Water-in-oil emulsion cosmetic

Abstract

The present invention aims to provide a water-in-oil emulsion composition suitable for water-in-oil emulsion cosmetics that offers excellent stability, feel (stickiness / moisturizing effect / tightness), and makeup effect, and in particular, a water-in-oil emulsion composition that is substantially free of silicone oil. [Solution] (A) Divalent inorganic salt (component A) 0.5-8% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (Component B) 1-10% by mass, (C) Polyhydric alcohol (component C) 2.5-25% by mass, and (D) Hydrophobic coloring agent (component D) 0.01-30% by mass A water-in-oil emulsion composition characterized by containing the following:

Description

Technical Field

[0001] The present invention relates to a water-in-oil emulsion composition. More specifically, the present invention relates to a water-in-oil emulsion composition suitable as a water-in-oil emulsified cosmetic.

Background Art

[0002] Water-in-oil emulsion compositions are widely used in makeup bases, sunscreens, makeup cosmetics, etc. because they have higher water repellency, water resistance, and sweat resistance than oil-in-water emulsion compositions and have an excellent moisturizing effect. In water-in-oil emulsion compositions, silicone oils and silicone-based surfactants (hereinafter sometimes collectively referred to as "silicone oils") have been long preferred and used because of their high water repellency, good elongation, a non-greasy feeling, and high safety as components. Furthermore, from the viewpoint of anti-corrosion and the like, it has been common to incorporate polyhydric alcohols into the aqueous phase component. On the other hand, since silicone oils are not usually biodegradable, there is a concern that they may accumulate in the environment for a long time, pollute the environment, and disrupt the ecosystem. In recent years, cosmetics called "silicone-free" or "non-silicone" that do not contain silicone oils have attracted attention. However, in conventional cosmetics, excluding silicone oils with a large molecular weight, problems such as difficulty in maintaining the stability (viscosity reduction, appearance color, state) of the cosmetics over time occur. Patent Document 1 discloses a water-in-oil emulsion cosmetic characterized by containing (A) 0.3 to 3.5% by mass of one or more emulsifiers selected from the group consisting of polyglyceryl-3 diisostearate dimer dilinoleate, polyglyceryl-4 (diisostearate / polyhydroxystearate / sebacate), and tri(polyglyceryl-3 / lauryl) hydrogenated trilinoleate, (B) 8 to 40% by mass of liquid hydrocarbon oil, (C) 0.15 to 2.5% by mass of organically modified clay mineral, and (D) 0.4 to 40% by mass of hydrophobized metal oxide. It is stated that such a water-in-oil emulsion cosmetic improves the longevity and stability over time, and does not require the use of silicone. Patent Document 2 discloses a water-in-oil emulsion composition comprising oil, a nonionic surfactant with an HLB value of 8 or less, an electrolyte substance, and a water-soluble polyhydric alcohol, particularly a water-in-oil emulsion composition comprising 5 to 50% by weight of oil, 0.5 to 15% by weight of a nonionic surfactant, 0.01 to 5% by weight of an electrolyte substance, and 5 to 50% by weight of a water-soluble polyhydric alcohol, wherein the mass ratio of oil to nonionic surfactant is 1:1 to 50:1, and the weight ratio of nonionic surfactant to water-soluble polyhydric alcohol is 1:2 to 1:30. It is stated that such a water-in-oil emulsion composition exhibits a good emulsified state, has excellent stability, and can be a suitable composition for cosmetics with a non-sticky feel. Furthermore, Patent Documents 3 to 7 report water-in-oil emulsion cosmetics containing salt. However, in all cases, stickiness occurs when the amount of salt added is increased, and there are concerns about precipitation, so the amount of salt added has been limited. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-035935 [Patent Document 2] Japanese Patent Publication No. 2006-335735 [Patent Document 3] Japanese Patent Publication No. 2024-001585 [Patent Document 4] Japanese Patent Publication No. 2019-099510 [Patent Document 5] Japanese Patent Publication No. 2012-131733 [Patent Document 6] Japanese Patent Publication No. 2007-161650 [Patent Document 7] Japanese Patent Publication No. 2007-217393 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to provide a water-in-oil emulsion composition suitable for water-in-oil emulsion cosmetics that offers excellent stability over time, feel (stickiness / moisturizing sensation / tightness), and makeup effect, and in particular, a water-in-oil emulsion composition that is substantially free of silicone oil. [Means for solving the problem]

[0005] In view of the above issues, the inventors diligently studied the formulation of each component in order to produce a water-in-oil emulsion composition that is excellent in terms of long-term stability and usability, and is also environmentally friendly. As a result, they found that even without substantially containing silicone oil, the long-term stability of the cosmetic composition due to the coalescence of emulsion particles (e.g., change in appearance color) can be improved by incorporating a certain amount or more of a divalent inorganic salt as a salt. Based on this finding, the inventors further identified the optimal formulation ratio of each component and completed the present invention.

