JP2017190300A - (f+w)/o type emulsion and a cosmetic composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic composition having excellent emulsion stability and high sustained cosmetic effect, and excellent feeling of use when applied to the skin.SOLUTION: According to the present invention, there is provided a (F+W)/O type emulsion in which a phase containing a fluorine-based oil agent and an aqueous phase are dispersed in an oil phase containing an oil agent incompatible with a fluorine-based oil agent. For the total mass of the emulsion, (A) 1-40 mass% of the fluorine-based oil agent, (B) 0.1-30 mass% of a powder coated with a compound containing a fluorine compound, (C) 10-70 mass% of the oil agent incompatible with the component (A), (D) 0.1-5 mass% of organically modified clay mineral, and (E) 1-60 mass% of the aqueous phase component are contained.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a (F + W) / O type emulsion in which a phase containing a fluorinated oil and an aqueous phase are dispersed in an oil phase containing an oil that is incompatible with the fluorinated oil, and a cosmetic composition containing the same.

It is well known that when a fluorinated oil is blended in a cosmetic composition, water resistance and oil resistance are imparted, and the effect of preventing makeup collapse due to sweat, sebum, etc. is high (for example, Japanese Patent No. 4261788) (Patent Document 1), Japanese Patent No. 5715816 (Patent Document 2)). However, it is difficult to obtain a stable formulation containing a fluorinated oil. Further, since the fluorine-based oil is expensive and the blending amount is limited, it is not easy to obtain a cosmetic composition having a long-lasting cosmetic effect, that is, having a long lasting makeup.
On the other hand, water-in-oil-in-oil emulsions have recently become mainstream in cosmetic compositions because they provide a smooth feel when applied to the skin and have a relatively long makeup. However, the reality is that the makeup lasting as when the fluorinated oil is blended is not obtained.
By the way, an emulsion stabilized by adsorbing fine particles at an interface is known as a “Pickering emulsion”, and application of the Pickering technique is also being studied in the field of cosmetics.
For example, Patent Document 1 describes an F / O emulsion that includes a fluorinated oil, an oil that is incompatible with the fluorinated oil, and a water-repellent oleophilic powder. It is described that the emulsion is stabilized by being localized at the interface between the oil agent and the oil agent that is incompatible with the oil agent. However, with this emulsion, it is difficult to obtain a fresh feeling when used on the skin.
Patent No. 5477883 (Patent Document 3) is excellent in emulsion stability by blending a hydrophobic treatment powder or a hydrophobic powder usually used in cosmetics with a small amount of a hydrophilic surfactant. It is described that a water-in-oil emulsion can be obtained. However, with this emulsion, the makeup effect cannot be sufficiently sustained.
As described above, a cosmetic composition that has a long cosmetic effect and can provide a fresh feeling when applied to the skin has not yet been obtained.

Japanese Patent No. 4261784 Japanese Patent No. 5715816 Japanese Patent No. 5477883

  Under such circumstances, there is a need to provide a cosmetic composition that has excellent emulsification stability, high persistence of cosmetic effects such as makeup effects and skin care effects, and excellent usability when applied to the skin. Yes.

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) a fluorine-based oil agent, (B) a powder coated with a compound containing a fluorine compound, (C) a component (A) and a phase A phase containing a fluorinated oil agent in an oil phase containing an oil agent that is incompatible with the fluorinated oil agent, by blending an insoluble oil agent, (D) an organically modified clay mineral, and (E) an aqueous phase component in a predetermined ratio; It was found that a (F + W) / O type emulsion in which the aqueous phase was dispersed was formed, and that a stable emulsion containing a fluorinated oil was obtained without requiring the use of a surfactant. It came to do. Without being bound by theory, in this emulsion, the interface between the oil phase containing an oil agent that is incompatible with the fluorine oil agent and the phase containing the fluorine oil agent was coated with a compound containing (B) a fluorine compound. (D) Organically modified clay mineral is adsorbed at the interface between the oil phase and the aqueous phase containing the oil that is incompatible with the fluorinated oil, and two types of pickering emulsions are formed in one system. It is considered that the (F + W) / O type emulsion is stabilized.

  That is, the present invention relates to an emulsion and a production method thereof, a cosmetic composition, a cosmetic method for skin care or makeup, and the like shown below.

