Water-in-oil emulsion cosmetics

Abstract

To provide a water-in-oil emulsion cosmetic that excels in dispersibility of metal oxide, smooth use feeling, non-stickiness, and uniformity of a cosmetic film.SOLUTION FOR THE PROBLEM: A water-in-oil emulsion cosmetic comprises following components (A)-(D): (A) electrolyte of 5-15 mass%, (B) hydrophobic metal oxide of 0.1-30 mass%, (C) nonionic surfactant with an HLB of 7 or less of 2-6 mass% and (D) organic modified clay mineral of 0.3-1.8 mass%.

Description

[Technical Field]

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

[0002] Makeup cosmetics such as foundations and primers are often required to have a skin-correcting effect. This effect is generally achieved by metal oxides, but ensuring their dispersibility has been a challenge due to the high coagulation tendency of metal oxides. At the same time, a smooth feel during use, non-stickiness, and a uniform makeup film are important factors desired for cosmetics. For this reason, numerous technologies have been developed to ensure the dispersibility of metal oxides, smooth feel during use, non-stickiness, and uniform makeup film.

[0003] As an example of the above technology, there is known a technology for water-in-oil cosmetics that have excellent emulsion stability by containing specific amounts of silicone oil, lipophilic surfactant, inorganic and / or organic powder, water, lower alcohol, one or more water-soluble oxyacids and oxyacid salts, one or more water-soluble polysaccharide sulfates, and one or more water-soluble monosaccharide sulfates (see, for example, Patent Document 1).

[0004] Furthermore, powder-containing water-in-oil emulsion cosmetics that have excellent usability (spreadability) and storage stability have been investigated by incorporating specific amounts of a specific cyclic silicone, sorbitan monoisostearate and / or diglyceryl monoisostearate, a specific polyether-modified silicone, rutile titanium oxide, and water (see, for example, Patent Document 2).

[0005] Furthermore, a low-viscosity water-in-oil emulsion cosmetic has been disclosed that combines specific amounts of a pigment, a lipophilic nonionic surfactant, a polyether-modified silicone, a cyclic silicone, and sodium chloride, and has a viscosity of 10,000 centipoise or less, thereby providing a good feel when used and excellent pigment dispersion stability and emulsion stability (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-167212 [Patent Document 2] Japanese Patent Application Publication No. 5-148121 [Patent Document 3] Japanese Patent Application Publication No. 7-277922 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0007] However, while conventional techniques have solved the problems of pigment dispersion stability and storage stability, they have not achieved satisfactory cosmetic film uniformity. To improve the dispersibility of metal oxides, hydrophobic treatment of metal oxides or the use of surfactants may be used. However, while these methods improve the dispersibility of metal oxides, it is difficult to improve usability or achieve good film uniformity. Therefore, in the course of various investigations, it was discovered that the dispersibility of hydrophobic treated metal oxides can be further improved by adding a large amount of electrolyte to the inner water layer of water-in-oil emulsion cosmetics. However, when the electrolyte content is high, the cosmetic tends to become sticky.

[0008] Therefore, an object of the present invention is to provide a water-in-oil emulsion cosmetic that is not sticky, has a smooth feel when used, and has excellent uniformity in the cosmetic film it forms, even when it contains a large amount of electrolyte to improve the dispersibility of a hydrophobic treated metal oxide. [Means for solving the problem]

[0009] In light of the above-mentioned circumstances, the present inventors conducted extensive research to solve the above-mentioned problems. As a result, they discovered that, when electrolytes are contained in an amount of 5 to 15% by mass, combining specific amounts of a nonionic surfactant with an HLB of 7 or less and an organically modified clay mineral to improve the dispersibility of metal oxides can unexpectedly suppress electrolyte-induced stickiness and produce a water-in-oil emulsion cosmetic with excellent cosmetic film uniformity. Furthermore, they discovered that hydrophobizing the metal oxide further improves the dispersibility of metal oxides without compromising the non-stickiness and smooth feel in use. Based on these findings, they discovered that combining specific amounts of electrolytes, hydrophobized surface-treated metal oxides, nonionic surfactants, and organically modified clay minerals to produce water-in-oil emulsion cosmetics results in good metal oxide dispersibility, a smooth feel in use, non-stickiness, and excellent cosmetic film uniformity, leading to the completion of the present invention.

[0010] That is, the present invention provides: [1] The following components (A) to (D): (A) Electrolyte 5~15% by mass (B) Hydrophobized metal oxide: 0.1 to 30% by mass (C) 2 to 6 mass% of a nonionic surfactant with an HLB of 7 or less (D) Organically modified clay mineral 0.3 to 1.8 mass% The present invention relates to a water-in-oil emulsion cosmetic containing [2] The present invention relates to the water-in-oil emulsion cosmetic according to [1], which contains two or more types of electrolytes as component (A). [3] The present invention relates to the water-in-oil emulsion cosmetic according to [1] or [2], wherein the metal oxide of component (B) is one or more selected from the group consisting of titanium dioxide, zinc oxide, and iron oxide. [4] The water-in-oil emulsion cosmetic according to any one of [1] to [3], wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.2 to 70. [5] The present invention relates to the water-in-oil emulsion cosmetic according to any one of [1] to [4], wherein the nonionic surfactant of the component (C) is a silicone surfactant. [6] The present invention further relates to a water-in-oil emulsion cosmetic composition according to any one of [1] to [5], which contains a silicone film-forming agent as component (E). [7] The water-in-oil emulsion cosmetic according to [6], wherein the content of the silicone film-forming agent as component (E) is 0.01 to 3 mass % based on the total amount of the water-in-oil emulsion cosmetic. [Effects of the Invention]

[0011] The water-in-oil emulsion cosmetic of the present invention has good dispersibility of metal oxides, and is smooth to use, non-sticky, and has excellent uniformity of cosmetic film. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. In this specification, the symbol "to" means a range including the numerical values ​​before and after it. The "average particle size" in this invention is D50 evaluated using image analysis. The average particle size of the powder is determined by observing the surface condition using a scanning electron microscope (JEOL, JSM-7800prime) and measuring with an image analyzer (Luzex AP, Nireco Corporation) to obtain the value (D50).

