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 a polyglyceryl group and an alkyl group having 10 or more carbon atoms; and (D) an ester oil that is liquid at 25° C.

Description

Water-in-oil emulsion composition

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

[0002] Conventionally, cosmetics have been developed in the form of a liquid cosmetic impregnated into a holder such as a sponge built into a compact container, and which is applied to the skin by taking it from the holder using a finger or an applicator at the time of use. For example, Patent Document 1 describes that a cosmetic comprising a polyether-based urethane foam impregnated with a cosmetic composition is excellent in stability, portability, and usability. Patent Document 2 describes that a cosmetic comprising a water-insoluble sponge impregnated with a cosmetic composition containing a specific organic UV-blocking agent is excellent in UV-blocking function. 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 the impregnation body.

[0003] (Patent Document 1) JP 2013-530252 A (Patent Document 2) JP 2017-088631 A (Patent Document 3) JP 2019-131489 A

[0004] The present invention relates to a water-in-oil emulsion composition for impregnation containing the following components (A), (B), (C), and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C.

[0005] The present invention also relates to a cosmetic product in which a holder impregnated with the water-in-oil emulsion composition is housed in a compact container. The present invention also relates to a method for using the cosmetic product, comprising taking the water-in-oil emulsion composition impregnated in the holder from the holder with a finger or an applicator and applying it to the skin. The present invention also relates to a cosmetic kit comprising a holder impregnated with a water-in-oil emulsion composition containing the following components (A), (B), (C), and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C, and a compact container.

[0006] The present invention also relates to a water-in-oil emulsion composition containing the following components (A), (B), (C), and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C. Detailed Description of the Invention

[0007] Conventional cosmetics have had problems such as poor adhesion to the skin, being prone to greasiness and makeup smudging, and poor makeup retention.

[0008] The present inventors have discovered that a water-in-oil emulsion composition comprising a combination of a cation-modified clay mineral, 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.

[0009] The water-in-oil emulsion composition of the present invention has improved adhesion to the skin, a good fit to the skin, does not cause makeup to smudge even after a long period of time, has excellent makeup durability, and is also excellent in emulsion stability. The water-in-oil emulsion composition is suitable for use as a cosmetic product impregnated into a support and contained in a compact container.

[0010] The cationically modified clay mineral of component (A) used in the present invention is substituted with a quaternary ammonium ion, and any cationically modified clay mineral that is used in ordinary cosmetics can be used without limitation. For example, a cationically modified clay mineral obtained by substituting a layered clay mineral such as bentonite, laponite, hectorite, montmorillonite, or magnesium aluminum silicate with a quaternary ammonium salt-type cationic surfactant is preferred. Here, the quaternary ammonium salt-type cationic surfactant is represented by the following formula (1):

[0011]

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

[0013] Specifically, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, Examples of the hydroxyethyl ammonium chloride 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 the above compounds in which the chloride is replaced with a bromide compound, and further include dipalmityl propyl ethyl ammonium methyl sulfate, etc. Among these, it is preferable to include one or more selected from benzyl dimethyl stearyl ammonium chloride and dimethyl distearyl ammonium chloride, and dimethyl distearyl ammonium chloride is more preferable.

[0014] The cation-modified clay mineral obtained by substituting a 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 one or more selected from dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite, and even more preferably dimethyl distearyl ammonium hectorite. Commercially available products include Benton 38, Benton 38 VCG, 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 in view of improved workability and excellent oil thickening effects. Specifically, it is preferable to use a premix gel in which the organically modified clay mineral is pre-dispersed in a solvent. The solvent is not limited as long as it can be thickened by the organically modified clay mineral. However, from the viewpoint of the oil thickening effect, it is preferable to include one or more solvents selected from C9-12 alkanes, C13-15 alkanes, hydrocarbon oils such as mineral oil, silicone oils such as phenyl trimethicone, tri(caprylic / capric)glyceryl, and alkyl benzoates (C12-15), and more preferably to include one or more solvents selected from tri(caprylic / capric)glyceryl and alkyl benzoates (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, thickening the oil, and suppressing oil separation from the thickened oily gel itself. As the premix gel, 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, BENTONE GEL TN V (all manufactured by Elementis Specialties) and the like can be used.