[1] A (F + W) / O type emulsion in which a phase containing a fluorinated oil and an aqueous phase are dispersed in an oil phase containing an oil that is incompatible with the fluorinated oil, with respect to the total mass of the emulsion ,
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
An emulsion.
[2] The emulsion according to [1], wherein component (A) is at least one selected from the group consisting of perfluoropolyethers and fluorosilicone oils.
[3] The emulsion according to [1] or [2], wherein the fluorine compound in component (B) is at least one selected from the group consisting of perfluoroalkyl phosphate esters and perfluoroalkylalkoxysilanes.
[4] The emulsion according to any one of [1] to [3], wherein the component (C) contains silicone oil.
[5] The emulsion according to any one of [1] to [4], wherein the component (D) is a water-swellable clay mineral treated with a quaternary ammonium compound.
[6] A cosmetic composition comprising the emulsion according to any one of [1] to [5].
[7] Use of the composition according to [6] for skin care or makeup.
[8] A cosmetic method for skin care or makeup comprising applying the composition according to [6] to the skin.
[9] A method for producing a (F + W) / O type emulsion in which a phase containing a fluorinated oil and an aqueous phase are dispersed in an oil phase containing an oil that is incompatible with the fluorinated oil, For mass
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
Combining the method.

  According to a preferred embodiment of the present invention, it is possible to provide an emulsion that has excellent emulsification stability, high persistence of a cosmetic effect, and gives a fresh feeling when used on the skin. The emulsion of the present invention can be suitably used as a cosmetic composition in various forms such as a liquid foundation, cream foundation, sunscreen, makeup base, face cream, hand cream, mascara and the like.

3 is a microscopic observation image of the cosmetic composition obtained in Example 2. FIG. It is the photographic image which compared the state of the purified water (0.05g) and squalane (0.03g) which were dripped at each liquid foundation obtained in Example 8 and Comparative Example 7. 2A shows a photographic image of Example 8, and FIG. 2B shows a photographic image of Comparative Example 7. It is a microscope observation image after leaving the cream foundation obtained in Example 9 for 1 month at 40 degreeC.

  Hereinafter, the emulsion of the present invention, a production method thereof, a cosmetic composition, a cosmetic method for skin care or makeup, and the like will be described in detail.

The emulsion of the present invention is a (F + W) / O type emulsion in which a phase containing a fluorinated oil and an aqueous phase are dispersed in an oil phase containing an oil that is incompatible with the fluorinated oil, and the total mass of the emulsion Against
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
It is characterized by including.

  The emulsion of the present invention contains components (A) to (E) at a predetermined blending ratio, so that a surfactant is not necessarily required, and an oil phase and an aqueous phase containing an oil agent that is not compatible with a fluorinated oil agent. The fluorine-based oil agent can be stably dispersed in the emulsion containing. Thereby, the emulsion of this invention is excellent in the sustainability of a cosmetic effect, and can give a fresh feeling of use when apply | coating to skin. Hereinafter, each component mix | blended with the emulsion of this invention is demonstrated.

(A) Fluorine-based oil agent The fluorine-based oil agent (component (A)) used in the present invention is not particularly limited, but those in a liquid state at 25 ° C. can be preferably used.
Examples of the fluorinated oil include perfluoropolyether, perfluoroalkyl polyether, fluorosilicone oil (perfluoroalkyl-modified silicone), perfluorocarbon, and perfluoro fatty acid.
Among these, in the present invention, perfluoropolyether, fluorosilicone oil, perfluorocarbon, perfluoro fatty acid or a combination thereof is preferably used, and perfluoropolyether, fluorosilicone oil or a combination thereof is more preferably used. Perfluoropolyether is particularly preferably used.

Examples of the perfluoropolyether include compounds represented by the formula (I).

[Wherein, R ¹ and R ² are each independently a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and l, m and n are each independently an integer of 0 to 200. Yes (provided that l, m, and n are not all zero). Moreover, each structural unit does not need to be located in this order, random polymerization may be sufficient and block polymerization may be sufficient. ]

In the formula (I), R ¹ and R ² are each independently a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and preferably have a linear or branched chain having 1 to 20 carbon atoms. More preferably, it has a linear or branched chain having 1 to 8 carbon atoms.