[0006] In other words, the present invention provides the following: [1] (A) Divalent inorganic salt (component A) 0.5-8% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (Component B) 1-10% by mass, (C) Polyhydric alcohol (component C) 2.5-25% by mass, and (D) Hydrophobic coloring agent (component D) 0.01-30% by mass A water-in-oil emulsion composition characterized by containing the following: [2] The composition according to [1], characterized in that it is substantially free of silicone oil. [3] The composition according to [1] or [2], comprising a divalent inorganic salt (component A) at a concentration of 1.5% by mass or more. [4] The composition according to any one of [1] to [3], wherein the salt concentration of the divalent inorganic salt (component A) represented by the following formula is 0.8 to 20% by mass: Amount of component A / (Amount of water contained in the water-in-oil emulsion composition + Amount of component A) × 100. [5] The composition according to [4], wherein the salt concentration is 5% by mass or more. [6] The composition according to any one of [1] to [5], wherein the divalent inorganic salt is magnesium sulfate or zinc sulfate. [7] A water-in-oil emulsion cosmetic, the composition according to any one of [1] to [6]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a water-in-oil emulsion cosmetic that has a light feel without any stickiness or grittiness, and has improved long-term stability and makeup effect. [Modes for carrying out the invention]

[0008] The water-in-oil emulsion composition of the present invention will be described in detail below. Unless otherwise specified, terms used herein have the meanings commonly used in the art.

[0009] The water-in-oil emulsion composition of the present invention is (A) Divalent inorganic salt (component A) 0.5-8% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (Component B) 1-10% by mass, (C) Polyhydric alcohol (component C) 2.5-25% by mass, and (D) Hydrophobic coloring agent (component D) 0.01-30% by mass This product is characterized by containing [specific ingredient]. This makes it possible to provide an oil-in-oil emulsion cosmetic with improved stability over time, feel, and makeup effect. Furthermore, since this composition eliminates the need to substantially use silicone oil, it is possible to provide an environmentally friendly oil-in-oil emulsion cosmetic. Here, "substantially free of silicone oil" means that in the water-in-oil emulsion composition, particularly in the entire water-in-oil emulsion cosmetic, the blending amount is less than 1%, preferably less than 0.1%, indicating that silicone oil is not intentionally blended, and it means that the blending amount is at a level where it may be unavoidably mixed in. Note that when used as a hydrophobizing agent for powders, or silicone powder blended as spherical powder does not correspond to silicone oil. In addition to the above components A to D, the water-in-oil emulsion composition of the present invention contains an oil component (component O) and an aqueous component (component W). Each component is described below.

[0010] 1. Component A (divalent inorganic salt) In the present invention, examples of the divalent inorganic salt blended as component A include salts of divalent metal ions harmless to the human body, preferably water-soluble salts. Specifically, salts of calcium (Ca 2+ ), magnesium (Mg 2+ ), iron (Fe 2+ ), zinc (Zn 2+ ), manganese (Mn 2+ ) can be mentioned. Preferred divalent inorganic salts include magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate, magnesium nitrate, calcium nitrate, zinc sulfate, etc. Particularly, magnesium sulfate or zinc sulfate is preferred. One kind or two or more kinds may be used. The blending amount (in the case of two or more kinds, the total thereof) is preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass, and most preferably 2 to 4% by mass with respect to the total amount of the water-in-oil emulsion composition obtained by the present invention. If it exceeds the upper limit, the feeling of use becomes heavy and sticky, and if it is below the lower limit, discoloration occurs over time. A preferred embodiment of the water-in-oil emulsion composition obtained by the present invention contains the divalent inorganic salt (component A) at a concentration of 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more. A preferred embodiment of the water-in-oil emulsion composition obtained by the present invention contains the divalent inorganic salt (component A) at a concentration of 8% by mass or less, 6% by mass or less, 4% by mass or less. Since the water-in-oil type emulsion composition of the present invention contains a hydrophobically treated colorant (described later), its stability over time becomes more important. However, by incorporating a certain amount of divalent inorganic salt, the stability can be maintained. In the present invention, as long as a certain amount of divalent inorganic salt is incorporated, other inorganic salts, such as monovalent inorganic salts, etc., may be incorporated within a range where the effects of the present invention are not impaired. The amount (content) of component A with respect to water in the water-in-oil type emulsion composition of the present invention, that is, the salt concentration, can be represented by the following formula. Salt concentration (mass%) = Amount of component A / (Amount of water contained in the water-in-oil type emulsion composition + Amount of component A) × 100 The salt concentration of the divalent inorganic salt is preferably 0.8 to 20% by mass, more preferably 1.8 to 17% by mass, and most preferably 3 to 13% by mass. If it exceeds the upper limit, the feeling of use becomes heavy and sticky, and if it is below the lower limit, discoloration occurs over time. In a preferred embodiment of the water-in-oil type emulsion composition obtained by the present invention, the salt concentration of the divalent inorganic salt is 0.8% by mass or more, 1.8% by mass or more, 3% by mass or more, 5% by mass or more. In a preferred embodiment of the water-in-oil type emulsion composition obtained by the present invention, the salt concentration of the divalent inorganic salt is 20% by mass or less, 17% by mass or less, 13% by mass or less.