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

[0017] 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. "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 4,000 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 methylphenyl polysiloxane, phenyl trimethicone, diphenylsiloxyphenyl trimethicone, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, trimethylpentaphenyl trisiloxane, etc. Among these, from the viewpoint of excellent adhesion of the coating film after application, it is preferable to contain one or more selected from methylphenyl polysiloxane, phenyl trimethicone, and diphenylsiloxyphenyl trimethicone, and it is more preferable to contain at least methylphenyl polysiloxane.

[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 Corning 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 trisiloxiane.

[0020] Of the component (B), alkyl-modified silicones that are 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, (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer, etc. 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 achieving excellent adhesion of the coating film after application and excellent conformability to the skin.

[0023] One or more types of component (B) can be used, and from the viewpoint of excellent adhesion of the coating film after application and excellent compatibility with the skin, the content is preferably 1% by mass or more, more preferably 6% by mass or more, even more preferably 11% by mass or more, and preferably 30% by mass or less, more preferably 21% by mass or less, and even more preferably 16% by mass or less, of the total composition of the water-in-oil emulsion composition. 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 of 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, and methylhydrogenpolysiloxane. The length of the silicone chain is not particularly limited, and any length commonly used in cosmetics and the like may be used. Furthermore, the modified silicone of component (C) may be a block copolymer type containing a polyoxyalkylene group or polyglyceryl group chain and a silicone chain within the main chain, or a terminal-modified type, or may be a side-chain-modified type in which a polyoxyalkylene group or a polyglyceryl group is bonded as a side chain of the siloxane skeleton. The oxyalkylene of the polyoxyalkylene group contained in the modified silicone has one or more types of ethylene oxide and propylene oxide per molecule, preferably 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, 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, the HLB (hydrophilic-lipophilic balance) indicates the molecular weight of the hydrophilic group portion relative to the total molecular weight of the surfactant, and is calculated using the following Griffin formula: HLB = 20 x (molecular weight of hydrophilic group / total molecular weight)

[0026] Specific examples of the modified silicone 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, and lauryl PEG / PPG-18 / 18 methicone.

[0027] Furthermore, the modified silicone of component (C) includes alkyl glyceryl ether-modified silicones represented by the following general formula (2).

[0028]

[0029] (R 11 and R 19 are each independently the same or different linear or branched hydrocarbon group having a carbon number of 1 to 32; R 12 ~R 18 are each independently the same or different, linear or branched hydrocarbon groups having 1 to 5 carbon atoms; Q is a divalent linear or branched hydrocarbon group having 3 to 20 carbon atoms; R 20 and R 21 are 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; p represents the number of repeating units, an average value of 5 to 60; q represents the number of repeating units, an average value of 2.5 to 10; and the constituent units of 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 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 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 general formula (2), R 12 ~R18 each independently represents a linear 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 coating by oils contained in food can be more effectively prevented. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, and pentyl; and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl. Of these, the methyl group is preferred from the viewpoint of ease of availability.

[0032] In general formula (2), Q represents a linear or branched divalent 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 groups are preferred.

[0033] Also, R 20 and R 21 are 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, R20 and R 21 Preferably, both are 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 By H-NMR, the terminal methyl groups of the hydrocarbon groups introduced at both ends of the polysiloxane were used as a reference, and R 14 and R 15 The value is calculated from the intensity ratio of the peaks assigned to the repeating units. q represents the number of repeating units, and is an average value of 2.5 to 10, preferably 3.0 to 6.0. Here, the average value of q is 1 By H-NMR, OR 20 and OR 21 The repeating number p and repeating number q are calculated from the intensity ratio of the peaks assigned to the methylene hydrogen and the methane added. The structural units having repeating numbers p and q may be either block copolymers or random copolymers, but random copolymers are preferred. It is also preferred 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 bisalkyl (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, forming a coating film on the skin that is resistant to makeup smudging, thereby suppressing makeup smudging and the occurrence of shine due to sebum, and improving makeup durability.

[0037] Component (C) can be used alone or in combination of two or more, and from the viewpoints of suppressing makeup breakdown, greasiness due to sebum, and the like, and improving makeup durability, 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, of the total composition of the water-in-oil emulsion composition. 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 of the total composition of the water-in-oil emulsion composition.