  Specific examples of perfluoropolyether include polyperfluoromethyl isopropyl ether and polyperfluoroisopropyl ether. These are commercially available, and can be obtained commercially, for example, under the product names “FOMBLINHC / 04”, “FOMBLINHC / 25” manufactured by Solvay Solexis, and the product name “Koflube” manufactured by Kobo Products.

  Examples of the perfluoroalkyl polyether include ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, and perfluorohexyl ethyl dimethyl butyl ether. These are commercially available, and can be obtained commercially, for example, under the product name “3M Cosmetic fluid CF-76” manufactured by 3M.

Examples of the fluorosilicone oil include polysiloxane having a perfluoroalkyl group in at least a part of the side chain. The perfluoroalkyl group preferably has a linear or branched chain having 1 to 20 carbon atoms, and more preferably has a linear chain having 1 to 10 carbon atoms.
Examples of the fluorosilicone oil include a compound represented by the formula (II).

[Wherein, m is an integer of 0 to 10, and n is an integer of 1 to 10. Moreover, x is an integer of 1 to 200, and y is an integer of 0 to 200. Each structural unit does not need to be arranged in this order, and may be random polymerization or block polymerization. ]

  Specific examples of the fluorosilicone oil include trifluoropropyl dimethicone, trifluoropropyl methicone and perfluorononyl dimethicone. These are commercially available, and can be obtained commercially as, for example, product names “CFF-3400” and “CFF-3401” manufactured by Nusil, and product names “Fluorosil H4” manufactured by Siltech.

The perfluorocarbon preferably has a straight or branched chain having 1 to 20 carbon atoms, and more preferably has a straight chain having 1 to 10 carbon atoms.
Specific examples of perfluorocarbon include perfluorodecalin, perfluoropentane, perfluorohexane, perfluorodecane, perfluoroisohexane, perfluoromethylcyclohexane, perfluoromethylcyclopentane, perfluoromethyldecalin, perfluorodimethylcyclohexane, Examples thereof include perfluorodimethylpentane and perfluoroheptane. These are commercially available, for example, C.I. I. Commercially available as “Fiflow 140” manufactured by T company.

The perfluoro fatty acid preferably has a straight or branched chain having 1 to 20 carbon atoms, and more preferably has a straight chain having 1 to 10 carbon atoms.
Specific examples of the perfluoro fatty acid include perfluorooctanoic acid, perfluorononanoic acid and perfluorododecanoic acid. These are commercially available, and can be commercially obtained, for example, as a reagent “tricosafluorododecanoic acid” manufactured by Tokyo Chemical Industry Co., Ltd.

  Alternatively, perfluorobutyltetrahydrofuran or the like can be used as the fluorinated oil. Perfluorobutyltetrahydrofuran is commercially available, for example, as a reagent “perfluoro (2-butyltetrahydrofuran)” manufactured by Tokyo Chemical Industry Co., Ltd.

  In the emulsion of the present invention, the blending amount of the fluorinated oil is 1 to 40% by mass, preferably 2% by mass or more, more preferably 3% by mass or more, preferably 20% by mass with respect to the total mass of the emulsion. Hereinafter, it is more preferably 10% by mass or less.

(B) Powder Coated with Compound Containing Fluorine Compound In the emulsion of the present invention, powder (component (B)) coated with a compound containing a fluorine compound is blended. This stabilizes the interface between the oil phase containing an oil agent that is incompatible with the fluorine oil agent and the phase containing the fluorine oil agent, and the oil phase containing the oil agent that is incompatible with the fluorine oil agent contains the fluorine oil agent. The phase can be stably dispersed. Note that “the powder is coated with a compound containing a fluorine compound” means that the compound containing the fluorine compound is chemically bonded or simply adhered to at least a part of the powder surface. means.
Examples of the powder that is the base material of the component (B) include inorganic powder, organic powder, metal powder pigment, and organic pigment.
Examples of the inorganic powder include titanium oxide, iron oxide, zinc oxide, zirconium oxide, cerium oxide, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, safmica, biotite. , Vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, silica, zeolite, barium sulfate, magnesium sulfate, calcined calcium sulfate ), Calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metal soap (for example, zinc myristate, calcium palmitate, aluminum stearate, magnesium stearate), boron nitride and the like.
Examples of the organic powder include polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, Examples thereof include cellulose powder and silk powder.
Examples of the metal powder pigment include aluminum powder and copper powder.
Examples of organic pigments include zirconium, barium and aluminum lakes.

