JP7611657B2 - Water-in-oil emulsion composition - Google Patents

Description

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

Cosmetics are required to have various appearances in order to be visually novel, and one of them is a cosmetic colored in black, red, etc. One method for obtaining such a cosmetic is to add color by mixing a color pigment into an emulsion, but if the emulsion is cloudy, the colored appearance will be dull and will not give a clean impression. Furthermore, when the cosmetic is applied to the skin, the skin will take on the color of the cosmetic, resulting in an unnatural makeup finish.
Conventionally, in order to obtain a transparent appearance, water-in-oil emulsion compositions in which the refractive indexes of the water phase and the oil phase are adjusted have been investigated (for example, Patent Documents 1 to 4).
However, when a coloring pigment is added to color these materials, the coloring pigment does not mix uniformly, and problems arise in terms of stability, such as separation and a decrease in viscosity.

Japanese Unexamined Patent Publication No. 64-22344 JP 2005-220076 A Japanese Patent Application Publication No. 3-217229 JP 2012-188392 A

The present invention relates to a water-in-oil emulsion composition that has a uniform, transparent appearance without dullness while being colored in black, red, or the like, and that leaves the skin after application with a transparent, lustrous appearance and a natural finish.

The inventors have discovered that by adjusting the refractive index of the water phase and the oil phase and by using a color pigment and a cationically modified clay mineral, it is possible to obtain a water-in-oil emulsion composition that is colored, uniform, and transparent, that gives the applied skin a transparent yet lustrous appearance, and that provides a natural finish and is highly stable.

The present invention comprises the following components (A), (B), (C), (D) and (E):
(A) a cation-modified clay mineral substituted with a quaternary ammonium ion;
(B) a color pigment,
(C) water,
(D) oil agent,
(E) The water-in-oil emulsion composition contains a surfactant, and the difference in refractive index between the aqueous phase and the oil phase, excluding components (A) and (B), is less than 0.07.

The water-in-oil emulsion composition of the present invention has a colored, uniform, and transparent appearance, and after application to the skin, the skin appears transparent and glossy, resulting in a clean, natural finish. In addition, separation and viscosity loss are suppressed, and the composition has excellent storage stability.

The cationic modified clay mineral substituted with quaternary ammonium ions, component (A) used in the present invention, is not limited as long as it is one used in ordinary cosmetics, but is preferably a cationic modified clay mineral in which a layered clay mineral such as bentonite, laponite, hectorite, montmorillonite, or magnesium aluminum silicate is treated with a quaternary ammonium salt type cationic surfactant to replace the sodium ions between the layers of the layered clay mineral with quaternary ammonium ions.

Here, the layered clay mineral is, for example, a layered silicate mineral belonging to the smectide genus, which is generally represented by the following formula (1):
(X,Y) _2-3 (Si,Al) ₄ O ₁₀ (OH) ₂ Z _1/3・nH ₂ O (1)
[In formula (1), X represents Al, Fe(III), Mn(III) or Cr(III); Y represents Mg, Fe(II), Ni, Zn, Li or Mn(II); and Z represents K, Na, 1/2Ca or 1/2Mg]
Preferred examples of the clay minerals include colloidal hydrous aluminum silicate having a three-layer structure represented by the following formula:
The quaternary ammonium salt type cationic surfactant for treating the layered clay mineral is
The following formula (2):

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

Specifically, dodecyl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, myristyl dimethyl ethyl ammonium chloride, cetyl dimethyl ethyl ammonium chloride, stearyl dimethyl ethyl ammonium chloride, behenyl dimethyl ethyl ammonium chloride, myristyl diethyl methyl ammonium chloride, cetyl diethyl methyl ammonium chloride, stearyl diethyl methyl ammonium chloride, behenyl diethyl methyl ammonium chloride, Examples of the above-mentioned compounds include benzyl dimethyl myristyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, benzyl dimethyl behenyl ammonium chloride, benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dihydroxyethyl ammonium chloride, and compounds in which the chloride of each of the above-mentioned compounds is replaced with a bromide compound, and further examples thereof include dipalmityl propyl ethyl ammonium methyl sulfate.
Among these, from the viewpoints of obtaining a colored, uniform and transparent appearance, making the skin look transparent and glossy after application, and suppressing separation and viscosity reduction after storage, it is preferable to contain at least one or more types selected from benzyl dimethylstearyl ammonium chloride and dimethyl distearyl ammonium chloride, and dimethyl distearyl ammonium chloride is more preferable.