[0011] 2. Component B (nonionic surfactant with an HLB value of 8 or less) The nonionic surfactant used in this invention is a nonionic surfactant with an HLB value of 8 or less. HLB (Hydrophilic-Lipophilic Balance) is a numerical value that represents the balance between the hydrophilicity and lipophilicity of a surfactant. If the HLB value exceeds 8, the hydrophilicity is high, making it difficult to obtain a stable water-in-oil emulsion composition. Nonionic surfactants with an HLB value of 8 or less include sorbitan fatty acid esters such as sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monoisostearate, and sorbitan sesquiisostearate; glyceryl or diglyceryl fatty acid esters such as glyceryl monomyristate, glyceryl monostearate, glyceryl monooleate, glyceryl monoisostearate, diglyceryl monostearate, and diglyceryl monooleate; propylene glycol fatty acid esters such as propylene glycol monolaurate and propylene glycol monostearate; and ethylene glycol monostearate. Ethylene glycol or polyethylene glycol fatty acid esters such as acid esters, diethylene glycol monostearate, polyoxyethylene (4E.O.) monostearate, diethylene glycol monooleate; polyoxyethylene alkyl ethers such as polyoxyethylene (2E.O.) lauryl ether, polyoxyethylene (4.2EO) lauryl ether, polyoxyethylene (2E.O.) palmityl ether, polyoxyethylene (2E.O.) oleyl ether; polyoxyethylene alkylphenyl ethers such as polyoxyethylene (2E.O.) nonylphenyl ether, polyoxyethylene (5E.O.) nonylphenyl ether, polyoxyethylene (3E.O.) octylphenyl ether; polyoxyethylene (3E.O.) castor oil, polyoxyethylene (10E.O.) castor oil, polyoxyethylene (5E.O.) hydrogenated castor oil, polyoxyethylene (7.Examples include polyoxyethylene castor oil or hydrogenated castor oils such as 5E.O.) hydrogenated castor oil and polyoxyethylene (10E.O.) hydrogenated castor oil, and polyglycerin fatty acid esters such as polyglyceryl-3 polyricinoleate, polyglyceryl-6 polyricinoleate, and hydrogenated tri(polyglyceryl-3) tri(polyglyceryl-3) trilinoleate. One or more of these are selected and used. The amount of these surfactants (the total amount if two or more are used) is preferably 1-10% by mass, more preferably 2-8% by mass, and most preferably 3-6% by mass, relative to the total amount of the water-in-oil emulsion composition obtained by this invention. Exceeding the upper limit results in a heavy, sticky feel, while below the lower limit leads to insufficient surfactant and poor emulsification. In this invention, other surfactants, such as those with an HLB value exceeding 8, may be included as long as a certain amount of nonionic surfactant with an HLB value of 8 or less is included and a good W / O emulsion structure is maintained.

[0012] 3. Component C (Polyhydric alcohol) The polyhydric alcohol used in this invention is water-soluble and has two or more hydroxyl groups in its molecule. It is not particularly limited as long as it is commonly used in cosmetics, and can be used from low polarity to high polarity. Examples include glycerin, propylene glycol, diethylene glycol, dipropylene glycol (DPG), 1,3-butylene glycol (BG), pentylene glycol, propanediol, polyglycerin, polyethylene glycol (PEG) 300-1500, polypropylene glycol (PPG), sorbitol, xylitol, mannitol, etc. These can be used individually or in combination of two or more. The amount used (total amount in the case of two or more) is preferably 2.5 to 25% by mass, more preferably 5 to 20% by mass, and most preferably 7.5 to 15% by mass, based on the total amount of the water-in-oil emulsion composition obtained by this invention. Exceeding the upper limit will result in a heavy feel and loss of freshness. Also, stability will decrease. Below the lower limit, the moisturizing effect will be lost.

[0013] 4. Component D (Hydrophobic coloring agent) The hydrophobic colorants used in the present invention are colorants that have undergone hydrophobic treatment, and as colorants, they are those commonly used in cosmetics, such as pigment-grade titanium dioxide, pigment-grade zinc oxide, yellow iron oxide, black iron oxide, red iron oxide, mica, Prussian blue, ultramarine blue, chromium oxide, chromium hydroxide and other metal oxides, metal complexes such as manganese violet and cobalt titanate, and inorganic pigments such as carbon black; Red No. 3, Red No. 104, Red No. 106, Red No. 20 Examples include organic pigments and their lake pigments such as No. 1, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 405, Red No. 505, Orange No. 203, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 401, Blue No. 1, Blue No. 404, etc.; natural organic pigments such as β-carotene, caramel, paprika pigment, etc., and complexes of these coloring pigments. However, pearl agents are not included in component D. The hydrophobic colorants of the present invention refer to these colorants that have been subjected to a hydrophobic treatment. Compounds of these colorants, or those surface-treated with general oils, silicone oils (in the present invention, it is preferable that silicone oils are not included in components O or B, but this does not apply to silicone oils used for hydrophobic treatment), fluorine compounds, or surfactants, can also be used, and one or more types can be used as needed.

[0014] Examples of such hydrophobic treatments include organosiloxane treatments such as methylhydrogenpolysiloxane treatment, silicone resin treatment, silicone gum treatment, acrylic silicone treatment, and fluorinated silicone treatment; metal soap treatments such as zinc stearate treatment; silane treatments such as silane coupling agent treatment and alkylsilane treatment; fluorine compound treatments such as perfluoroalkylsilane, perfluoroalkyl phosphate salt, and perfluoropolyether treatment; amino acid treatments such as N-lauroyl-L-lysine treatment; oil treatments such as squalane treatment; acrylic treatments such as alkyl acrylate treatment; and treatments with acylated amino acids. Preferably, treatments are performed with acylated amino acids and aluminum hydroxide (Al hydroxide). In the present invention, the amount of component D (total amount if there are two or more components) is preferably 0.01 to 30% by mass, more preferably 0.1 to 25% by mass, and most preferably 0.5 to 20% by mass, relative to the total amount of the water-in-oil emulsion composition obtained by the present invention. Exceeding the upper limit results in a powdery texture and a squeaky feeling. Also, stability decreases. Below the lower limit, sufficient makeup effect cannot be obtained.