In the present invention, the powder is used after being treated with a surface treatment agent containing a fluorine compound. By treating the powder with a surface treatment agent containing a fluorine compound, the compound containing the fluorine compound is chemically bonded or attached to at least a part of the powder surface, and water and oil repellency can be imparted.
Preferred examples of the fluorine compound include perfluoroalkyl phosphate esters and perfluoroalkyl sulfonate esters, perfluoroalkylalkoxysilanes, copolymers containing perfluoroalkyl acrylates, and combinations thereof.
The perfluoroalkyl group of the perfluoroalkyl phosphate ester and the perfluoroalkyl sulfonate ester preferably has a linear or branched chain having 1 to 28 carbon atoms, and has a linear or branched chain having 4 to 18 carbon atoms. It is more preferable.
Examples of perfluoroalkyl phosphate esters include perfluoroalkyl phosphates such as potassium perfluorohexylethyl phosphate, sodium perfluorohexylethyl phosphate, perfluorohexylethyl phosphate diethanolamine, and perfluoroalkyl (C6-16). ) Ammonium ethyl phosphate and the like.
Examples of the perfluoroalkyl sulfonic acid ester include perfluoroalkyl (C9-10) ammonium sulfonate which is a perfluoroalkyl sulfonate.
The perfluoroalkyl group of the perfluoroalkylalkoxysilane preferably has a linear or branched chain having 1 to 28 carbon atoms, and more preferably has a linear or branched chain having 4 to 22 carbon atoms. Moreover, it is preferable that an alkoxy group has a C1-C12 linear or branched chain, and it is more preferable that it has a C4-C10 linear or branched chain.
Examples of perfluoroalkylalkoxysilanes include perfluorooctylethyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctyltrisiloxane, perfluorooctyltriethoxysilane, and perfluorooctyltrimethoxysilane.
As a copolymer containing perfluoroalkyl acrylate, a copolymer containing perfluorohexyl ethyl acrylate, which is “Polyacrylate-37” under the INCI name (name according to the international nomenclature of cosmetic raw materials), (perfluoroalkyl acrylate (C6-14)) Ethyl) copolymer and the like.
As for the usage-amount of a fluorine compound, 0.5-20 mass% is preferable normally with respect to the mass of the powder before surface treatment, More preferably, it is 1-10 mass%, More preferably, it is 2-5 mass%.
Surface treatment agents include fluorine compounds, as well as silicone compounds such as methicone, dimethicone, dimethicone / methicone copolymer; amino acid compounds such as sodium stearoyl glutamate and magnesium palmitoyl glutamate; fatty acid compounds such as stearic acid and magnesium stearate. And lauroyllysine; isostearyl sebacate which is an ester oil compound; trimethoxycaprylylsilane and triethoxycaprylylsilane which are trialkoxyalkylsilane compounds.

  The method for treating the powder with the surface treating agent containing a fluorine compound is not particularly limited. For example, the powder surface can be treated by a wet manufacturing method in which a powder is coated with a surface treatment agent in a solvent.

  In this invention, you may use a commercial item as a powder coat | covered with the compound containing (B) a fluorine compound. For example, perfluorooctyltriethoxysilane-treated iron oxide and perfluorooctyltriethoxysilane-treated titanium oxide manufactured by Daito Kasei Kogyo Co., Ltd., perfluoroalkyl (C6-16) ethyl phosphate-treated titanium oxide and perfluoroalkyl manufactured by Sensient (C6-16) ethyl phosphate-treated iron oxide or the like is preferably used.

  In the emulsion of the present invention, the blending amount of the powder coated with the compound containing (B) the fluorine compound is 0.1 to 30% by mass, preferably 0.5% by mass with respect to the total mass of the emulsion. As mentioned above, More preferably, it is 1 mass% or more. The emulsion does not become unstable due to the large amount of component (B), but considering the overall balance, the amount of component (B) is 30% by mass or less, preferably 20% by mass or less. More preferably, it is 15 mass% or less. In addition, the preferable compounding quantity of a component (B) changes with compounding quantities of a component (A). For example, when the amount of component (A) is 5% by mass, the preferable amount of component (B) is 0.2% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass. That's it. Moreover, when the compounding quantity of a component (A) is 10 mass%, the preferable compounding quantity of a component (B) is 1 mass% or more, More preferably, it is 2 mass% or more, More preferably, it is 4 mass% or more. is there. Moreover, when the compounding quantity of a component (A) is 20 mass%, the preferable compounding quantity of a component (B) is 3 mass% or more, More preferably, it is 4 mass% or more, More preferably, it is 8 mass% or more. is there.