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

One or more types of component (A) can be used, and from the viewpoints of obtaining a colored, uniform, and transparent appearance, making the skin appear transparent and glossy after application, suppressing separation and viscosity reduction after storage, and improving elongation, the content is preferably 0.1 to 4 mass% of the total composition, more preferably 0.5 to 2.5 mass%, and even more preferably 1 to 1.8 mass%.

Examples of the color pigment of component (B) include metal oxides such as titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red iron oxide, Prussian blue, ultramarine, chromium oxide, and chromium hydroxide, metal complexes such as manganese violet and cobalt titanate, and inorganic pigments such as carbon black; Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, and Red No. 220. synthetic organic pigments such as 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, and Blue No. 404; natural organic pigments such as β-carotene, caramel, and paprika color, and composites of these color pigments and composite pigments combining these color pigments with pearl pigments. Examples of pearl pigments that can be combined with color pigments include natural or synthetic inorganic powders such as mica, phlogopite, talc, silica, sericite, mica, glass, kaolin, bismuth oxychloride, cerium oxide, calcium sulfate, barium sulfate, magnesium sulfate, and plate-like alumina powder. Specific examples of composite pigments include titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated titanium mica, iron oxide-coated synthetic phlogopite, chromium oxide-coated titanium mica, titanium oxide-coated glass powder, iron oxide-coated glass powder, titanium oxide-containing glass powder, and iron oxide-containing glass powder.
From the viewpoints of obtaining a colored, transparent appearance and making the skin appear transparent yet lustrous after application, the color pigment of component (B) preferably contains at least one or more selected from titanium oxide, yellow iron oxide, black iron oxide, red iron oxide (red iron oxide) and black iron oxide-coated glass powder, more preferably contains at least one or more selected from black iron oxide, red iron oxide (red iron oxide) and black iron oxide-coated glass powder, and even more preferably contains at least one or more selected from red iron oxide (red iron oxide) and black iron oxide-coated glass powder.

These color pigments can be used as they are, or can be used after hydrophobization treatment, such as surface treatments including fluorine compound treatment, silicone treatment, alkyl treatment, alkylsilane treatment, metal soap treatment, water-soluble polymer treatment, amino acid treatment, acylated amino acid treatment, lecithin treatment, organic titanate treatment, polyol treatment, acrylic resin treatment, methacrylic resin treatment, and urethane resin treatment.
The hydrophobization treatment preferably includes at least one or more treatments selected from an amino acid treatment and an acylated amino acid treatment, and more preferably includes at least an acylated amino acid treatment, from the viewpoints of obtaining a colored, transparent appearance and making the skin after application look transparent and glossy.
Examples of amino acids for treating color pigments include proline, hydroxyproline, alanine, glycine, sarcosine, lysine, aspartic acid, glutamic acid, and the like, including salts thereof. The fatty acid constituting the acyl group of the acylated amino acid is preferably a fatty acid having 1 to 23 carbon atoms, more preferably a fatty acid having 8 to 20 carbon atoms, and among these, stearoyl glutamic acid, lauroyl aspartic acid, dilauroyl glutamic acid lysine, and lauroyl lysine are even more preferred. Examples of salts thereof include Na, Ca, Al, Mg, Zn, Zr, and Ti salts.
Specifically, from the viewpoint of obtaining a colored, transparent appearance and making the skin after application look transparent and glossy, those treated with disodium stearoyl glutamate, sodium lauroyl aspartate, etc. are preferred, and among these, those treated with disodium stearoyl glutamate are more preferred.
The color pigment can be subjected to a hydrophobic treatment by a conventional method.