[0013] The electrolyte (A) of the present invention is a substance that, when dissolved in water or other solvent, gives the resulting solution electrical conductivity. For example, any of the compounds commonly used in topical skin preparations, such as water-soluble cosmetic ingredients (e.g., whitening agents, anti-inflammatory agents, etc.) that are dermatologically effective for the skin, moisturizers, pH adjusters, chelating agents, etc., can be used, regardless of whether they are organic or inorganic compounds.

[0014] Specific examples of such agents include ascorbic acids such as ascorbic acid, ascorbic acid phosphate, ascorbic acid sulfate, and ascorbic acid glucoside; whitening agents such as tranexamic acid or a derivative thereof, niacinamide, and kojic acid; anti-inflammatory agents such as glycyrrhizinic acid or a derivative thereof, glycyrrhetinic acid or a derivative thereof, salicylic acid or a derivative thereof, and alum; urea or a derivative thereof; moisturizing agents such as amino acids or derivatives thereof, or metal salts thereof; pH adjusters such as organic compounds such as lactic acid, phosphoric acid, citric acid, pyrosulfite, and pyrrolidonecarboxylic acid, or metal salts thereof; inorganic salts such as sodium chloride and magnesium chloride; and chelating agents such as ethylenediaminetetraacetic acid (EDTA), ethylenetriaminepentaacetic acid (DTPA), ethyleneglycolbis(2-aminoethylether)tetraacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), and ethylenediaminetetra(methylenephosphonic acid) or salts thereof. The metal salts used for the salts include potassium, sodium, magnesium, calcium, and the like.

[0015] Examples of amino acids or salts thereof include L-alanine, β-alanine, L-arginine, L-arginine hydrochloride, L-asparagine monohydrate, L-aspartic acid, polyaspartic acid, L-citrulline, L-cysteine, L-cysteine ​​hydrochloride monohydrate, L-dopa, L-glutamic acid, L-glutamic acid hydrochloride, L-glutamine, polyglutamic acid, glycine, trimethylglycine, L-histidine, L-histidine hydrochloride monohydrate, L-hydroxyproline, L-isoleucine, L-leucine, L-lysine, L-lysine hydrochloride, L-methionine, L-ornithine hydrochloride, L-proline, L-phenylalanine, L-serine, L-threonine, L-tryptophan, L-tyrosine, and L-valine. As an embodiment of the electrolyte, for example, naturally occurring aqueous solutions containing electrolytes such as deep sea water, hot spring water, etc. These can be used alone or in combination of two or more types as needed.

[0016] Among these, from the viewpoint of imparting cosmetic effects such as emulsion stability, whitening, and moisturizing, in addition to the dispersibility of metal oxides, preferred are one or more selected from the group consisting of whitening agents, moisturizing agents, and pH adjusters, more preferred are one or more selected from the group consisting of whitening agents and moisturizing agents, and even more preferred are combinations of two or more selected from the group consisting of whitening agents and moisturizing agents. In particular, containing two or more electrolytes as component (A) of the present invention is more preferred, as this provides better dispersibility of metal oxides and uniformity of cosmetic film. Furthermore, it is preferred to combine niacinamide and tranexamic acid as component (A) of the present invention, and using these two in combination is more preferred, as it provides viscosity to the internal aqueous phase in water-in-oil emulsion cosmetics, thereby further enhancing the dispersibility of metal oxides.

[0017] The content of component (A) in the present invention is 5 to 15% by mass (hereinafter simply referred to as "%") of the total amount of the water-in-oil emulsion cosmetic, but is preferably 6% or more, more preferably 7% or more. It is also preferably 13% or less, more preferably 10% or less. It is also preferably 6 to 13%, more preferably 7 to 10%. This range is more preferable because it provides better dispersibility of the metal oxide and uniformity of the cosmetic film.

[0018] The hydrophobized metal oxide (component (B)) of the present invention is a metal oxide whose surface has been treated with a hydrophobizing agent. Any hydrophobized metal oxide suitable for use in conventional cosmetics can be used. The metal oxide is not particularly limited, but examples include zinc oxide, iron oxide, titanium dioxide, zirconium oxide, cerium oxide, and chromium oxide. One or more of these can be used. Among these, one or more selected from the group consisting of titanium dioxide, zinc oxide, and iron oxide are more preferred from the viewpoint of uniformity of the cosmetic film. The average particle size is not particularly limited and can be selected according to the intended use. For example, fine particle metal oxides (100 nm or less) can be used to impart UV protection, and pigment-grade metal oxides (greater than 100 nm) can be used to impart skin coverage. In the present invention, an average particle size in the range of 0.01 to 1 μm is more preferred. This range is preferred because it provides superior uniformity of the cosmetic film and, secondarily, superior UV protection and coverage of pores, wrinkles, etc.

[0019] The hydrophobic treatment applied to the surface of the metal oxide of component (B) is not particularly limited, and any treatment that can impart hydrophobicity to the metal oxide can be used, such as silicone treatment, alkylalkoxysilane treatment, fluorine compound treatment, organic titanate treatment, fatty acid treatment, N-acylamino acid treatment, phospholipid treatment, polyalkylene oxide treatment, and ceramide treatment. More specifically, examples of the treatment include silicone treatments such as methylhydrogenpolysiloxane treatment and dimethylpolysiloxane treatment, alkylalkoxysilane treatments such as triethoxycaprylylsilane treatment, fluorine compound treatments such as perfluoroalkyl phosphate ester treatment and perfluoroalkylalkoxysilane treatment, organic titanate treatments such as isopropyl titanium triisostearate treatment, fatty acid treatments such as stearic acid treatment and myristic acid treatment, N-acylamino acid treatments such as lauroyl lysine treatment, sodium dilauroyl glutamate lysine treatment, disodium stearoyl glutamate treatment and sodium lauroyl aspartate treatment, phospholipid treatments such as lecithin treatment and hydrogenated lecithin treatment, and polyalkylene oxide treatments such as polyethylene oxide, and these can be used alone or in combination. By subjecting metal oxides to hydrophobic treatment, the dispersibility of the metal oxides is improved, which is preferable.