[0038] In the present invention, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from smudging over a long period of time, providing excellent makeup durability, and achieving excellent emulsion stability at high temperatures, 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, and preferably 3 or less, more preferably 1 or less, and even more preferably 0.6 or less. Furthermore, 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, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from smudging over a long period of time, providing excellent makeup durability, and achieving excellent emulsion stability at high temperatures, 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, and preferably 15 or less, more preferably 7 or less, and even more preferably 5.5 or less. Furthermore, 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, as with component (B). The viscosity is measured using the same method as for component (B). The ester oil of component (D) may be any oil commonly used in cosmetics, and examples thereof include monoester oils such as ethylhexyl paramethoxycinnamate, cetyl ethylhexanoate, octyldodecyl myristate, isotridecyl isononanoate, and isononyl isononanoate; diester oils such as neopentyl glycol dicaprate, propylene glycol dicaprate, and diisostearyl malate; triester oils such as glyceryl tri-2-ethylhexanoate and glyceryl tri(caprylate / caprate); and tetraester oils such as dipentaerythrityl tetraisostearate.

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

[0042] Component (D) can be used alone or in combination of two or more types, and from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from smudging over a long period of time, and achieving excellent makeup durability, the content is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 25% by mass or less, and even more preferably 16% by mass or less, of 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 of the total composition of the water-in-oil emulsion composition.

[0043] In the present invention, from the viewpoints of improving adhesion to the skin, providing a good fit to the skin, preventing makeup from smudging over a long period of time, providing excellent makeup durability, and achieving excellent emulsion stability at high temperatures, 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, and preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less. Furthermore, 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 product and the feeling of a beautiful makeup finish on the entire face. The color pigment may be one that is used in ordinary cosmetics, such as titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red iron oxide, Prussian blue, ultramarine blue, chromium oxide, chromium hydroxide, and other metal oxides, manganese violet, cobalt titanate, and other metal complexes, as well as 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, and Red No. 227. Examples of suitable color pigments include synthetic organic pigments, organic dyes, and lake pigments thereof, such as Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 405, Red No. 505, Orange No. 203, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 401, Blue No. 1, and Blue No. 404; and natural organic dyes, such as β-carotene, caramel, and paprika pigment, as well as complexes of these color pigments and mixed pigments obtained by diluting these color pigments with an extender pigment, such as barium sulfate or talc. From the viewpoint of providing skin coverage and an aesthetic makeup effect, the color pigment preferably contains a metal oxide, more preferably one or more selected from titanium oxide, zinc oxide, yellow iron oxide, black iron oxide, and red iron oxide, and even more preferably one or more 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 applied to ordinary cosmetic powders, and dry treatment, wet treatment, or the like may be carried out using a surface treatment agent such as a silicone compound, a metal soap, an amino acid compound, lecithin, an oil, 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 silicones, crosslinked silicones, silicone resins, and acrylic-modified silicones; 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, hydrogenated lecithin; oils such as polyisobutylene, waxes, oils and fats, and fatty acids; and organic titanates such as isopropyl triisostearoyl titanate. The acylated amino acid includes a salt of the acylated amino acid, and examples of the salt of the acylated amino acid include Na, Ca, Al, Mg, Zn, Zr, and Ti salts, preferably including one or more selected from Na and Ca salts, and more preferably including Na salts. Furthermore, from the viewpoints of improving adhesion to the skin, providing a good feeling of fitting to the skin, excellent cosmetic lasting properties, and excellent stability at high temperatures, the acylated amino acid salt preferably includes one or more selected from disodium stearoyl glutamate and sodium lauroyl aspartate, and more preferably including disodium stearoyl glutamate.From the viewpoints of improving adhesion to the skin, providing a good fit to the skin, excellent cosmetic lasting effect, 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, stearoyl glutamate disodium, lauroyl aspartate sodium, and isopropyl triisostearoyl titanate, even more preferably contains one or more selected from dimethylpolysiloxane, alkylalkoxysilane, stearoyl glutamate disodium, and isopropyl triisostearoyl titanate, and even more preferably contains one or more selected from dimethylpolysiloxane, alkylalkoxysilane, stearoyl glutamate disodium, and isopropyl triisostearoyl titanate, and disodium stearoyl glutamate is still more preferred.