Component (B) can be used alone or in combination with two or more kinds. From the viewpoint of obtaining a colored, transparent appearance and making the skin after application appear transparent and lustrous, the content is preferably 0.01 to 1.5 mass %, more preferably 0.1 to 1.1 mass %, and even more preferably 0.15 to 0.8 mass %, of the total composition.
Furthermore, when component (B) is black iron oxide or black iron oxide-coated glass powder, from the viewpoints of obtaining a colored, transparent appearance and making the skin after application appear transparent and glossy, the content is preferably 0.1 to 0.8 mass %, more preferably 0.15 to 0.7 mass %, even more preferably 0.2 to 0.6 mass %, and even more preferably 0.25 to 0.4 mass %, of the total composition.
Furthermore, when component (B) is red iron oxide (red iron oxide), from the viewpoints of obtaining a colored, transparent appearance and making the skin after application appear transparent yet lustrous, the content is preferably 0.01 to 1.5 mass %, more preferably 0.1 to 1.1 mass %, even more preferably 0.13 to 0.8 mass %, and even more preferably 0.15 to 0.7 mass %, of the total composition.
In the present invention, the content of the color pigment of component (B) when used after hydrophobization is the content of only the color pigment, not including the hydrophobization treatment agent, and the content of the composite pigment when used is the content of only the color pigment, not including the pearl pigment.

In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.5 to 30, more preferably 1 to 15, and even more preferably 1.6 to 8, from the viewpoints of obtaining a colored and transparent appearance, making the skin after application appear transparent and glossy, suppressing separation and viscosity reduction after storage, and improving spreadability.

In the present invention, the content of water in component (C) is preferably 20 to 45% by mass, more preferably 25 to 40% by mass, and even more preferably 30 to 36% by mass, of the total composition, from the viewpoint of obtaining a colored and transparent appearance and making the skin after application look transparent and glossy.

Examples of the oil agent of component (D) include hydrocarbon oils, ester oils, ether oils, silicone oils, and higher alcohols having 10 to 24 carbon atoms.

More specifically, examples of hydrocarbon oils include squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, etc. Among these hydrocarbon oils, from the viewpoints of obtaining a colored and transparent appearance, making the skin after application look transparent and glossy, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more types selected from liquid paraffin, liquid isoparaffin, and squalane, and it is more preferable to include at least one type selected from liquid isoparaffin and squalane.

Ester oils include monoester oils, diester oils, triester oils and tetraester oils.
Examples of monoester oils include monoesters of aliphatic or aromatic monocarboxylic or dicarboxylic acids having 2 to 24 carbon atoms. Specific examples include cetyl 2-ethylhexanoate, cetyl octanoate, isononyl isononanoate, isotridecyl isononanoate, hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, octyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, isocetyl isostearate, decyl oleate, isodecyl benzoate, octyl methoxycinnamate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, 2-ethylhexyl succinate, 2-hexyldecyl adipate, and alkyl benzoates (C12 to C15). Among these, from the viewpoints of obtaining a colored, transparent appearance, making the skin after application look transparent yet glossy, and suppressing separation and viscosity reduction after storage, it is preferable to contain at least one or more types selected from cetyl ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, and octyl methoxycinnamate, it is more preferable to contain at least one or two or more types selected from cetyl ethylhexanoate, isononyl isononanoate, and isotridecyl isononanoate, and even more preferable to contain at least one or two or more types selected from cetyl ethylhexanoate and isononyl isononanoate.

Diester oils include diesters of dicarboxylic acids having 3 to 18 carbon atoms, difatty acid esters of polyhydric alcohols, etc. Specific examples include propylene glycol dicaprylate, neopentyl glycol dicaprate, glycol distearate, propylene glycol diisostearate, glyceryl diisostearate, glyceryl monomyristate monoisostearate, glycerin di-2-heptylundecanoate, di-2-ethylhexyl succinate, diisopropyl sebacate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, diisobutyl adipate, di-2-heptylundecyl adipate, di-2-ethylhexyl sebacate, etc. Among these, from the viewpoints of obtaining a colored, transparent appearance, making the skin look transparent and glossy after application, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more selected from propylene glycol dicaprylate, neopentyl glycol dicaprate, glycol distearate, diisostearyl malate, and propylene glycol diisostearate, more preferably to include at least one or more selected from propylene glycol dicaprylate, neopentyl glycol dicaprate, and diisostearyl malate, even more preferably to include at least one or more selected from neopentyl glycol dicaprate and diisostearyl malate, and even more preferably to include diisostearyl malate.

Triester oils include tri-fatty acid esters of trihydric or higher polyhydric alcohols, and specific examples thereof include glycerin trimyristate, glycerin triisopalmitate, glycerin tri-2-heptylundecanoate, trimethylolpropane triethylhexanoate, trimethylolpropane trioctanoate, tri(caprylic/capric)glycerin, trioleate, glycerin tri-2-ethylhexanoate, glycerin triisostearate, olive oil, jojoba oil, etc. Among these, from the viewpoints of obtaining a colored and transparent appearance, making the skin after application look transparent and glossy, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more selected from tri(caprylic/capric)glycerin, trioleate, glycerin tri-2-ethylhexanoate, and glycerin triisostearate, and tri(caprylic/capric)glycerin is more preferable.