(C) Oil agent incompatible with component (A) The oil agent (component (C)) incompatible with component (A) used in the present invention is not particularly limited as long as it is insoluble or hardly soluble in water and component (A). Not. Among these, those in a liquid state at 25 ° C. can be preferably used. Preferred examples of the oil used as the component (C) in the present invention include low-viscosity liquid oils, hydrocarbon oils, synthetic ester oils, and silicone oils that are generally used in cosmetic compositions.

  Examples of liquid fats and oils (oils and fats in a liquid state at room temperature (25 ° C.)) include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, Wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnabari oil, Japanese kiri oil, jojoba oil, germ oil , Triglycerin, meadow foam oil and the like.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, hydrogenated polydecene, isododecane and the like.

  Synthetic ester oils include dineopentanoic acid tripropylene glycol, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, cetyl octanoate, cetyl isooctanoate, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, butyl stearate, lauric acid Hexyl acid, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate , Dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate , Diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, tri-2- Glyceryl ethylhexanoate, glyceryl trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, Castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-oct Ludodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate , 2-ethylhexyl succinate, triethyl citrate, dimer dilinoleic acid dimer dilinoleyl bis (behenyl / isostearyl / phytosteryl), lauroyl glutamic acid (phytosteryl / behenyl / octyldodecyl / isostearyl), tri (caprylic acid / capric acid) ) Glyceryl, triethylhexanoin and the like.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethicone (dimethylpolysiloxane), methyltrimethicone, caprylylmethicone, phenyltrimethicone, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, Octamethylcyclotetrasiloxane, cyclopentasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, poly Ether-modified polysiloxane, alkyl-modified polysiloxane, etc.).

  The oil agent (component (C)) incompatible with these components (A) may be used alone or in combination of two or more. Especially, in this invention, it is preferable that at least 1 sort (s) of silicone oil is included as an oil agent (component (C)).

  The content of the oil agent (component (C)) that is incompatible with the component (A) in the emulsion of the present invention is 10 to 70% by mass, preferably 20% by mass or more, more preferably based on the total mass of the emulsion. Is 25% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less.

(D) Organically modified clay mineral The organically modified clay mineral (component (D)) used in the present invention has an exchangeable cation intercalated between crystal layers of clay minerals such as montmorillonite, saponite, hectorite, bentonite and smectite. It is formed by ion exchange using a compound. In the present invention, any organic modified clay mineral generally used in cosmetics can be used without any particular limitation.
Especially, in this invention, what was obtained by ion-exchanging a water swelling clay mineral using a quaternary alkyl ammonium salt type | mold cationic surfactant can be used preferably.

Examples of the water-swellable clay mineral include a general formula:
(X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ Z _1/3 · nH ₂ O (1)
[Wherein X is Al, Fe (III), Mn (III) or Cr (III), Y is Mg, Fe (II), Ni, Zn, Li or Mn (II), Z is , K, Na, 1 / 2Ca or 1 / 2Mg. ]
Colloidal hydrous aluminum silicate having a three-layer structure represented by

  Among them, natural or synthetic montmorillonite group such as montmorillonite, bentonite and hectorite (for example, OH group in general formula (1) substituted with fluorine); sodium silicic mica, sodium teniolite or lithium teniolite, etc. Synthetic mica is preferable, and montmorillonite, bentonite, and hectorite are particularly preferable.

As the quaternary alkyl ammonium salt type cationic surfactant, for example, a general formula:

[Wherein, R ¹ is alkyl or benzyl having 10 to 22 carbon atoms, R ² is methyl or alkyl having 10 to 22 carbon atoms, and R ³ and R ⁴ are each independently a carbon number. 1 to 3 alkyl or hydroxyalkyl, and X is a halogen atom (F, Cl, Br or I) or a methyl sulfate residue. ] The compound shown by this is mentioned.