[0046] The hydrophobic treatment can be carried out by a conventional method. The amount of the hydrophobic treatment is preferably 0.1 to 15% by mass, more preferably 1 to 12% by 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 types, and 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 content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and 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. 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. By volatile, we mean an oil having 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 (1 cs), decamethyltetrasiloxane (1.5 cs), and dimethylpolysiloxane (2 cs); 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. Of 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 feeling of fit on the skin, the volatile oil is one or more oils selected from hydrocarbon oils and silicone oils, and preferably includes one or more oils selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxanes having a kinematic viscosity of 2 cSt or less at 25° C. The kinematic viscosity can be measured using, for example, an Ubbelohde viscometer.

[0050] Commercially available products of hexamethyldisiloxane and dimethylpolysiloxanes 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" manufactured by Dow Toray Co., Ltd. Examples include "SILICONE FLUID 0.65CS".

[0051] The volatile oil may be used alone or in combination of two or more, and from the viewpoints of forming a uniform coating film on the skin, improving adhesion, and improving the feeling of fit to the skin, the content is preferably 1% by mass or more, more preferably 4% by mass or more, even more preferably 8% by mass or more, and 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. 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 environmental friendliness, excellent usability, and excellent stability at high temperatures, the water-in-oil emulsion composition of the present invention preferably contains 1% by mass or less of organic resin powders such as microplastics in the total composition, more preferably 0.1% by mass or less, and even more preferably substantially no organic resin powders are contained. Specifically, this refers to organic resin powders other than cellulose powder, which are highly biodegradable. Examples of organic resin powders include polyamide resins, nylon resins, polyester resins, polyethylene resins, polytetrafluoroethylene resins, polypropylene resins, polystyrene resins, benzoguanamine resins, polymethylbenzoguanamine resins, polyurethane resins, vinyl resins, fluororesins, acrylic resins, and melamine resins; and crosslinked or non-crosslinked organic resin powders such as powders of one or more polymers or copolymers selected from butyl acrylate-vinyl acetate copolymers, styrene-acrylic acid copolymers, silicone resins, and divinylbenzene-styrene copolymers.

[0053] In the water-in-oil emulsion composition of the present invention, the water content is preferably 3 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, of the total composition, 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 commonly used in cosmetics, such as oily components other than those mentioned above, surfactants, water-soluble polymers, antioxidants, ultraviolet absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, disinfectants, and skin activators.

[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 formulation such as a liquid, emulsion, paste, cream, gel, or solid. The water-in-oil emulsion composition of the present invention can also 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 cream, overcoat, and lipstick; UV protection cosmetics such as a sunscreen emulsion and sunscreen cream; and skin care cosmetics such as a skin care emulsion, skin care cream, BB cream, and serum. It is particularly 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 viscosity of the water-in-oil emulsion composition of the present invention at 30°C is preferably 3,000 to 30,000 mPa·s, and more preferably 5,000 to 25,000 mPa·s. The viscosity was measured using a Brookfield viscometer (TVB-10 model, manufactured by Toki Sangyo Co., Ltd.) at 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 of 2,500 mPa·s or more but less than 10,000 mPa·s: Rotor No. 3, Viscosity of 10,000 mPa·s or more: Rotor No. 4. In Table 1, the viscosity of the water-in-oil emulsion composition of Example 1 was 12,000 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 impregnated with and holds the fluid water-in-oil emulsion composition, and examples thereof include nonwoven fabrics made of a single or mixed material such as resin, pulp, or cotton, resin-treated fibers, foams such as sponges, porous bodies with continuous structures, and fiber aggregates. Examples of materials include NBR (acrylonitrile butadiene rubber), SBR (styrene butadiene rubber), NR (natural rubber), urethane, nylon, polyolefin, polyester, EVA (ethylene vinyl acetate), PVA (polyvinyl alcohol), and silicone elastomers, but are not limited to these materials as long as the support can contain the contents. Among these, an aggregate of polyester fibers is preferred, and an aggregate of polyester fibers having a layer structure in which a surface layer and a back layer are connected by a crosslinked yarn may also be used. A fibrous body formed using polyester fibers, which preferably has a hardness of 40 to 60 (measured by an F hardness meter) and an apparent density (in accordance with JIS K 6400-1) of 0.006 to 0.1 g / cm 3 is preferred, and 0.02 to 0.1 g / cm 3 It is more preferable to use one of the following:

[0058] Among these, the fiber assembly can be an assembly of fibers with a core-sheath structure. The core-sheath fiber is composed of fibers in which a core is surrounded by a sheath, and the fibers are preferably made of a thermoplastic resin, with the core being made of a thermoplastic resin having a higher melting point than the sheath. Furthermore, the materials of the core and sheath in the core-sheath fiber are not particularly limited, but polyolefin resins are preferred because they are not subject to deterioration over time due to 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 an 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, I-shaped, polygonal, or star-shaped, or hollow.

[0061] The core-sheath fiber aggregate can be manufactured by a known method. Examples include thermal bonding, needle punching, and hydroentangling. A core-sheath fiber aggregate in which the sheath portion of the core-sheath fiber is partially fused is more preferred. The manufacturing method is not limited, and can be, for example, a hot air conveyor furnace method, a mold molding method, or a method using a mesh belt (the method described in Japanese Patent No. 4195043), followed by cutting to 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 (in accordance with JIS K 6400-1) of 0.02 to 0.1 g / cm 3 The size of the aggregate of core-sheath fibers is not particularly limited and can be determined depending on the ease of use, the size of the container in which it will be stored, etc.

[0063] The support may be 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 may be, for example, any of plain weave, 1 / 2 twill weave, 2 / 1 twill weave, twill weave, ramie weave, half ramie weave, and satin weave. Examples of screen nets include those made from polyurethane, TPE (thermoplastic plastic elastomer), polyester, polyether, acrylic, olefin, etc. The thickness of the fibers constituting the screen net is preferably 0.01 to 1.0 mm.

[0064] The screen net is preferably in close contact with the support impregnated with the emulsion composition so as to be completely attached thereto, or the absorbent material and the screen net are preferably not attached to each other but 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. Alternatively, 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, taking it from the screen net with a finger or an applicator, and applying it to the skin. Applicators for applying to the skin include sponges, puffs, tips, etc., which are typically 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 in which a holder impregnated with the composition is housed in a compact container.The water-in-oil emulsion composition of the present invention can be used as a cosmetic product in which a holder impregnated with the composition is placed adjacent to a screen net and housed in a compact container.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 in a support.

[0068] In relation to the above-described embodiment, the present invention further discloses the following compositions and the like.

[0069] <1> A water-in-oil emulsion composition for impregnation, comprising the following components (A), (B), (C), and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C.

[0070] <2> A cosmetic product having a holder impregnated with a water-in-oil emulsion composition containing the following components (A), (B), (C), and (D) in a compact container: (A) a cation-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; and (D) an ester oil that is liquid at 25°C.

[0071] <3> 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 a compound represented by the following formula (1):

[0072]

[0073] (In the formula, R 1 represents an alkyl group having 10 to 22 carbon atoms or a benzyl group, and R 2 represents a methyl group or an alkyl group having 10 to 22 carbon atoms, and R 3 and R 4the cosmetic composition according to <2> above, wherein the cationic modified clay mineral is obtained by substituting a quaternary ammonium salt-type cationic surfactant represented by the formula (I) (where X 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), and the cosmetic composition according to <2> above, further preferably contains one or more surfactants selected from dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, and benzyl dimethyl stearyl ammonium hectorite, even more preferably contains one or more surfactants selected from dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite, and even more preferably contains dimethyl distearyl ammonium hectorite. <4> The cosmetic composition according to <2> or <3> above, wherein the content of component (A) 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, of the total composition of the water-in-oil emulsion composition.