Examples of tetraester oils include tetra-fatty acid esters of polyhydric alcohols having 4 or more valences, and specifically include pentaerythritol tetra(behenic acid/benzoic acid/ethylhexanoic acid), pentaerythritol tetraethylhexanoate, pentaerythritol tetraoctanoate, and pentaerythritol tetra 2-ethylhexanoate. Among these, from the viewpoints of obtaining a colored and transparent appearance, making the skin after application look transparent and glossy, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more selected from pentaerythritol tetraethylhexanoate, pentaerythritol tetraoctanoate, and pentaerythritol tetra 2-ethylhexanoate, and more preferably pentaerythritol tetraethylhexanoate.

Ether oils include dialkyl ethers, specifically dihexyl ether, dicaprylyl ether, cetyl-1,3-dimethylbutyl ether, etc. Among these, from the viewpoints of obtaining a colored and transparent appearance, making the skin look transparent and glossy after application, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more types selected from dicaprylyl ether and cetyl-1,3-dimethylbutyl ether, and more preferably to include cetyl-1,3-dimethylbutyl ether.

Examples of silicone oils include crosslinked methylpolysiloxane, reticular methylpolysiloxane, dimethylpolysiloxane, methyltrimethicone, dimethylcyclopolysiloxane, methylphenylpolysiloxane such as diphenylsiloxyphenyltrimethicone, higher alcohol-modified organopolysiloxane, etc. Among these, from the viewpoints of obtaining a colored and transparent appearance, making the skin after application look transparent and glossy, and suppressing separation and viscosity reduction after storage, it is preferable to contain at least one or two or more selected from dimethylpolysiloxane, methyltrimethicone, dimethylcyclopolysiloxane, and methylphenylpolysiloxane, more preferably to contain at least one or two or more selected from dimethylpolysiloxane, methyltrimethicone, and methylphenylpolysiloxane, and even more preferably to contain at least one or two or more selected from dimethylpolysiloxane, methyltrimethicone, and diphenylsiloxyphenyltrimethicone. Even more preferably, the silicone oil comprises a volatile silicone oil.
Examples of volatile silicone oils include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1cs), dimethylpolysiloxane (1.5cs), and dimethylpolysiloxane (2cs); branched siloxanes such as methyltrimethicone, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. It is preferable to contain at least one or two or more types selected from linear dimethylpolysiloxanes and branched siloxanes, and it is more preferable to contain at least one or two or more types selected from dimethylpolysiloxane (1.5cs) and methyltrimethicone.

From the viewpoint of reducing the emulsion particle size and further improving the refreshing feeling, the higher alcohol having 10 to 24 carbon atoms preferably contains at least one or more types selected from higher alcohols having 12 to 22 carbon atoms, more preferably contains at least one or more types selected from higher alcohols having 16 to 22 carbon atoms, even more preferably contains at least one or more types selected from higher alcohols having 18 to 22 carbon atoms, and even more preferably contains at least one or more types selected from higher alcohols having 18 and 22 carbon atoms.

From the viewpoints of obtaining a colored, transparent appearance, making the skin look transparent yet lustrous after application, and suppressing separation and viscosity reduction after storage, the oil agent of component (D) preferably contains at least one or more types selected from ester oils and silicone oils, more preferably contains at least one or more types selected from monoester oils, diester oils, and silicone oils, and even more preferably contains at least one or more types selected from monoester oils, diester oils, dimethylpolysiloxanes, methyltrimethicones, and methylphenylpolysiloxanes.
The oil agent of component (D) is preferably one that is liquid at 25° C., from the viewpoints of obtaining a colored, transparent appearance, making the skin after application look transparent and glossy, and suppressing separation and viscosity reduction after storage. It is more preferable that the oil agent contains at least a volatile silicone oil.

One or more types of component (D) may be used, and from the viewpoints of obtaining a colored, transparent appearance, making the skin appear transparent and glossy after application, and suppressing separation and viscosity reduction after storage, the content is preferably 35 to 63 mass% of the total composition, more preferably 40 to 58 mass%, even more preferably 45 to 53 mass%, and even more preferably 47 to 51 mass%.