[0015] 5. Ingredient O (Oily component) Oily components commonly used in cosmetics can be used. For example, regardless of their origin (animal oils, vegetable oils, synthetic oils, etc.) or their properties (solid oils, semi-solid oils, liquid oils, volatile oils, etc.), oils and fats, waxes, hydrocarbons, ester oils, higher fatty acids, higher alcohols, and fluorinated oils can be used.Specifically, for example, oils and fats such as hydrogenated oil, Japanese wax, cocoa butter, hydrogenated castor oil, olive oil, castor oil, macadamia nut oil, evening primrose oil, etc.; waxes such as beeswax, lanolin, candelilla wax, carnauba wax, jojoba wax, jojoba oil, liquid lanolin, etc.; hydrocarbons such as paraffin wax, ceresin, microcrystalline wax, polyethylene wax, liquid paraffin, squalane, polybutene, heavy liquid isoparaffin (hydrogenated polybutene), hydrogenated polyisobutene, etc.; cetyl palmitate, isopropyl myristate, isopropyl palmitate Cetyl 2-ethylhexanoate, octyldodecyl myristate, octyl stearate, octyl palmitate, isononyl isononanoate, diisopropyl adipate, di-2-ethylhexyl sebacate, neopentyl glycol dicaprate, glyceryl trimyristate, glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, caprylic / capric triglyceride, glyceryl behenate / eicosanedioate, diglyceryl diisostearate, diglyceryl triisostearate, tetra-2-ethylhexanoate Ester oils such as pentaerythritol acid, pentaerythritol dioctanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, diisostearyl malate, dicaprylyl carbonate, and alkyl benzoates (C12-C15); higher fatty acids such as stearic acid, palmitic acid, myristic acid, 12-hydroxystearic acid, behenic acid, isostearic acid, and oleic acid; cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol, isostearyl alcohol, and oleyl alcohol. Examples include higher alcohols such as ethanol and octyldodecanol; fluorinated oils such as perfluoropolyethers, perfluorodecalin, and perfluorooctane; and oil-soluble UV absorbers such as ethylhexyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homomenthyl salicylate, polysilicone-15, isoamyl methoxycinnamate, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, and t-butyl methoxydibenzoylmethane.The water-in-oil emulsion composition of the present invention may optionally contain one or more of these oily components. In the present invention, it is preferable that the oily component does not contain silicone oil.

[0016] 6. Ingredient W (Water-based ingredient) Component W (aqueous component) used in the present invention is used as a medium for uniformly dispersing or dissolving component A (divalent inorganic salt) and component C (polyhydric alcohol), and is mainly water. The water used is not particularly limited, as long as it is the type commonly used in cosmetics and the like. In addition to purified water, deep-sea water or steam-distilled water from plants such as rose water or lavender water may also be used, as long as they do not impair the effects of the present invention. One or more of these may be appropriately selected and used as needed. Other aqueous components are not particularly limited and can be used as a medium for uniformly dispersing or dissolving components A and C together with water; examples include water-soluble components. Examples include monohydric lower alcohols such as ethyl alcohol and isopropyl alcohol; water-soluble ultraviolet absorbers such as oxybenzone-3, oxybenzone-4, phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, methylenebisbenzotriazolyltetramethylbutylphenol, and trisbiphenyltriazine; and plant extracts such as aloe vera, witch hazel, witch hazel, cucumber, lemon, lavender, and rose. The water content in component W is not particularly limited as long as a water-in-oil emulsion composition can be produced, i.e., as long as it can take the structure of a W / O type emulsion, and is usually the residue after blending each component.

[0017] In preparing cosmetics, the water-in-oil emulsion composition of the present invention may, in addition to the above components A to D, O and W, further contain powders commonly used in cosmetics, as needed, within a range that does not impair the effects of the present invention. For example, ultraviolet scattering agents such as titanium dioxide and zinc oxide with a primary average particle size of 100 nm or less (e.g., 10 to 100 nm), mica such as talc, kaolin, muscovite, fluorphlogopite, rosemary, biotite, thiamite, synthetic mica, and sericite, inorganic powders such as anhydrous silicic acid, magnesium silicate, aluminum silicate, barium silicate, calcium silicate, bentonite, sericite, bismuth oxychloride, barium sulfate, boron nitride, light calcium carbonate, and heavy calcium carbonate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, vinyl acetate, propylene Examples of composite powders include acrylic polymers having vinyl ionate, vinyl lauryl stearate, vinyl stearate, styrene, vinyltoluene, (meth)acrylamide, (meth)acrylic acid, itaconic acid, maleic acid, etc. as constituent monomers; organic powders such as polyethylene, cellulose, magnesium stearate, zinc stearate, N-acyllysine, nylon, (vinyl dimethicone / methicone silsesquioxane) crosspolymer, and polymethylsilsesquioxane; and colored or colorless pearl pigments such as titanium mica and barium sulfate-coated titanium mica. The water-in-oil emulsion cosmetic of the present invention can use one or more of these components selected arbitrarily.

[0018] The powder may be surface-treated. Such surface treatments are not limited to those commonly used for cosmetic powders, but examples include N-stearoyl-L-glutamate disodium aluminum hydroxide treatment, palmitoyl proline, palmitoyl sarcosinate sodium magnesium palmitoyl glutamate palmitic acid treatment, isostearyl sebacate, stearoyl glutamate disodium aluminum hydroxide treatment, dimyristate aluminum treatment, hydrogenated lecithin, trimyristate aluminum hydroxide treatment, and sodium alginate treatment.