[0020] Among these, from the viewpoint of dispersibility of the metal oxide and uniformity of the cosmetic film, one or more treatments selected from the group consisting of silicone treatment, alkylalkoxysilane treatment, organic titanate treatment, N-acylamino acid treatment, phospholipid treatment, and ceramide treatment are preferred, and one or more treatments selected from the group consisting of triethoxycaprylylsilane treatment, isopropyl titanium triisostearate treatment, lauroyl lysine treatment, sodium dilauroyl glutamate lysine treatment, disodium stearoyl glutamate treatment, and hydrogenated lecithin treatment are more preferred.

[0021] The amount of the treatment agent used in the hydrophobic treatment is not particularly limited, but is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.3% or more, based on the hydrophobic treated metal oxide. It is also preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. It is also preferably 0.1 to 20%, more preferably 0.2 to 15%, and even more preferably 0.3 to 10%. This range is more preferable because it provides better dispersibility of the metal oxide and uniformity of the cosmetic film.

[0022] The content of component (B) in the present invention is 0.1 to 30% of the total amount of the water-in-oil emulsion cosmetic, preferably 0.5% or more, more preferably 1% or more, and even more preferably 3% or more. It is also preferably 25% or less, more preferably 22% or less, and even more preferably 20% or less. It is also preferably 0.5 to 25%, more preferably 1 to 22%, and even more preferably 3 to 20%. This range is more preferable because it provides better dispersibility of the metal oxide, a smooth feel when used, and uniformity of the cosmetic film.

[0023] In the present invention, the mass ratio (A) / (B) of component (A) to component (B) is not particularly limited, but is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. It is also preferably 70 or less, more preferably 30 or less, and even more preferably 10 or less. It is also preferably 0.2 to 70, more preferably 0.3 to 30, and even more preferably 0.5 to 10. This range is more preferable because it provides better dispersibility of the metal oxide and uniformity of the cosmetic film.

[0024] Any nonionic surfactant with an HLB of 7 or less can be used as component (C) in the present invention, as long as it is suitable for use in ordinary cosmetics. Here, HLB is a value that represents the balance between the hydrophilicity and lipophilicity of a surfactant, and in the present invention, it can be calculated using the Kawakami formula below. HLB = 7 + 11.7 log(Mw / Mo) (Here, Mw represents the molecular weight of the hydrophilic base, and Mo represents the molecular weight of the new oil base.)

[0025] In the present invention, the HLB of the nonionic surfactant is 7 or less, but from the viewpoint of improving the dispersibility of the metal oxide, the HLB is preferably 6 or less, and more preferably 5 or less.

[0026] Examples of such surfactants include polyglycerin fatty acid esters, sorbitan fatty acid esters, and silicone surfactants. Silicone surfactants may be graft copolymers having organopolysiloxane groups as their main chains and hydrophilic groups as their side chains, or may contain linear block copolymers or crosslinked polymers in which organopolysiloxane groups and hydrophilic groups are alternately bonded. Specific examples of surfactants having linear organopolysiloxane groups as their main chains and polyoxyalkylene groups as their side chains include polyoxyalkylene-modified organopolysiloxanes and polyoxyalkylene-alkyl co-modified organopolysiloxanes. Examples of surfactants having hydrophilic groups include polyether-modified silicones having polyether chains and polyglycerin-modified silicones having polyglycerin chains.

[0027] More specifically, polyglycerin fatty acid esters such as diglyceryl monostearate (HLB 5.0), diglyceryl monooleate (HLB 6.5), diglyceryl dioleate (HLB 7.0), diglyceryl monoisostearate (HLB 5.5), tetraglyceryl monostearate (HLB 6.0), tetraglyceryl monooleate (HLB 6.0), and hexaglyceryl tristearate (HLB 2.5); sorbitan fatty acid esters such as sorbitan monostearate (HLB 4.7), sorbitan sesquistearate (HLB 4.2), sorbitan sesquiisostearate (HLB 4.0), and sorbitan sesquioleate (HLB 3.7); polyoxyethylene-methylpolysiloxane copolymer (HLB 5.0), methylpolysiloxane copolymer (HLB 5.0), and methylpolysiloxane copolymer (HLB 5.0). Examples include polyether-modified silicones such as lysiloxane-cetylmethylpolysiloxane-poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer (HLB 5.0), poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer (cosmetic ingredient name: PEG / PPG-20 / 22 butyl ether dimethicone) (HLB 7.0), PEG-9 polydimethylsiloxyethyl dimethicone (HLB 4.0), and lauryl PEG-9 polydimethylsiloxyethyl dimethicone (HLB 3.0), and block copolymer-type silicone surfactants such as poly(oxyethylene-oxypropylene)-butylene-methylpolysiloxane copolymer (HLB 6.0). One or more of these can be used.

[0028] Among the nonionic surfactants having an HLB of 7 or less used in the present invention, silicone surfactants are preferred from the viewpoint of non-sticky feel when used, and polyether-modified silicones having polyoxyethylene groups are more preferred because they provide a smooth, non-sticky feel when used.