The surfactant of component (E) preferably includes a nonionic surfactant.
Examples of the surfactant of component (E) include nonionic surfactants other than silicone-based surfactants and silicone-based nonionic surfactants.
[0043] The nonionic surfactants other than silicone-based surfactants are not limited as long as they are used in ordinary cosmetics, and examples thereof include sorbitan fatty acid esters such as sorbitan monoisostearate, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, and the like.
Examples of silicone-based nonionic surfactants include linear or branched polyether-modified silicones such as polyoxyethylene-methylpolysiloxane copolymers and polyoxyethylene-polydimethylsiloxyethyl dimethicone (specifically, PEG-9 polydimethylsiloxyethyl dimethicone); alkyl-modified polyether-modified silicones (specifically, cetyl PEG/PPG-10/1 dimethicone); and alkyl-chain-co-modified polyether-modified silicones such as alkyl-modified polyoxyethylene-polydimethylsiloxyethyl dimethicone (specifically, lauryl PEG-9 polydimethylsiloxyethyl dimethicone).

Among these, from the viewpoints of obtaining a colored, uniform, and transparent appearance, making the skin look transparent and glossy after application, and suppressing separation and viscosity reduction after storage, it is preferable to include at least one or more selected from sorbitan fatty acid esters, linear or branched polyether modified silicones, alkyl modified polyether modified silicones, and alkyl modified polyoxyethylene-polydimethylsiloxyethyl dimethicone, more preferably to include at least one or more selected from sorbitan fatty acid esters, linear or branched polyether modified silicones, and alkyl modified polyether modified silicones, and more preferably to include at least one or more selected from sorbitan fatty acid esters and alkyl modified polyether modified silicones. It is also preferable to use a silicone nonionic surfactant in combination with a nonionic surfactant other than a silicone surfactant.

From the viewpoints of obtaining a colored, uniform and transparent appearance, making the skin after application appear transparent and glossy, and suppressing separation and viscosity reduction after storage, these nonionic surfactants preferably have an HLB of 2 to 9, more preferably 3 to 8, and even more preferably 4 to 7.
Here, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of a surfactant, and for nonionic surfactants, it is calculated by Griffin's formula. The HLB of a mixed surfactant consisting of two or more nonionic surfactants is calculated as follows. The HLB of a mixed surfactant is the phase arithmetic average of the HLB values of each nonionic surfactant based on their blending ratio.
Mixed HLB=Σ(HLBx×Wx)/ΣWx
HLBx indicates the HLB value of nonionic surfactant X. Wx indicates the weight (g) of nonionic surfactant X having the value of HLBx.

When a non-silicone nonionic surfactant and a silicone nonionic surfactant are used in combination as the surfactants of component (E), the mass ratio of the silicone nonionic surfactant to the non-silicone nonionic surfactant is preferably (silicone nonionic surfactant)/(non-silicone nonionic surfactant)=0.5 to 20, more preferably 1 to 10, and even more preferably 2 to 5, from the viewpoints of obtaining a uniform appearance and suppressing separation and viscosity reduction after storage.

One or more types of surfactants may be used as component (E), and the content is preferably 0.1 to 5 mass% of the total composition, more preferably 0.5 to 4 mass%, and even more preferably 1 to 3 mass%, from the viewpoints of obtaining a uniform appearance and suppressing separation and viscosity reduction after storage.

The water-in-oil emulsion composition of the present invention may contain, in addition to the above-mentioned components, components that are usually used in cosmetics, such as oil components other than those mentioned above, water-soluble polymers, antioxidants, fragrances, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, disinfectants, skin activators, moisturizers, and cooling agents.

In the present invention, the difference in refractive index between the aqueous phase, excluding components (A) and (B), and the oil phase is less than 0.07, preferably less than 0.06, more preferably less than 0.055, even more preferably less than 0.045, and even more preferably less than 0.04, in order to obtain a transparent appearance.
In the present invention, the refractive index is measured by measuring the aqueous phase and the oil phase prepared by mixing the aqueous phase components excluding components (A) and (B) respectively, at 25° C. using a refractometer (PAL-RI, manufactured by Atago Co., Ltd.).
The refractive index of the aqueous phase is preferably 1.35 to 1.41, and more preferably 1.36 to 1.40, and the refractive index of the oil phase is preferably 1.38 to 1.43, and more preferably 1.39 to 1.42.