[0019] The water-in-oil emulsion composition of the present invention may contain pharmaceuticals in addition to the above-mentioned components. The pharmaceuticals that can be incorporated into the water-in-oil emulsion composition of the present invention are not particularly limited, but examples include steroids, anti-inflammatory and analgesic agents, antibiotics, antibacterial agents, immunomodulators, antitumor agents, vitamins, etc. The content of these pharmacoactive ingredients is based on the approved concentration for pharmaceuticals already approved as ointments or creams, but is preferably 0.001 to 50% by mass, more preferably 0.001 to 10% by mass.

[0020] A preferred embodiment of the water-in-oil emulsion composition of the present invention is a water-in-oil emulsion cosmetic. In the present invention, a water-in-oil emulsion cosmetic is one that can be used on the human body, etc., and is mainly a cosmetic, but does not exclude its use as a quasi-drug, pharmaceutical, etc. Furthermore, the aforementioned cosmetic includes basic cosmetics, makeup cosmetics, hair cosmetics, etc. Moreover, since the water-in-oil emulsion cosmetic of the present invention is a water-in-oil emulsion cosmetic with improved usability, makeup effect, and long-term stability, it is particularly suitable for sunscreen cosmetics and makeup cosmetics.

[0021] In addition to the above-mentioned components, the water-in-oil emulsion cosmetic composition of the present invention may optionally contain other components commonly used in cosmetics, as long as they do not impair the effects of the present invention. Examples of such optional components include humectants, thickeners, dyes, lower alcohols, organic acids, organic amines, metal ion chelating agents, pH adjusters, antioxidants, preservatives, and fragrances.

[0022] Another embodiment of the water-in-oil emulsion composition of the present invention is characterized by containing the following components A to D. (A) Divalent inorganic salt (component A) 0.5-8% by mass or 1-6% by mass or 2-4% by mass (B) Nonionic surfactant with an HLB value of 8 or less (Component B) 1-10% by mass, 2-8% by mass, or 3-6% by mass (C) Polyhydric alcohol (component C) 2.5-25% by mass or 5-20% by mass or 7.5-15% by mass (D) Hydrophobic coloring agent (component D) 0.01-30% by mass or 0.1-25% by mass or 0.5-20% by mass

[0023] A preferred embodiment of the water-in-oil emulsion composition of the present invention is: (A) Divalent inorganic salt (component A) 1-6% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (Component B) 2-8% by mass, (C) Polyhydric alcohol (component C) 5-20% by mass, and (D) Hydrophobic coloring agent (component D) 0.1-25% by mass It is characterized by containing [the following].

[0024] A more preferred embodiment of the water-in-oil emulsion composition of the present invention is: (A) Divalent inorganic salt (component A) 2-4% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (component B) 3-6% by mass, (C) Polyhydric alcohol (component C) 7.5-15% by mass, and (D) Hydrophobic coloring agent (component D) 0.5-20% by mass It is characterized by containing [the following].

[0025] Furthermore, in the present invention, the method for producing a water-in-oil emulsion composition can be the conventional method for producing a water-in-oil emulsion composition, and generally, it can be produced by mixing an aqueous component with an oily component. For example, a water-in-oil emulsion composition can be prepared by preparing an oil phase containing an oily component (O), a nonionic surfactant with an HLB value of 8 or less (B), a hydrophobic coloring agent (D), etc., and an aqueous phase containing an aqueous component (W), a divalent inorganic salt (A), a polyhydric alcohol (B), etc., and then emulsifying the mixture by adding the aqueous phase to the oil phase. Alternatively, the oil phase and aqueous phase can be heated as needed.

[0026] The conditions for preparing the oil phase of the present invention can be appropriately selected depending on the constituent components of the oil phase used.

[0027] Furthermore, the conditions for preparing the aqueous phase of the present invention can be appropriately selected depending on the constituent components of the aqueous phase used.

[0028] Next, the aqueous phase is gradually added to the oil phase while stirring the oil phase, and further stirring and degassing are performed to obtain the desired water-in-oil emulsion composition. The temperature for emulsification is appropriately selected depending on the types of oil and aqueous phases, but is usually room temperature to 70°C, preferably room temperature to 50°C. If the temperature is too low, emulsification may be difficult, and if it is too high, it may affect liquid crystal formation. Therefore, if the oil phase is dissolved at a high temperature, it is desirable to cool it to a predetermined temperature when adding it to the aqueous phase. However, since emulsification becomes difficult if the oil phase solidifies, the temperature at which fluidity can be maintained is the limit. [Examples]

[0029] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Furthermore, the reagents and materials used are commercially available unless otherwise specified. Unless otherwise noted, abbreviations used herein are the same as those commonly used in the art. (Examples 1-40, Comparative Examples 1-13) Examples 1-40 and Comparative Examples 1-13 of water-in-oil emulsion cosmetics were prepared by mixing the ingredients listed in Tables 1-4 below using the conventional procedure, i.e., by mixing the ingredients listed in Tables 1-4 below. The obtained water-in-oil emulsion cosmetics were subjected to stability tests over time and sensory tests (stickiness / moisturizing effect / tightness / makeup effect) based on the following criteria, and the results are shown in Tables 1-4 below. If emulsification was not possible and evaluation could not be performed, it was marked with "-". The numerical values ​​for each ingredient represent the mass percentage of that ingredient when the total mass of the water-in-oil emulsion cosmetic is set to 100%, and water was adjusted to 100% by mass as the "residue".