[0029] Commercially available examples of such silicone surfactants include KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.), 5200 Formulation Aid (manufactured by Dow Corning Toray Co., Ltd.), ABIL EM97S (manufactured by EVONIC GOLDSCHMIDT), KF-6028, KF-6038 (all manufactured by Shin-Etsu Chemical Co., Ltd.), ABIL EM90 (manufactured by EVONIC GOLDSCHMIDT), KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-2250, FZ-2233 (all manufactured by Dow Corning Toray Co., Ltd.), and SILWET 236-L (manufactured by Nippon Unicar Co., Ltd.).

[0030] The content of component (C) in the present invention is 2 to 6% of the total amount of the water-in-oil emulsion cosmetic, preferably 2.3% or more, more preferably 2.5% or more. It is also preferably 5.8% or less, more preferably 5.5% or less. It is also preferably 2.3 to 5.8%, more preferably 2.5 to 5.5%. This range is more preferable because it provides better dispersibility of the metal oxide and less stickiness.

[0031] The organically modified clay mineral (component (D)) of the present invention is a clay mineral in which the interlayer metal ions of the clay mineral have been substituted with a cation modifier such as a quaternary alkylammonium ion. The clay mineral used in the present invention is not particularly limited, but examples thereof include smectite clays such as bentonite, montmorillonite, hydrite, hectorite, and saponite, as well as fluorinated swelling mica. The cation used to replace the interlayer metal ions is not particularly limited, but examples thereof include those represented by the following general formula (1):

[0032] [ka] In the formula, R 1 is an alkyl group having 1 to 30 carbon atoms or a benzyl group, and R 2 , R 3 , and R 4 is an alkyl group having 1 to 30 carbon atoms. 2 ~R 4 may be the same or different from each other.

[0033] The method for modifying a clay mineral with a cation is not particularly limited, but examples include adding a quaternary alkylammonium salt to a suspension of a clay mineral dispersed in water and thoroughly mixing, or adding a clay mineral suspension to a quaternary alkylammonium salt solution and thoroughly mixing. The modification reaction proceeds satisfactorily at room temperature, but heating may be performed if necessary. The maximum temperature when heating is determined by the heat resistance of the quaternary alkylammonium salt used and can be set at any temperature below its decomposition point. The solid-liquid separation is then performed, and the product is washed with water to thoroughly remove by-product electrolytes. The product is then dried and, if necessary, pulverized for use. The amount of quaternary alkylammonium salt added to modify the clay mineral is preferably equivalent to the cation exchange capacity of the clay mineral in terms of quaternary alkylammonium ions. More specifically, the amount of quaternary alkylammonium salt added relative to the cation exchange capacity of the clay mineral is preferably 0.5 to 1.5 times (molar equivalent), and even more preferably 0.8 to 1.4 times (molar equivalent).

[0034] Examples of the organically modified clay mineral component (D) used in the present invention include dimethyl distearyl ammonium hectorite (disteardimonium hectorite), dimethyl distearyl ammonium bentonite, benzyl dimethyl stearyl ammonium hectorite (stearalkonium hectorite), dioctadecyl dimethyl ammonium montmorillonite, octadecyl dimethyl benzyl ammonium montmorillonite, dihexadecyl dimethyl ammonium montmorillonite, quaternium-18 hectorite, and distearyl dimethyl ammonium chloride-treated magnesium aluminum silicate. Among these, from the viewpoints of smooth feel and non-stickiness, one or two selected from the group consisting of dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite are preferred, and it is more preferred to include dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite.

[0035] Commercially available organically modified clay minerals as component (D) include, for example, BENTONE 27V and BENTONE 38V BC (both manufactured by Elementis), Lucentite SAN, and Lucentite SAN-P (both manufactured by Co-op Chemical).

[0036] The content of component (D) in the present invention is 0.3 to 1.8% of the total amount of the water-in-oil emulsion cosmetic, preferably 0.4% or more, more preferably 0.5% or more, and even more preferably 0.6% or more. It is also preferably 1.7% or less, more preferably 1.6% or less, and even more preferably 1.5% or less. It is also preferably 0.4 to 1.7%, more preferably 0.5 to 1.6%, and even more preferably 0.6 to 1.5%. This range is more preferable because it provides better dispersibility of the metal oxide and a smooth feel when used.

[0037] The present invention can further contain a silicone film-forming agent (Component (E)). Component (E) of the present invention is a film-forming polymer having a silicone skeleton in the main chain or side chain. The silicone film-forming agent of the present invention is not particularly limited as long as it forms a film. A typical example of a silicone film-forming agent is one in which a 40% solution of the silicone film-forming agent in a soluble solvent is applied to a glass plate with a 400 μm thick applicator and allowed to dry at room temperature for 24 hours, forming a film. Any silicone film-forming agent that can be used in ordinary cosmetics can be used as component (E) of the present invention. Examples include trimethylsiloxysilicate, polymethylsilsesquioxane, trifluoroalkyldimethyltrimethylsiloxysilicate, and acrylic-silicone graft copolymers. Among these, from the viewpoint of forming a uniform cosmetic film, one or more selected from the group consisting of trimethylsiloxysilicate, polymethylsilsesquioxane, and trifluoroalkyldimethyltrimethylsiloxysilicate are preferred, and one or two selected from the group consisting of trimethylsiloxysilicate and trifluoroalkyldimethyltrimethylsiloxysilicate are more preferred.

[0038] Commercially available products obtained by dissolving these in a volatile solvent (for example, methylpolysiloxane (dimethicone), decamethylcyclopentasiloxane (cyclomethicone), methyltrimethicone, isododecane, hydrogenated polyisobutene, etc.) can also be used. Commercially available silicone film-forming agents include, for example, Silicon X-21-5250 (50% decamethylcyclopentasiloxane solution), Silicon X-21-5250L (50% volatile dimethicone solution), KF-7312T (60% methyltrimethicone solution), KF-7312J (50% decamethylcyclopentasiloxane solution), KF-7312K (60% dimethicone solution), KF-9021 (50% decamethylcyclopentasiloxane solution), and KF-9021L (50% volatile dimethicone solution) (all manufactured by Shin-Etsu Chemical Co., Ltd.), and SILFORM FLEXIBLE Examples include RESIN (100% resin), SR1000 (100% resin), SS4267 (35% dimethicone solution), SILSOFT74 (75% isododecane solution), XS66-B8226 (50% decamethylcyclopentasiloxane solution), XS66-C1191, and XS66-B8636 (50% dimethicone solution) (all manufactured by Momentive Performance Materials).