  Specifically, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dilauryl dimethyl ammonium chloride, Examples include dipolyoxyethylene chloride (15EO) coconut oil alkylmethylammonium chloride, dipolyoxyethylene (4EO) lauryl ether dimethylammonium, stearyltrimethylammonium bromide, cetyltrimethylammonium bromide, and lauryltrimethylammonium bromide. .

  The method for ion-exchange of the water-swellable clay mineral using a quaternary alkyl ammonium salt type cationic surfactant is not particularly limited. For example, in a low-boiling solvent such as water, acetone or lower alcohol, the water-swelling clay mineral and the quaternary alkyl ammonium salt type cationic surfactant are stirred to remove the low-boiling solvent. The exchangeable cation of the clay mineral can be ion-exchanged using a quaternary alkyl ammonium salt type cationic surfactant.

As the organically modified clay mineral (component (D)) used in the present invention, distearyldimethylammonium hectorite (= quaternium-18 hectorite), distearyldimethylammonium bentonite (= quaternium-18 bentonite) is particularly preferably used. it can.
These are commercially available, for example, as “Benton 38VCG” (= quaternium-18 hectorite), “Benton 34” (= quaternium-18 bentonite) (both manufactured by Elementis Specialties) and are commercially available. be able to.

  The content of the organically modified clay mineral (component (D)) in the emulsion of the present invention is 0.1 to 5% by mass, preferably 0.5% by mass or more, more preferably based on the total mass of the emulsion. It is 1 mass% or more, preferably 4 mass% or less, more preferably 3 mass% or less. In addition, an organic modified clay mineral may be used individually by 1 type, or may use 2 or more types.

(E) Water phase component In the emulsion of this invention, a water phase component (component (E)) is included. The aqueous phase component is not particularly limited as long as it forms an aqueous phase in the emulsion of the present invention, and examples thereof include water, a water-soluble solvent, or a mixture thereof.
The water-soluble organic solvent is not particularly limited, and those commonly used in cosmetic compositions can be preferably used. For example, lower alcohols (preferably alcohols having 1 to 5 carbon atoms) such as methanol, ethanol, propanol, isopropanol; ethylene glycol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, polyethylene glycol, polyoxy Examples thereof include polyhydric alcohols such as ethylene methyl glucoside, glycerin, and diglycerin. These water-soluble organic solvents may be used alone or in combination of two or more.

  Content of a water phase component (component (E)) is 1-60 mass% with respect to the total mass of the emulsion of this invention, Preferably it is 5 mass% or more, More preferably, it is 15 mass% or more, Preferably Is 50% by mass or less, more preferably 40% by mass or less.

The emulsion of the present invention contains components (A) to (E) at a predetermined ratio, so that a surfactant is not required, and a fluorine-based oil agent is contained in an oil phase containing an oil agent that is not compatible with the fluorine-based oil agent. A (F + W) / O type emulsion in which a phase containing water and an aqueous phase are stably dispersed can be formed. In the emulsion, although not bound by theory, the interface between the oil phase containing an oil that is incompatible with the fluorine oil and the phase containing the fluorine oil was coated with a compound containing a fluorine compound (B). (D) Organically modified clay mineral is adsorbed at the interface between the oil phase and the aqueous phase containing the oil that is incompatible with the fluorinated oil, and two types of pickering emulsions are formed in one system. It is thought that. In the emulsion of the present invention, it is considered that the emulsion stability can be enhanced by the presence of the two kinds of pickering emulsions in an appropriate balance in one system.
Since the emulsion of the present invention can stably contain a fluorine-based oil agent that has a high effect of preventing makeup collapse, when used as a cosmetic composition for skin care or makeup, particularly as a cosmetic composition for makeup Furthermore, it is possible to provide a cosmetic composition excellent in the sustainability of the cosmetic effect.
Further, as described above, in the present invention, the oil phase including an oil agent that is incompatible with the fluorine-based oil agent, the water phase, and the phase including the fluorine-based oil agent are included in a balanced manner, and a surfactant is not required. Since an emulsion having excellent emulsification stability can be obtained, a fresh feeling of use can be given when applied to the skin.
As long as the object of the present invention is not impaired, the emulsion of the present invention may further contain a surfactant. However, it is preferable to minimize the amount of the surfactant used. For example, it is preferable that the amount of the surfactant used is 2.0% by mass or less with respect to the total mass of the emulsion.