[0030] <Stability Test> (Evaluation method) 50 ml of each example composition was placed in a 60 ml glass vial. The sample vials were sealed and placed in a 50°C constant temperature bath. After 3 months, the Lab values ​​of the compositions were measured using a SE6000 spectrophotometer from Nippon Denshoku Corporation. The color difference ΔE was calculated from the resulting Lab values ​​and evaluated according to the following evaluation criteria. (Evaluation Criteria) ◎: The color difference (ΔE) is 1.0 or less. ○: The color difference (ΔE) is greater than 1.0 and less than or equal to 1.5. △: The color difference (ΔE) is greater than 1.5 and less than or equal to 2.0. ×: Chromatic difference (ΔE) exceeds 2.0.

[0031] <Stickyness Test> (Evaluation method) Regarding the feel of each example composition, a panel of 10 experts applied each sample to their skin and evaluated the feel (non-stickiness) according to the following criteria. (Evaluation Criteria) ◎: 9-10 people rated it as not sticky. ○: 6-8 people rated it as not sticky. △: 3 to 5 people rated it as not sticky. ×: Two or fewer people rated it as not sticky.

[0032] <Moisture-retaining test> (Evaluation method) Regarding the feel of each example composition, a panel of 10 experts applied each sample to their skin and evaluated the duration of moisturizing effect (hydration) from the time of application to 3 hours later, according to the following criteria. (Evaluation Criteria) ◎: 9-10 people rated it as moisturizing. ○: 6-8 people rated it as moisturizing. △: 3 to 5 people rated it as moisturizing. ×: Two or fewer people rated it as moisturizing.

[0033] <Squeak test> (Evaluation method) Regarding the feel of each example composition, a panel of 10 experts applied each sample to their skin and evaluated the feel (squeakiness) according to the following criteria. (Evaluation Criteria) ◎: 9-10 people rated it as having no creaking sensation. ○: 6-8 people rated it as having no creaking sensation. △: 3 to 5 people rated it as having no creaking sensation. ×: Two or fewer people rated it as having no creaking sensation.

[0034] <Makeup effectiveness test> (Evaluation method) Regarding the makeup effect of each example composition, a panel of 10 experts applied each sample to their skin and evaluated whether the skin tone brightened (tone-up) after application according to the following criteria. (Evaluation Criteria) ◎: 9-10 people rated it as having improved skin tone. ○: 6-8 people reported an improvement in skin tone. △: 3 to 5 people rated it as having improved skin tone. ×: Two or fewer people reported a tone-up effect.

[0035] [Table 1]

[0036] [Table 2]

[0037] [Table 3]

[0038] [Table 4]

[0039] The results shown in Table 1 indicate that a water-in-oil emulsion composition with excellent temporal stability can be produced by incorporating a certain amount of divalent inorganic salt. The results shown in Table 2 indicate that by incorporating a certain amount of surfactant with an HLB value of 8 or less, it is possible to produce a water-in-oil emulsion composition with excellent temporal stability and feel (stickiness). The results shown in Table 3 indicate that by incorporating a certain amount of polyhydric alcohol, it is possible to produce a water-in-oil emulsion composition with excellent usability (stickiness and moisturizing effect). The results shown in Table 4 indicate that by incorporating a certain amount of hydrophobic coloring agent, it is possible to produce a water-in-oil emulsion composition with excellent feel (squeakiness) and makeup effect. Similar efficacy tests were conducted on formulation examples 1-6 below, and excellent results were obtained in terms of "long-term stability (discoloration)," "feel (stickiness)," "usability (moisturizing feeling)," "usability (squeakiness)," and "makeup effect." Furthermore, formulation examples 1-4 have an SPF of 30-50 and UVA of approximately ++-++++. The values ​​for each ingredient represent the mass percentage of that ingredient when the total mass of the water-in-oil emulsion cosmetic is set to 100%, and water was adjusted to 100% by mass as the "residue."

[0040] Formulation Example 1: Water-in-oil emulsion cosmetic (primer) [Ingredients] (Amount %) Tocopherol 0.05% Quaternium-90 Bentonite 1% Undecane 3% Tridecane 3% Ethylhexyl palmitate 5% Ethyl isostearate 3% (Caprylic / Capric Acid) Coconut Alkyl 3% Phytosteryl / Octyldodecyl Lauroyl Glutamate 0.5% Isostearyl isostearate 3% Isopropyl myristate 3% Hexyl Lauryl Sodium 3% Octyldodecanol 0.5% Polyhydroxystearic acid 0.3% Isostearic acid 0.7% Polyglyceryl-6 polyricinoleate (HLB: 3.3) 1% Hydrogenated trilinoleate tri(polyglyceryl-3 / lauryl) (HLB:8) 3% Disodium cocoyl glutamate, aluminum hydroxide-treated silica, 3% Saccharomyces culture treated with lauroyl lysine 3% Rosehip oil 0.01% water residue Magnesium sulfate 2% BG 3% Pentylene glycol 2% Propanediol 5% Glycerin 1% Xanthan gum 0.05% Wasabi root fermented extract 0.01% Centella asiatica leaf / stem extract 0.01% Grapefruit seed extract 0.01% Edelweiss flower / leaf extract 0.01% Royal jelly extract 0.01% Disodium cocoyl glutamate, treated with aluminum hydroxide, pearlescent agent 2% Disodium stearoyl glutamate, aluminum hydroxide-treated iron oxide black, 0.01% Disodium stearoyl glutamate, aluminum hydroxide-treated iron oxide (red), 0.15% Disodium stearoyl glutamate, aluminum hydroxide-treated iron oxide (yellow), 0.2% Disodium stearoyl glutamate, aluminum hydroxide-treated mica 1% Stearic acid, aluminum hydroxide-treated titanium dioxide microparticles 6% Isostearic acid-treated zinc oxide microparticles 4%