[0039] The content of component (E) in the present invention is not particularly limited, but is preferably 0.01% or more, more preferably 0.1% or more, and even more preferably 0.3% or more, based on the total amount of the water-in-oil emulsion cosmetic. It is also preferably 3% or less, more preferably 2.8% or less, and even more preferably 2.6% or less. It is also preferably 0.01 to 3%, more preferably 0.1 to 2.8%, and even more preferably 0.3 to 2.6%. This range is more preferable because it provides excellent dispersibility of the metal oxide, a smooth feel when used, and no stickiness.

[0040] In addition to the above-mentioned components (A) to (E), the water-in-oil emulsion cosmetic of the present invention may contain components that are commonly used in cosmetics, such as oily components other than component (E), powders other than component (B), surfactants other than component (C), gelling agents other than component (D), ultraviolet absorbers, fibers, alcohols, water-soluble polymers, antioxidants, antifoaming agents, cosmetic ingredients other than component (A), preservatives, fragrances, etc., within the scope that does not impair the effects of the present invention.

[0041] The water-in-oil emulsion cosmetic of the present invention is an emulsion cosmetic having an oil phase as an outer phase and an aqueous phase as an inner phase. The oil phase can contain an oily component (e.g., an oil agent, etc.), and the aqueous phase can contain an aqueous component (e.g., water, alcohols, etc.).

[0042] The oil agent in the present invention may be in any form, such as solid, paste, or liquid, as long as it is one that is normally used in cosmetics, and any of these may be used. For example, solid oils include waxes such as beeswax, carnauba wax, candelilla wax, cotton wax, shellac wax, Japan wax, and hydrogenated oils; mineral waxes such as ozokerite, ceresin, paraffin wax, and microcrystalline wax; synthetic waxes such as polyethylene wax, Fischer-Tropsch wax, and ethylene-propylene copolymers; higher alcohols such as behenyl alcohol, cetyl alcohol, and stearyl alcohol; and higher fatty acids such as stearic acid and behenic acid. Paste oils include hydrocarbons such as petrolatum, and esters such as diglyceryl adipate mixed fatty acid esters, pentaerythritol rosinate, phytosterol fatty acid esters, lanolin, isopropyl lanolinate, octyldodecyl lanolinate, hydrogenated castor oil fatty acid esters, and phytosteryl macadamia nut oil fatty acid. Liquid oils include hydrocarbons such as liquid paraffin, heavy liquid isoparaffin, squalane, polyisobutylene, and polybutene. , olive oil, castor oil, jojoba oil, mink oil, macadamia nut oil and other oils and fats, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diglyceryl diisostearate, diglyceryl triisostearate, diisostearyl malate, propylene glycol dicaprate, cetyl 2-ethylhexanoate, 2-ethylhexyl hydroxystearate, pentaerythrityl tetraisostearate, stearoyl oxystearate Examples of the oil include ester oils such as octyldodecyl tearate and 2-ethylhexyl paramethoxycinnamate, fatty acids such as isostearic acid and oleic acid, higher alcohols such as lauryl alcohol, oleyl alcohol, isostearyl alcohol, octyldodecanol and decyltetradecanol, silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and dimethiconol, and fluorine-based oils such as perfluorodecane, perfluorooctane and perfluoropolyether. Furthermore, a volatile oil may be used as the oil.Examples of volatile hydrocarbon oils include isododecane and isohexadecane, and examples of volatile silicone oils include methyl trimethicone, caprylyl trimethicone, low-molecular-weight dimethylpolysiloxane (kinematic viscosity at 25°C 1 to 5CS), decamethylcyclopentasiloxane, decamethyltetrasiloxane, and ethyltrisiloxane, and one or more of these can be used.

[0043] In particular, the use of a volatile oil as the oil is more preferable because it provides a smooth feel in use and is not sticky. As the volatile oil, from the viewpoint of a smooth feel in use and is not sticky, one or more selected from the group consisting of isododecane, isohexadecane, low-molecular-weight dimethylpolysiloxane, and decamethylcyclopentasiloxane are preferred, and one or more selected from the group consisting of isododecane, low-molecular-weight dimethylpolysiloxane, and decamethylcyclopentasiloxane are more preferred.

[0044] In the present invention, the content of the volatile oil is not particularly limited, but is preferably 10% or more, more preferably 13% or more, and even more preferably 15% or more, based on the total amount of the water-in-oil emulsion cosmetic. It is also preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less. It is also preferably 10 to 40%, more preferably 13 to 35%, and even more preferably 15 to 30%. This range is more preferable because it provides a smooth feel in use and is less sticky.

[0045] In the present invention, the content of the oil agent (however, components (A) to (E) are not included in the content of the oil agent) is not particularly limited, but is preferably 15% or more, more preferably 18% or more, and even more preferably 20% or more, based on the total amount of the water-in-oil emulsion cosmetic. It is also preferably 60% or less, more preferably 55% or less, and even more preferably 50% or less. It is also preferably 15 to 60%, more preferably 18 to 55%, and even more preferably 20 to 50%. This range is more preferable because it provides a smooth feel in use and is less sticky.

[0046] The water used in the present invention may be tap water, purified water purified by distillation or the like, hot spring water, deep sea water, etc. Plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose water may also be used.