[0074] <5> The cosmetic preparation according to any one of the above items <2> to <4>, wherein the phenyl-modified silicone that is liquid at 25°C as component (B) is preferably methylphenyl polysiloxane, phenyl trimethicone, diphenylsiloxyphenyl trimethicone, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, or trimethylpentaphenyl trisiloxane, more preferably contains one or more selected from methylphenyl polysiloxane, phenyl trimethicone, and diphenylsiloxyphenyl trimethicone, and even more preferably contains at least methylphenyl polysiloxane. <6> The cosmetic preparation according to any one of <2> to <4> above, wherein the alkyl-modified silicone of component (B) that is liquid at 25°C is preferably caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, behenoxy dimethicone, or (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer, more preferably contains at least one or more selected from caprylyl methicone, cetyl dimethicone, alkyl (C26-28) dimethicone, stearyl dimethicone, and behenoxy dimethicone, and even more preferably contains at least caprylyl methicone.

[0075] <7> The cosmetic preparation according to any one of the above items <2> to <6>, wherein component (B) is preferably a combination of a phenyl-modified silicone and an alkyl-modified silicone that are liquid at 25° C. <8> The cosmetic preparation according to any one of the above items <2> to <7>, wherein the content of component (B) 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, of the total composition of the water-in-oil emulsion composition.

[0076] <9> The cosmetic preparation according to any one of the above <2> to <8>, wherein component (C) preferably has an HLB of 2 to 7, more preferably an HLB of 2 to 5. <10> The cosmetic preparation according to any one of the above <2> to <9>, wherein component (C) preferably comprises a glyceryl ether silicone modified at both ends with alkyl groups. <11> The cosmetic preparation according to any one of the above <2> to <10>, wherein component (C) preferably comprises 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.

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

[0078]

[0079] (R 11 and R 19 are each independently the same or different linear or branched hydrocarbon group having a carbon number of 1 to 32; R 12 ~R 18 are each independently the same or different, linear or branched hydrocarbon groups having 1 to 5 carbon atoms; Q is a divalent linear or branched hydrocarbon group having 3 to 20 carbon atoms; R 20 and R 21 are 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; p represents the number of repeating units and is an average number of 5 to 60; q represents the number of repeating units and is an average number of 2.5 to 10; and the constituent units of 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), and glyceryl undecyl dimethicone and bisalkyl (C16-18) glyceryl undecyl dimethicone are more preferred.

[0080] <13> The cosmetic preparation according to any one of the above items <2> to <12>, wherein 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, based on the total composition of the water-in-oil emulsion composition, and is preferably 12% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0081] <14> The cosmetic preparation according to any one of the above <2> to <13>, wherein 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. <15> The cosmetic preparation according to any one of the above <2> to <14>, wherein 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.

[0082] <16> The cosmetic preparation according to any one of the above <2> to <15>, wherein component (D) is preferably an ester oil having a molecular weight of 300 or more, more preferably one or two or more selected from monoesters and diesters, even more preferably one or two or more selected from diisostearyl malate, neopentyl glycol dicaprate, isotridecyl isononanoate, cetyl ethylhexanoate, and propylene glycol dicaprate, and even more preferably at least one or two selected from diisostearyl malate and neopentyl glycol dicaprate. <17> The cosmetic preparation according to any one of the above <2> to <16>, wherein the content of component (D) 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, of the total composition of the water-in-oil emulsion composition.

[0083] <18> The cosmetic preparation according to any one of the above <2> to <17>, wherein 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, and is preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less. <19> The cosmetic preparation according to any one of the above <2> to <18>, wherein the content of component (A) is preferably 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%.

[0084] <20> The cosmetic according to any one of <2> to <19> above, wherein the water-in-oil emulsion composition preferably further contains a hydrophobized color pigment, and more preferably contains 1 to 30 mass% of the hydrophobized color pigment in the total composition of the water-in-oil emulsion composition. <21> The cosmetic according to <20> above, wherein the color pigment preferably contains a metal oxide, and more preferably contains one or more species selected from titanium oxide, zinc oxide, yellow iron oxide, black iron oxide, and red iron oxide, and even more preferably contains one or more species selected from titanium oxide, yellow iron oxide, black iron oxide, and red iron oxide.