  The emulsion of the present invention can optionally contain components other than those described above as long as the object and effects of the present invention are not impaired. For example, a component that can be blended in an external composition such as a pharmaceutical, a quasi-drug, or a cosmetic can be included. An arbitrary component can be mix | blended with the emulsion of this invention by mix | blending in the oil phase containing the oil agent which is not compatible with a fluorine-type oil agent, or the water phase. A person skilled in the art can appropriately determine which phase is added depending on the type of the optional component.

  Examples of optional components that can be used in the present invention include powder components, surfactants, solid fats and oils, waxes, silicone elastomers, dispersants, cosurfactants, film agents, thickeners, gelling agents, and inorganic minerals. , Sequestering agent, polyhydric alcohol, monosaccharide, oligosaccharide, amino acid, organic amine, polymer emulsion, vitamins, antioxidant, antioxidant aid, moisturizer, emollient, anti-aging agent, anti-contamination Agents, keratolytic agents, anti-inflammatory (anti-inflammatory) agents, whitening agents (whitening agents), skin nutrients, blood flow promoters, bactericides, cell (skin) activators, cooling agents, astringents, sunscreen agents, Preservatives, plant extracts, buffering agents, fragrances and the like can be appropriately blended as necessary. These optional components may be appropriately selected according to the intended dosage form and application.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, vermiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, silica, zeolite, barium sulfate, magnesium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic Powder, metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate, magnesium stearate), boron nitride, etc.); organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, Methyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); metal powder pigment (eg, aluminum powder, copper powder, etc.); Organic pigments such as zirconium, barium or aluminum lake; natural pigments (for example, chlorophyll, β-carotene, etc.) and the like. The powder component may be hydrophobized.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a lipophilic nonionic surfactant, a hydrophilic nonionic surfactant, and a silicone-based surfactant.

  Examples of the anionic surfactant include fatty acid soap (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acids (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyl taurate, Palm oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; Phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate etc.); Sulfosuccinate ( For example, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkylbenzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, linear dodecyl benzene sulfone) Acid triethanolamine, linear dodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfates (eg, hydrogenated coconut oil fatty acid sodium glyceryl sulfate); N-acyl glutamate (eg, monosodium N-lauroyl glutamate, N-stearoyl) Disodium glutamate, N-myristoyl-L-monosodium glutamate, etc.); sulfated oil (eg funnel oil); PO -Alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester; higher fatty acid alkylolamide sulfate ester; lauroyl monoethanolamide succinate Examples include sodium acid; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (for example, stearyltrimethylammonium chloride and lauryltrimethylammonium chloride); alkylpyridinium salts (for example, cetylpyridinium chloride); distearyldimethylammonium dialkyldimethylammonium chloride Poly (N, N′-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE-alkylamine Alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexyl); glycerin polyglycerin fatty acids (for example, mono-cotton oil fatty acid glycerin, mono-erucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α′-oleic acid pyroglutamic acid glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (for example, , Propylene glycol monostearate, etc.); hardened castor oil derivative; glycerin alkyl ether; steareth-2 and the like.

Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-monooleate, POE-distearate, P) E-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core) Stanol ether, etc.); Pluronic type (for example, Pluronic, etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP-monobutyl ether, POE · POP-hydrogenated lanolin, POE · POP-glycerin ether, etc.); steareth-21 and the like.
Examples of silicone surfactants include polyether-modified silicones (PEG-10 dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone). Polyglycerin-modified silicones (polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone); bis (polyglyceryl-3oxyphenylpropyl) dimethicone, and the like. In addition, a polyether-modified silicone crosslinked product ((dimethicone / (PEG-10 / 15)) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer) which is a silicone elastomer into which polyether is introduced; polyglycerin is introduced And polyglycerin-modified silicone cross-linked products ((dimethicone / polyglycerin-3, lauryl dimethicone / polyglycerin-3) crosspolymer) which are silicone elastomers.

  Examples of solid fats and oils (solid fats and oils at room temperature (25 ° C.)) include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, palm kernel oil, owl kernel oil, hydrogenated oil, owl and hydrogenated castor. Oil etc. are mentioned.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojoba wax. , Hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  Examples of silicone elastomers include non-emulsifying organopolysiloxane elastomers and emulsifying organosiloxane elastomers. Examples of the non-emulsifying organopolysiloxane elastomer include dimethicone / vinyl dimethicone cross polymer, lauryl dimethicone / vinyl dimethicone cross polymer, and the like.