[0047] The water content in the present invention is not particularly limited, but is preferably 10% or more, more preferably 20% or more, and even more preferably 25% or more, based on the total amount of the water-in-oil emulsion cosmetic. It is also preferably 60% or less, more preferably 55% or less, and even more preferably 50% or less. It is also preferably 10 to 60%, more preferably 20 to 55%, and even more preferably 25 to 50%. This range is more preferable because it provides a smoother feel during use.

[0048] In the present invention, the composition may further contain alcohols. Examples of alcohols include monohydric alcohols and dihydric or higher polyhydric alcohols. More specific examples include monohydric alcohols such as ethanol and isopropanol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, 1,2-pentanediol, 1,2-hexylene glycol, caprylyl glycol, 1,3-propanediol, sorbitol, and polyethylene glycol.

[0049] The content of alcohols in the present invention is not particularly limited, but is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more, based on the total amount of the water-in-oil emulsion cosmetic. It is also preferably 20% or less, more preferably 18% or less, and even more preferably 15% or less. It is also preferably 1 to 20%, more preferably 2 to 18%, and even more preferably 3 to 15%. This range is more preferable because it provides a smoother feel when used and also provides a secondary moisturizing effect.

[0050] The water-in-oil emulsion cosmetic of the present invention is not particularly limited and can be produced by a conventional method. For example, it can be produced by uniformly dissolving and mixing component (A) in an aqueous component, uniformly dissolving and mixing components (B) to (E), adding an aqueous component containing component (A) to the mixture, and emulsifying. If necessary, the above-mentioned optional components can be added when adding and mixing each component.

[0051] The water-in-oil emulsion cosmetic of the present invention may be in any form, including, but not limited to, liquid, solid, gel, emulsion, cream, and the like.

[0052] The water-in-oil emulsion cosmetic of the present invention is not particularly limited, and can be used, for example, as a cosmetic for skin (including quasi-drugs), and examples thereof include makeup cosmetics such as emulsions, creams, beauty serums, massage products, pack products, hand creams, body lotions, body creams, sunscreens, primers, foundations, BB creams, concealers, eye shadows, mascaras, eyebrow products, and lipsticks, with makeup cosmetics being particularly preferred, and primers, foundations, and BB creams being more preferred. [Example]

[0053] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0054] Examples 1 to 19 and Comparative Examples 1 to 9: Water-in-oil foundation Water-in-oil foundations with the formulations shown in Tables 1 to 4 below were prepared by the manufacturing method shown below, and evaluated for (i) dispersibility of metal oxides, (ii) smooth feel in use, (iii) non-stickiness, and (iv) uniformity of cosmetic film using the evaluation methods shown below. The results are also shown in Tables 1 to 4.

[0055] [Table 1]

[0056] *1: KF-6028 (Shin-Etsu Chemical Co., Ltd.) *2: KF-6105 (Shin-Etsu Chemical Co., Ltd.) *3: BENTONE 38V BC (manufactured by Elementis) *4: BENTONE 27V (manufactured by Elementis) *5: SR1000 (Momentive Performance Materials) *6: SILFORM FLEXIBLE RESIN (manufactured by Momentive Performance Materials)

[0057] [Table 2]

[0058] [Table 3]

[0059] [Table 4]

[0060] (Manufacturing method) A: Mix ingredients (3) to (20) uniformly. B: Components (1) to (2) and (21) to (23) are mixed uniformly. D: B was gradually added to A to emulsify, and a water-in-oil foundation was obtained.

[0061] (Evaluation method) A panel of 10 cosmetic evaluation experts visually evaluated the water-in-oil foundations of the Examples and Comparative Examples, and applied them to perform a sensory evaluation, rating them on a 5-point scale according to the following evaluation criteria, and assigned scores. For "A. Dispersibility of metal oxides," 60 g of the water-in-oil foundations of the Examples and Comparative Examples were filled into No. 8 standard bottles, and visually evaluated one week later. For "B. Smooth feel in use" and "C. Non-stickiness," evaluations were performed during use, and for "D. Uniformity of cosmetic film," evaluations were performed on the finished film immediately after use. The scores of all panels were then averaged and judged according to the following criteria.

[0062] (Evaluation items) Dispersibility of metal oxides: Whether or not there are streaky color variations such as black, white, or red on the side of the standard bottle due to metal oxides. B. Smooth application: Whether the water-in-oil foundation spreads smoothly without getting caught on the skin during use C. Non-stickiness: Whether or not the makeup film feels sticky when it settles 2. Uniformity of the makeup layer: Is there any unevenness in the color of the makeup layer?

[0063] [Evaluation criteria] [Score]:[Evaluation result] 4 points: Very good 3 points: Good 2 points: Average 1 point: Bad 0 points: Very bad [Judgment criteria] [Judgment]: [Average score] ◎: 3.5 or above ○: 2.5 or more and less than 3.5 △: 1.5 or more and less than 2.5 ×: Less than 1.5

[0064] As is clear from the results in Tables 1 to 4, the water-in-oil foundations of Examples 1 to 19 of the present invention were excellent in metal oxide dispersibility, smooth feel in use, non-stickiness, and cosmetic film uniformity. In contrast, Comparative Example 1, in which the content of component (A) was less than 5%, was poor in metal oxide dispersibility and cosmetic film uniformity. Comparative Example 2, in which the content of component (A) was more than 15%, was significantly sticky and did not achieve satisfactory quality in terms of cosmetic film uniformity. Comparative Example 3, in which non-hydrophobized titanium dioxide was used instead of component (B), was poor in metal oxide dispersibility and cosmetic film uniformity. Comparative Example 4, in which the content of component (B) was more than 30%, was poor in metal oxide dispersibility, smooth feel in use, and cosmetic film uniformity. Comparative Example 5, in which polysorbate 80 was used instead of component (C), exhibited poor emulsification and was therefore unfeasible for evaluation. Comparative Example 6, in which the content of component (C) was less than 2%, was inferior in dispersibility of the metal oxide, smooth feel in use, and uniformity of the cosmetic film. Comparative Example 7, in which the content of component (C) was greater than 6%, was inferior in smooth feel in use and non-stickiness. Comparative Example 8, in which the content of component (D) was less than 0.3%, was inferior in dispersibility of the metal oxide and uniformity of the cosmetic film. Comparative Example 9, in which the content of component (D) was greater than 1.8%, was inferior in smooth feel in use and uniformity of the cosmetic film.