[0041] Formulation Example 2: Water-in-oil emulsion cosmetic (primer) [Ingredients] (Amount %) Tocopherol 0.05% (C15-C19) Alkanes 3% Disteardimonium hectorite 0.5% Dicaprylyl carbonate 3% Caprylic / Capric Triglyceride 5% Diethyl sebacate 5% Isostearyl neopentanoate 1% Ethylhexyl Methoxycinnamate 7% Ethylhexyl salicylate 3% Ethylhexyltriazone 0.5% Bis-ethylhexyloxyphenol methoxyphenyl triazine 1% Diethylaminohydroxybenzoyl hexyl benzoate 3% Polyhydroxystearic acid 0.5% Isostearic acid 0.5% Polyglyceryl-2 Triisostearate 0.5% Polyglyceryl-3 polyricinoleate (HLB:4) 3% Hydrogenated trilinoleate tri(polyglyceryl-3 / lauryl) (HLB:8) 1% PEG-2 stearate (HLB:5) 0.5% Aluminum Starch Octenylsuccinate 1% Lauroyl lysine-treated Saccharomyces culture 1% Orange oil 0.01% water residue Magnesium sulfate 1.5% Calcium chloride 1% PG 3% Pentylene glycol 2% Propanediol 3% Caprylyl glycol 0.5% Phenoxyethanol 0.5% Glucosyltrehalose 0.5% Hydrolyzed hydrogenated starch 0.5% Artemisia capillaris flower extract 0.01 Clove extract 0.01% Callicarpa japonica fruit extract 0.01% Wild thyme extract 0.01% Disodium cocoyl glutamate, treated with aluminum hydroxide, 1% pearlescent agent. Isopropyl titanium triisostearate-treated black iron oxide 0.1% Isopropyl titanium triisostearate-treated red iron oxide 0.15% Isopropyl titanium triisostearate-treated iron oxide yellow 1.2% Isopropyl titanium triisostearate-treated mica 0.8% Isostearic acid, aluminum hydroxide-treated, titanium dioxide microparticles, 4% Isostearic acid-treated zinc oxide microparticles 8%

[0042] Formulation Example 3: Water-in-oil emulsion cosmetic (foundation) [Ingredients] (Amount %) Tocopherol 0.05% Dimethylsilylated silica 1% Squalane 5% (C13-C15) Alkanes 3% Hexyl laurate 5% Ethyl isostearate 5% Isostearyl isostearate 3% Methylheptyl laurate 2% Stearyl stearate 0.5% Macadamia nut fatty acid phytosteryl 0.5% Octyldodecyl stearoyl oxystearate 0.5% Polyhydroxystearic acid 0.5% Isostearic acid 0.5% Polyglyceryl-6 polyricinoleate (HLB: 3.3) 1% Polyglyceryl-3 polyricinoleate (HLB:4) 3% Rice bran wax powder 2% Hydrogen dimethicone-treated silica 2% water residue Magnesium chloride 2% BG 3% Pentylene glycol 2% Propanediol 3% Ethanol 2% Sorbitol 1% (Sodium Acrylate / Sodium Acryloyldimethyl Taurate) Copolymer 0.05% Scutellaria baicalensis root extract 0.01% Cocoa seed extract 0.01% Job's Tears Seed Extract 0.01% Licorice leaf extract 0.01% Triethoxycaprylylsilane-treated iron oxide black 0.1% Triethoxycaprylylsilane-treated red iron oxide 0.2% Triethoxycaprylylsilane-treated yellow iron oxide 1.3% Triethoxycaprylylsilane-treated mica 1.5% 7% Titanium Dioxide Microparticles Treated with Alumina Stearate Triethoxycaprylylsilane-treated zinc oxide microparticles 8%