The surfactant of component (E) is contained in the phase in which it is uniformly dissolved when the oil phase and the water phase are separately prepared and mixed with each other.
The total content of the oil phase is preferably from 38 to 65% by mass, more preferably from 43 to 58% by mass, and even more preferably from 48 to 54% by mass, of the entire composition.
The aqueous phase also contains water-soluble components such as polyhydric alcohols, ethanol, salts, etc. The total content of the aqueous phase is preferably 35 to 58% by mass, more preferably 39 to 54% by mass, and even more preferably 43 to 49% by mass, of the entire composition.
From the viewpoints of improving the spread when applied to the skin and the ejection properties when filled into a container such as a bottle or a tube for use, the viscosity of the water-in-oil emulsion composition of the present invention is preferably 100 to 50,000 mPa·s, more preferably 500 to 30,000 mPa·s, even more preferably 1,000 to 25,000 mPa·s, and even more preferably 1,500 to 10,000 mPa·s at 25° C. The viscosity can be measured using a B-type viscometer (TV-B type, manufactured by Tokyo Keiki Co., Ltd.).

The water-in-oil emulsion composition of the present invention can be produced according to a conventional method.
The cationically modified clay mineral of component (A) is preferably dispersed in advance in a portion of component (D) to prepare a premix composition, and then mixed in. When preparing the premix, it is preferable to further mix one or more selected from ethanol and water in order to improve workability.
The content of the cation-modified clay mineral (A) in the premix composition is preferably 6 to 20% by mass, more preferably 8 to 18% by mass, and even more preferably 10 to 16% by mass, from the viewpoints of obtaining a colored, uniform and transparent appearance, making the skin after application appear transparent and glossy, and suppressing separation and viscosity reduction after storage.
The water-in-oil emulsion composition of the present invention can be produced, for example, by dispersing component (A) in a portion of component (D) (further, ethanol, etc.) to prepare a premix composition, adding and mixing this to a mixture of oil phase components containing the remaining component (D) and powder components containing component (B), and further mixing with an aqueous phase component containing component (C).
The water-in-oil emulsion composition of the present invention is obtained as a colored, transparent composition, but it can also be made into a two-layer type that is shaken before use, or a one-layer cream type.

The water-in-oil emulsion composition of the present invention is suitable as a water-in-oil emulsion cosmetic, and can be used as makeup cosmetics such as a makeup base, foundation, concealer, blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc.; UV protection cosmetics such as a sunscreen lotion, a sunscreen cream, etc.; skin care cosmetics such as a skin care lotion, a skin care cream, a BB cream, a beauty serum, etc. Of these, makeup cosmetics are preferred, and makeup bases are more preferred.
When the water-in-oil emulsion composition of the present invention is used as a makeup base, it can be applied to the skin to control the skin color, and then a foundation can be applied to obtain a beautiful and natural finish. It can also be used by mixing it with a liquid or cream foundation.
By using the color pigment of component (B), a beautiful finish can be obtained, but depending on the type of color pigment, various finishes such as texture and complexion can be expressed. For example, when black iron oxide is used, a glossy finish with a firm impression can be obtained, and when red iron oxide is used, a complexion with a lively impression can be obtained.

Examples 1 to 6, Comparative Examples 1 to 2
A water-in-oil emulsion composition (makeup base) having the composition shown in Table 1 was prepared.
The refractive indexes of the oil phase and the water phase were measured, and the transparency of the appearance (visual and colorimetric values), the coating color, the stability (appearance and viscosity), and the uniformity of the appearance were evaluated. The results are shown in Table 1.

(Production method)
Component (A) was dispersed in a mixture of a portion of component (D) and ethanol to prepare a premix composition, which was then added to the remaining oil phase components containing component (D) and component (E) and a mixture containing component (B) and mixed using a disperser. Thereafter, the aqueous phase component containing component (C) was added and mixed using a disperser, and the mixture was further stirred using a homomixer to obtain a water-in-oil emulsion composition.

(Evaluation Method)
(1) Refractive index:
The oil phase and the aqueous phase were prepared by mixing the oil phase and the aqueous phase, respectively, and the refractive index was measured using a refractometer (PAL-RI, manufactured by Atago Co., Ltd.) at 25° C. The oil phase and the aqueous phase were each measured three times, and the average value was recorded as the refractive index.