[0065] Example 20: Water-in-oil foundation (Component) (%) 1. Hydrogen Dimethicone 5% / Isopropyl Titanium Triisostearate 3% Treatment Zinc oxide (average particle size 0.025 μm) 10.0 2. Triethoxycaprylylsilane 2% treated red iron oxide 0.3 3. Yellow iron oxide treated with 2% triethoxycaprylylsilane 1.0 4. Triethoxycaprylylsilane 2% treated black iron oxide 0.05 5. 0.5% lecithin-treated titanium dioxide (average particle size 0.3 μm) 6.0 6. (Acrylates / Ethylhexyl acrylate / Dimethicone methacrylate) Copolymer*7 2.0 7. PEG-9 Polydimethylsiloxyethyl Dimethicone*1 2.8 8. Methyl trimethicone*8 10.0 9. Dimer Dilinoleic Acid (Phytosteryl / Isostearyl) / Cetyl / Stearyl / Behenyl) 3.0 10. Dimethyl distearyl ammonium hectorite*1 1.0 11. 2-Ethylhexyl para-methoxycinnamate 7.0 12. Dimethylpolysiloxane (2cs) 5.0 13. Trifluoroalkyldimethyltrimethylsiloxysilicate 2.5 14. Bis-ethylhexyloxyphenol methoxyphenyl triazine 0.5 15. Silica (spherical, average particle size 10 μm) 3.0 16. (Fluoride / Hydroxide / Oxide) / (Mg / K / Silicon) 5.0 17. Phenylbenzimidazole sulfonic acid 2.0 18. Ethanol 5.0 19. Niacinamide 5.0 20. Tranexamic acid 2.0 21. Ascorbic acid glucoside 1.0 22. Sodium pyrosulfite 0.01 23. Remaining purified water *7: KP-578P (Shin-Etsu Chemical Co., Ltd.) *8: Silicon TMF-1.5 (Shin-Etsu Chemical Co., Ltd.)

[0066] (Manufacturing method) A. Disperse ingredients 1 to 7 evenly using three rollers. B. Mix ingredients 8 to 16 uniformly at 80°C, cool to room temperature, then add A and disperse. C. Mix ingredients 17 to 23 until uniformly dissolved. C was added to DB and emulsified to obtain a water-in-oil foundation.

[0067] The water-in-oil foundation of Example 20 obtained in this manner was excellent in dispersibility of metal oxides, smooth feel in use, non-stickiness, and uniformity of the cosmetic film.

[0068] Example 21: Water-in-oil primer (Component) (%) 1. Dimethicone 3% treated titanium dioxide (average particle size 0.035 μm) 3.0 2. 0.5% ceramide treated titanium dioxide (average particle size: 0.30 μm) 3.0 3. Red No. 226 0.15 4. Ceramide 0.5% treated red iron oxide 0.02 5. Ceramide 0.5% treated yellow iron oxide 0.05 6. Ceramide 0.5% treated black iron oxide 0.01 7. Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl dimethicone*2 2.6 8. 2-Ethylhexyl paramethoxycinnamate 5.0 9. Isododecane 15.0 10. Diethylaminohydroxybenzoylhexyl benzoate 1.0 11. Bis-ethylhexyloxyphenol methoxyphenyl triazine 1.0 12. (Dimethicone / (PEG-10 / 15)) Crosspolymer*9 1.0 13. Dimethyl distearyl ammonium hectorite*3 0.3 14. Benzyl dimethyl stearyl ammonium hectorite*4 0.2 15. Trimethylsiloxysilicate*5 1.0 16. (Acrylates / Dimethicone) Copolymer 1.0 17. Methylparaben 0.1 18. Ethanol 5.0 19. Glycerin 3.0 20. Rosemary extract 0.1 21. Niacinamide 6.0 22. Tranexamic acid 3.0 23. Sodium chloride 0.8 24. Sodium pyrosulfite 0.005 25. Remaining purified water 26.Fragrance 0.03 27. Methylenebisbenzotriazolyl Tetramethylbutylphenol*10 2.0 *9: KSG-210 (Shin-Etsu Chemical Co., Ltd.) *10: K22-M40 (manufactured by Dai Nippon Kasei Co., Ltd.)

[0069] (Manufacturing method) A. Disperse ingredients 1 to 8 evenly using three rollers. B. Mix ingredients 9 to 16 uniformly at 80°C, cool to room temperature, then add A and disperse. C. Mix ingredients 17 to 27 until uniformly dissolved. C was added to DB and emulsified to obtain a water-in-oil base.

[0070] The water-in-oil foundation of Example 21 obtained in this manner was excellent in dispersibility of metal oxides, smooth feel in use, non-stickiness, and uniformity of the cosmetic film.