[0085] <22> The cosmetic according to <20> or <21> above, wherein the surface treatment agent for hydrophobization preferably contains one or more selected from silicone compounds, acylated amino acids, and organic titanates, more preferably one or more selected from dimethylpolysiloxane, methylhydrogenpolysiloxane, alkylalkoxysilane, stearoyl glutamate disodium, sodium lauroyl aspartate, and isopropyl triisostearoyl titanate, even more preferably one or more selected from dimethylpolysiloxane, alkylalkoxysilane, stearoyl glutamate disodium, and isopropyl triisostearoyl titanate, and even more preferably distearoyl glutamate disodium. <23> The cosmetic according to any one of the above items <20> to <22>, wherein 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.

[0086] <24> The cosmetic according to any one of <2> to <23> above, wherein the water-in-oil emulsion composition preferably further contains a volatile oil, and more preferably contains 1 to 50% by mass of the volatile oil in the total composition of the water-in-oil emulsion composition. <25> The cosmetic according to <24> above, wherein the volatile oil is preferably one or more oils selected from volatile hydrocarbon oils and volatile silicone oils, and more preferably includes one or more oils selected from isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 2 cSt or less. <26> The cosmetic according to <24> or <25> above, wherein the content of the volatile oil 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, of the total composition of the water-in-oil emulsion composition.

[0087] <27> The cosmetic according to any one of the above <2> to <26>, wherein the water-in-oil emulsion composition preferably contains an organic resin powder in an amount of 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably substantially free of organic resin powder, based on the total composition. <28> The cosmetic according to any one of the above <2> to <27>, wherein the water-in-oil emulsion composition preferably contains water in an amount 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.

[0088] <29> The cosmetic according to any one of the above <2> to <28>, wherein the water-in-oil emulsion composition is preferably a liquid water-in-oil emulsion cosmetic. <30> The cosmetic according to any one of the above <2> to <29>, wherein 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.

[0089] <31> The cosmetic according to any one of the above <2> to <30>, wherein the support is preferably a foam, a porous body, or an aggregate of fibers, more preferably an aggregate of polyester fibers. <32> A method for using the cosmetic according to any one of the above <2> to <31>, wherein 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.

[0090] <33> A cosmetic kit comprising a holder impregnated with a water-in-oil emulsion composition containing the following components (A), (B), (C), and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C, and a compact container.

[0091] <34> A water-in-oil emulsion composition containing the following components (A), (B), (C) and (D): (A) a cation-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, and (D) an ester oil that is liquid at 25°C.

[0092] Production Example 1 (Production of a both-terminally alkyl (C16-18)-modified dimethylsiloxane-methyl (undecylglyceryl 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 Spiers catalyst (2 mass % solution of chloroplatinic acid in 2-propanol) were added to a three-necked flask and heated to 70°C. 174.2 g of α-olefin ("Linearene 168" manufactured by Idemitsu Kosan Co., Ltd., a 57 / 43 (mass ratio) mixture of 16 and 18 carbon atoms) was added dropwise at 70°C under a nitrogen atmosphere, followed by stirring for 2 hours. After cooling, the reaction system was neutralized with aqueous sodium hydroxide solution and purified by distillation under reduced pressure. The resulting product 1 H-NMR spectrum (400 MHz) confirmed that the resulting product was a 1,1,3,3-tetramethyldisiloxane derivative bearing 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 within the silicone chain): 44.8 g of the 1,1,3,3-tetramethyldisiloxane derivative having alkyl groups with 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-necked flask and refluxed for 12 hours. After cooling, the mixture was purified by distillation under reduced pressure. The resulting product 1From the H-NMR spectrum, it was confirmed that the obtained product 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 substituted with alkyl groups at both ends and graft-modified with alkyl glyceryl ether groups at the side chains): 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 a 5% by mass platinum-supported carbon catalyst were added to a three-necked flask and stirred at 70°C for 3 hours. After cooling, the mixture was purified by distillation under reduced pressure. The resulting product 1 From the H-NMR spectrum, the obtained product was confirmed to be a dimethylsiloxane-methyl(undecylglyceryl ether)siloxane copolymer (p=23, q=4) having alkyl groups with 16 and 18 carbon atoms at both ends (63.0 g, yield: 95%). The obtained copolymer is a random copolymer of general formula (2) as shown below. R 11 and R 19 R = an alkyl group having a mode of 18 carbon atoms; 12 ~R 18 = methyl group, Q = alkylene group having 11 carbon atoms, R 20 and R 21 = Hydrogen atom p (average value) = 23, q (average value) = 4.0

[0095] Examples 1 to 8, Comparative Example 1 Water-in-oil emulsion cosmetics (liquid foundations) were produced with the compositions shown in Tables 1 and 2. A support was impregnated with the obtained water-in-oil emulsion cosmetics, and the makeup retention, fit to the skin, and emulsion stability were evaluated after 6 hours. The results are also shown in Tables 1 and 2.