[0043] Formulation Example 4: Water-in-oil emulsion cosmetic (foundation) [Ingredients] (Amount %) Tocopherol 0.05% (C13-C15) Alkanes 2% Squalane 2% Quaternium-90 Bentonite 0.5% Dicaprylyl carbonate 3% Alkyl (C12-15) benzoate 3% Caprylic / Capric Triglyceride 2% Diethyl sebacate 4% Diisopropyl sebacate 4% Isodecyl neopentanoate 2% Ethylhexyl salicylate 5% Ethylhexyltriazone 1% Bis-ethylhexyloxyphenol methoxyphenyl triazine 1.5% Diethylamino hydroxybenzoyl hexyl benzoate 4% Polyhydroxystearic acid 0.5% Isostearic acid 0.5% Polyglyceryl-3 polyricinoleate (HLB:4) 3.5% PEG-5 Hydrogenated Castor Oil (HLB:6) 0.5% Aluminum Starch Octenylsuccinate 1% Carnauba wax spherical powder 1% Lavender oil 0.01% water residue Magnesium sulfate 2% Pentylene glycol 2% Propanediol 4% Ethylhexylglycerin 0.05% Phenoxyethanol 0.5% Diglycerin 2% Sodium hyaluronate 0.01% Geranium robertianum extract 0.01% Tabebuia impetiginosa bark extract 0.01% Rehmannia glutinosa root extract 0.01% Hydroxypropyl methylcellulose stearoxy ether 0.05% PEG / PPG / Polybutylene Glycol-8 / 5 / 3 Glycerin 0.5% Disodium Cocoyl Glutamate, Aluminum Hydroxide Treated Iron Oxide Black, 0.05% Disodium Cocoyl Glutamate, Aluminum Hydroxide-Treated Iron Oxide (Red), 0.25% Disodium Cocoyl Glutamate, Aluminum Hydroxide-Treated Iron Oxide (Yellow) 1% Disodium Cocoyl Glutamate, Aluminum Hydroxide Treated Mica 1.5% 8% Titanium Dioxide Microparticles Treated with Alumina Stearate Dimethicone-treated zinc oxide microparticles 8%

[0044] Formulation Example 5: Water-in-oil emulsion cosmetic (blush) [Ingredients] (Amount %) Tocopherol 0.05% (C13-C15) Alkanes 4% Squalane 4% Disteardimonium hectorite 1.5% Dextrin isostearate 0.4% Isostearyl isostearate 5% Hexyl laurate 5% Caprylic / Capric Triglyceride 4% Diethyl sebacate 3% Isostearic acid 0.5% Polyglyceryl-2 Diisostearate 0.5% Aluminum starch octenyl succinate 3% Polyglyceryl-3 polyricinoleate (HLB: 3.3) 4% Steerless-2 (HLB:4) 0.5% water residue Zinc sulfate 2.5% BG 5% Pentylene glycol 1% DPG 2% Glycerin 2% PPG-9 Diglyceryl 0.5% Evening Primrose Seed Extract 0.01% Artichoke leaf extract 0.01% Yuzu fruit extract 0.01% Acetyl hexapeptide-8 (appropriate amount) Triethoxycaprylylsilane, aluminum hydroxide-treated pigment-grade titanium dioxide, 3% Triethoxycaprylylsilane-treated iron oxide black 0.01% Triethoxycaprylylsilane-treated red iron oxide 0.01% Triethoxycaprylylsilane-treated yellow iron oxide 0.01% Triethoxycaprylylsilane-treated mica 0.01% Triethoxycaprylylsilane-treated Red 226 0.16% Dimethicone-treated ultramarine 0.01% Dimethicone-treated pearl agent 3%

[0045] Formulation Example 6: Water-in-oil emulsion cosmetic (blush) [Ingredients] (Amount %) Tocopherol 0.05% (C15-C19) Alkanes 3% Squalane 5% Disteardimonium hectorite 0.5% Dextrin palmitate 1% Ethyl isostearate 5% Octyldodecyl myristate 2% Caprylic / Capric Triglyceride 5% Isopropyl myristate 4% Isostearic acid 0.5% Polyglyceryl-2 Triisostearate 0.5% Magnesium stearate-treated silica 3% Polyglyceryl-3 polyricinoleate (HLB: 3.3) 3.5% Behenez-5 (HLB:7) 0.5% water residue Zinc sulfate 1% Magnesium sulfate 1.5% BG 3% Pentylene glycol 2% PG 2% Diglycerin 2% Carrageenan 0.05% PEG-400 0.5% Honeysuckle flower extract 0.01% Peony root extract 0.01% Somei Yoshino cherry leaf extract 0.01% Bilberry leaf extract 0.01% Disodium Cocoyl Glutamate, Aluminum Hydroxide-Treated Pigment-Grade Titanium Dioxide 2% Disodium cocoyl glutamate, aluminum hydroxide-treated iron oxide black, 0.01% Disodium cocoyl glutamate, aluminum hydroxide-treated iron oxide (red), 0.06% Disodium cocoyl glutamate, aluminum hydroxide-treated iron oxide (yellow), 0.01% Disodium cocoyl glutamate, aluminum hydroxide-treated mica 0.01% Disodium cocoyl glutamate, treated with aluminum hydroxide, 0.8% Magnesium stearate treated pearl agent 4% [Industrial applicability]

[0046] Even without containing silicone oil, it is possible to provide a water-in-oil emulsion cosmetic that has a light feel without squeaking or stickiness, and has improved long-term stability and makeup effect.

Claims

1. (A) Divalent inorganic salt (component A) 0.5 to 8% by mass, (B) Nonionic surfactant with an HLB value of 8 or less (component B) 1 to 10% by mass, (C) Polyhydric alcohol (component C) 2.5 to 25% by mass, and (D) Hydrophobic coloring agent (component D) 0.01 to 30% by mass A water-in-oil emulsion composition characterized by containing the following:

2. The composition according to claim 1, characterized in that it is substantially free of silicone oil.

3. The composition according to claim 1, comprising a divalent inorganic salt (component A) at a concentration of 1.5% by mass or more.

4. The composition according to claim 1, wherein the salt concentration of the divalent inorganic salt (component A) represented by the following formula is 0.8 to 20% by mass: Amount of component A / (Amount of water contained in the water-in-oil emulsion composition + Amount of component A) × 100.

5. The composition according to claim 4, wherein the salt concentration is 5% by mass or more.

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