[0071] Example 22: Water-in-oil emulsion sunscreen (Component) (%) 1. 20% stearic acid treated titanium dioxide (average particle size: 0.008 μm) 2.0 2. Lauroyl lysine 15% treated zinc oxide (average particle size: 0.025 μm) 10.0 3. (Acrylates / Ethylhexyl acrylate) / Dimethicone methacrylate copolymer*7 2.0 4. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone*11 3.0 5. PEG-9 Polydimethylsiloxyethyl Dimethicone*1 1.0 6. Decamethylcyclopentasiloxane 15.0 7. Dimethylpolysiloxane (2CS) 10.0 8. Isododecane 3.0 9. Glyceryl tri-2-ethylhexanoate 2.0 10. Diethylhexyl succinate 2.0 11. Trifluoroalkyldimethyltrimethylsiloxysilicate 5.0 12. Trimethylsiloxysilicate*5 1.0 13. Propylene Glycol Dicaprate 4.0 14. 2-Ethylhexyl paramethoxycinnamate 7.0 15. Diethylaminohydroxybenzoylhexyl benzoate 2.5 16. Bis-ethylhexyloxyphenol Methoxyphenyltriazine 1.5 17. Dimethyl distearyl ammonium hectorite*3 0.5 18. Dimethicone 10% treated spherical silica (average particle size 15 μm) 0.5 19. Phenoxyethanol 0.1 20. 1,3-Butylene Glycol 3.0 21. Ethanol 5.0 22. Niacinamide 6.0 23. Tranexamic acid 2.0 24. Dipotassium glycyrrhizinate 0.1 25. Sodium pyrosulfite 0.003 26. Tremella fuciformis polysaccharide 0.8 27. Glycerin 1.0 28. Remaining purified water *11: KF-6038 (Shin-Etsu Chemical Co., Ltd.)

[0072] (Manufacturing method) A: Disperse ingredients 1 to 6 evenly. B: Components 7 to 16 are dissolved and mixed at 80°C. After cooling to room temperature, A and components 17 to 18 are added and dispersed. C: Mix ingredients 19 to 28 uniformly and dissolve. D: C was added to B and emulsified to obtain a water-in-oil emulsion sunscreen.

[0073] The water-in-oil emulsion sunscreen of Example 22 obtained in this manner had excellent dispersibility of metal oxides, a smooth feel when used, no stickiness, and a uniform cosmetic film.

[0074] Example 23: Water-in-oil emulsion solid foundation (Component) (%) 1. Titanium dioxide treated with 2% triethoxycaprylylsilane (Average particle size 0.3μm) 7.0 2. Hydrogen Dimethicone 5% / Isopropyl Titanium Triisostearate 3% Treatment Zinc oxide (average particle size 0.025 μm) 5.0 3. Hydrogenated lecithin 0.5% treated red iron oxide 0.35 4. Hydrogenated lecithin 0.5% treated yellow iron oxide 1.5 5. Hydrogenated lecithin 0.5% processed black iron oxide 0.2 6. Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl dimethicone*2 2.0 7. PEG-9 Polydimethylsiloxyethyl Dimethicone*1 1.0 8. Dimethylpolysiloxane (1.5CS) 2.0 9. Decamethylcyclopentasiloxane 5.0 10. Trifluoropropyldimethyltrimethylsiloxysilicate 1.8 11. Isohexadecane 10.0 12. Liquid Paraffin 5.0 13. Dextrin palmitate*12 2.0 14. Candelilla Wax*13 2.0 15. Inulin stearate*14 2.0 16. Glyceryl Tribehenate*15 2.0 17. Methylenebisbenzotriazolyltetramethylbutylphenol 2.0 18. Dimethyl distearyl ammonium hectorite 1.0 19. Benzyl dimethyl stearyl ammonium hectorite 0.5 20. Silica dimethyl silylate*16 3.0 21. (PEG-240 / Decyltetradeceth-20 / HDI) copolymer*17 0.1 22. Methyl parahydroxybenzoate 0.1 23. Niacinamide 6.0 24. Tranexamic acid 3.0 25. Dipotassium glycyrrhizinate 0.1 26. Sodium pyrosulfite 0.01 27. 1,3-Butylene Glycol 5.0 28. Monosodium L-glutamate 0.2 29. Remaining purified water *12: Leopard KL2 (manufactured by Chiba Flour Mills) *13: Refined Candelilla Wax SR-3 (Nippon Natural Products Co., Ltd.) *14: Leopard ISK2 (manufactured by Chiba Flour Mills) *15: SYNCROWAX HR-C-FL-(JP) (manufactured by Croda) *16: AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.) *17: ADEKA NOL GT-700 (ADEKA Corporation)

[0075] (Manufacturing method) A: Mix ingredients 1 to 17 uniformly at 80°C. B: After cooling to room temperature, add ingredients 18 to 20 to A and disperse. C: Mix ingredients 21 to 29 uniformly and dissolve. D: C was added to B heated to 60°C and emulsified, then filled into a resin dish container and cooled to room temperature to obtain a solid water-in-oil base.

[0076] The water-in-oil emulsified solid foundation of Example 23 obtained in this manner was excellent in dispersibility of metal oxides, smooth feel in use, non-stickiness, and uniformity of the cosmetic film.

Claims

1. The following components (A) to (D): (A) Electrolyte 5-15% by mass (B) Hydrophobized metal oxide: 0.1 to 30% by mass (C) Nonionic surfactant with HLB of 7 or less: 2 to 6% by mass (D) Organically modified clay mineral 0.3 to 1.8 mass% A water-in-oil emulsion cosmetic containing

2. 2. The water-in-oil emulsion cosmetic according to claim 1, comprising two or more types of electrolytes as component (A).

3. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the metal oxide of component (B) is one or more selected from the group consisting of titanium dioxide, zinc oxide, and iron oxide.

4. 4. The water-in-oil emulsion cosmetic according to claim 1, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.2 to 70.

5. 5. The water-in-oil emulsion cosmetic according to claim 1, wherein the nonionic surfactant of component (C) is a silicone surfactant.

6. The water-in-oil emulsion cosmetic according to any one of claims 1 to 5, further comprising a silicone film-forming agent as component (E).

7. 7. The water-in-oil emulsion cosmetic according to claim 6, wherein the content of the silicone film-forming agent as component (E) is 0.01 to 3% by mass based on the total amount of the water-in-oil emulsion cosmetic.

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