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

[0097] (Evaluation Method) (1) Freedom of makeup from smudging after 6 hours: Three expert panelists took each water-in-oil emulsion composition (support-impregnated foundation) with a puff and applied it to the skin, and then performed a sensory evaluation of the freeness of makeup from smudging after 6 hours using the following criteria. The results were shown as the total score of the three panelists: 5: No makeup smudging at all. 4: No makeup smudging. 3: Very little makeup smudging. 2: Some makeup smudging. 1: Some makeup smudging.

[0098] (2) Fit to skin: Three expert panelists took each water-in-oil emulsion composition (support-impregnated foundation) with a puff and applied it to the skin, and then sensory evaluated the fit to the skin according to the following criteria. The results were shown as the total score of the three panelists: 5: Very good adhesion to skin. 4: Good adhesion to skin. 3: Fairly good adhesion to skin. 2: Not very good adhesion to skin. 1: Poor adhesion to skin.

[0099] (3) Emulsion stability: Each water-in-oil emulsion composition (support-impregnated foundation) was stored in a 40°C environment 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: Slight decrease in viscosity. C: Slight decrease in viscosity, and oil bleeding was observed. D: Separation was observed.

[0100]

[0101]

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

Claims

1. A water-in-oil emulsion composition for impregnation, comprising 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, and (D) an ester oil that is liquid at 25°C.

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

4. Component (C) is represented by general formula (2): (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 and is an average number of 5 to 60; q represents the number of repeating units and is an average number of 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.

5. The cosmetic preparation according to any one of claims 2 to 4, 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. The cosmetic preparation according to any one of claims 2 to 5, wherein the mass ratio (A) / (C) of component (A) to component (C) is 0.05 to 3.

7. The cosmetic preparation according to any one of claims 2 to 6, wherein the mass ratio (B) / (C) of component (B) to component (C) is 0.5 to 15.

8. The cosmetic preparation according to any one of claims 2 to 7, wherein component (D) has a viscosity at 25°C of 10,000 mPa·s or less.

9. The cosmetic preparation according to any one of claims 2 to 8, wherein the mass ratio (B) / (D) of component (B) to component (D) is 0.2 to 5.

10. A cosmetic preparation according to any one of claims 2 to 9, wherein the water-in-oil emulsion composition further contains 1 to 30% by mass of a hydrophobically treated color pigment.

11. A cosmetic preparation according to any one of claims 2 to 10, wherein the water-in-oil emulsion composition further contains 1 to 50% by mass of a volatile oil.

12. A cosmetic preparation according to any one of claims 2 to 11, wherein the water content in the water-in-oil emulsion composition is 3 to 50 mass %.

13. A cosmetic preparation according to any one of claims 2 to 12, wherein the water-in-oil emulsion composition has a viscosity at 30°C of 3,000 to 30,000 mPa·s.

14. The cosmetic preparation according to any one of claims 2 to 13, wherein the support is a foam, a porous body, or an aggregate of fibers.

15. The cosmetic material according to any one of claims 2 to 14, wherein the support is an assembly of polyester fibers.

16. A method for using the cosmetic preparation according to any one of claims 2 to 15, comprising taking the water-in-oil emulsion composition impregnated in the support from the support with a finger or an applicator and applying it to the skin.

17. Use as a makeup cosmetic by impregnating a support with a water-in-oil emulsion composition containing 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, and (D) an ester oil that is liquid at 25°C.

18. A cosmetic kit comprising a holder impregnated with a water-in-oil emulsion composition containing 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, and (D) an ester oil that is liquid at 25°C, and a compact container.

19. A water-in-oil emulsion composition containing 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, and (D) an ester oil that is liquid at 25°C.

Images