(2) Transparency of appearance (visual inspection):
40 g of each water-in-oil emulsion composition was placed in a 60 mL sample bottle (Tokyo Glass Co., Ltd., PS-6K), and the transparency of the appearance was visually evaluated by five expert evaluators on the following four-point scale. The results are shown as the average score of the five evaluators.
4: There is a clear sense of transparency (there is a clear sense of transparency and the colors look vivid).
3: Feels transparent (transparent, colors look vivid).
2: Not very transparent (not very transparent, the color looks cloudy).
1: No sense of transparency (no transparency, the color looks cloudy).

(3) Transparency of appearance (colorimetric value):
Each water-in-oil emulsion composition was measured for color using a color difference meter (Color i5, manufactured by X-rite) to determine the L value. The measurement was performed at 25°C one day after production, and the average value of 10 measurements was taken as the color measurement value. A high L value indicates cloudiness and lack of transparency, whereas a low L value indicates clear transparency.

(4) Coating color (visual inspection):
After each water-in-oil emulsion composition was applied to the skin with a finger, five expert evaluators sensorily evaluated the appearance of the skin on the following four-point scale. The results are shown as the average score of the five evaluators.
4: It has a transparent yet glossy appearance.
3: Transparent yet slightly glossy.
2: It is transparent but does not look glossy.
1: It lacks transparency and does not look glossy.

(5) Stability (appearance):
40 g of each water-in-oil emulsion composition was placed in a 60 mL sample bottle (Tokyo Glass Co., Ltd., PS-6K) and stored at 30°C for one week. The state of separation at 30°C was then evaluated in terms of the proportion (mm) of a transparent layer that appeared after separation.

(6) Stability: (viscosity):
40 g of each water-in-oil emulsion composition was placed in a 60 mL sample bottle (Tokyo Glass Co., Ltd., PS-6K), and after production, measurements were performed under the following conditions.
The viscosity was measured at 30°C after one day and after one week of storage at 30°C. The viscosity was measured under the following conditions: B-type viscometer (TV-B type, manufactured by Tokyo Keiki Co., Ltd.)
When the viscosity is 0 or more and less than 10,000 mPa·s: Rotor No. 3, rotation speed 12 rpm, 30 seconds When the viscosity is 10,000 or more and less than 50,000 mPa·s: Rotor No. 4, rotation speed 12 rpm, 30 seconds

(7) Uniformity of Appearance:
40 g of each water-in-oil emulsion composition was placed in a 60 mL sample bottle (Tokyo Glass Co., Ltd., PS-6K), and the uniformity of appearance was evaluated immediately after production, and after storage at 30° C. for one week, after the bottle was held in one hand and shaken up and down 10 times at a distance of 30 cm. Note that one shake means shaking the bottle from top to bottom and then back up.
3: Appears uniform.
2: Appears slightly uneven.
1: Looks uneven.

Examples 7 to 10
In the same manner as in Examples 1 to 6, water-in-oil emulsion compositions having the compositions shown in Table 2 were produced.
The refractive indexes of the oil phase and the water phase were measured, and the transparency of the appearance (visual observation), the coating color, the stability (appearance, viscosity), and the uniformity of the appearance were evaluated in the same manner as in Examples 1 to 6. The results are shown in Table 2.

Claims (5)

The following components (A), (B), (C), (D) and (E):
(A) a cation-modified clay mineral substituted with a quaternary ammonium ion;
(B) Colored pigment 0.01 to 1.5% by mass ,
(C) water,
(D) oil agent,
(E) A water-in-oil emulsion composition containing a surfactant, in which the difference in refractive index between the aqueous phase and the oil phase, excluding components (A) and (B), is less than 0.06 . The water-in-oil emulsion composition according to claim 1, wherein the content of component (A) is 0.1 to 4 mass%. 3. The water-in-oil emulsion composition according to claim 1 , wherein the mass ratio (A)/(B) of component (A) to component (B) is 0.5 to 30. The water-in-oil emulsion composition according to any one of claims 1 to 3, wherein component (E) comprises at least one or more selected from the group consisting of sorbitan fatty acid esters, linear or branched polyether-modified silicones, alkyl -modified polyether-modified silicones, and alkyl-modified polyoxyethylene-polydimethylsiloxyethyl dimethicones. The water-in-oil emulsion composition according to any one of claims 1 to 4 , which is a cosmetic.