  Dimethicone / vinyl dimethicone crosspolymers are commercially available under the names “DC9040” and “DC9045” from DOW CORNING (Midland, Michigan), “SFE839” and “Velvasil” series products from Shinmentec, Shin-Etsu Chemical Commercially available under the names of “KSG-15”, “KSG-16”, “KSG-18” from Kogyo Co., Ltd. ([Dimethicone / Phenylvinyldimethicone crosspolymer]), “Gransil” (from GRANT INDUSTRIES) Trademark) series products.

Examples of lauryl dimethicone / vinyl dimethicone crosspolymers are commercially available from Shin-Etsu Chemical Co., Ltd. under the names such as “KSG-41”, “KSG-42”, “KSG-43” and “KSG-44”. Can be mentioned.
In addition, as (lauryl polydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) crosspolymer, commercially available under the names of “KSG-042Z”, “KSG-045Z”, “KSG-048Z”, etc., from Shin-Etsu Chemical Co., Ltd. Etc.

Examples of the emulsified organosiloxane elastomer include polyether-modified silicone elastomer, polyalkoxylated silicone elastomer, and polyglycerolated silicone elastomer.
Examples of the polyether-modified silicone elastomer include cross-polymers (dimethicone (PEG-10 / 15)) commercially available from Shin-Etsu Chemical Co., Ltd. under names such as “KSG-210” and “KSG-240”.

  Polyalkoxylated silicone elastomers are commercially available under the names “DC9010” and “DC9011” from DOW CORNING, and “KSG-310”, “KSG-320” and “KSG-” from Shin-Etsu Chemical Co., Ltd. 330 "," KSG-340 "and" KSG-320Z "," KSG-350Z "," KSG-360Z "," KSG-380Z ", and the like.

  Polyglycerolated silicone elastomers are commercially available from Shin-Etsu Chemical Co., Ltd. under names such as “KSG-710”, “KSG-810”, “KSG-820”, “KSG-830”, and “KSG-840”. And the like. In addition, as a silicone elastomer into which two types of branches of a silicone chain and an alkyl chain are introduced, those that are commercially available under the names of “KSG-820Z”, “KSG-850Z”, etc., from Shin-Etsu Chemical Co., Ltd. Etc.

  Moreover, you may use the silicone elastomer which contains a polyalkyl ether group as a pendant or bridge | crosslinking. Particularly suitable silicone elastomers containing polyalkyl ether groups are those according to the International Nomenclature of Cosmetic Ingredients (INCI), bis-vinyl dimethicone / bis-isobutyl PPG-20 crosspolymer, bis- Examples thereof include vinyl dimethicone / PPG-20 crosspolymer, dimethicone / bis-isobutyl PPG-20 crosspolymer, dimethicone / PPG-20 crosspolymer, and dimethicone / bis-isobutyl PPG-20 crosspolymer. Such a crosslinked elastomer is obtained from DOW CORNING under the names of test compounds such as “SOEB-1”, “SOEB-2”, “SOEB-3”, “SOEB-4”, and “DC EL-8052 IH”. It can be obtained under a trade name (draft) such as “Si Organic Elastomer Blend”. These elastomer particles are provided by pre-swelling in each solvent (isododecane is used for SOEB-1 and SOEB-2, isohexadecane is used for SOEB-3, and isodecyl neopentanoate is used for SOEB-4). The

As the coating agent, a silicone-based coating agent is preferably exemplified. Examples of the silicone coating agent include silicone resin, acrylic silicone resin, silicone-modified pullulan, adhesive silicone, fluorosilicone resin, and silicone-urethane coating agent.
Examples of the silicone resin include trimethylsiloxysilicic acid commercially available under the trade name “Belsil TMS 803” from Wacker, and polypropyl sesquioxane available under the trade name “670 Fluid” from Toray Dow Corning. And MQ resins such as polypropyl sesquioxane and trimethylsiloxysilicic acid commercially available under the trade name “MQ1640 Flakes Resin”, or T-resin and MTQ resin.
As the acrylic silicone resin, for example, “FA4002ID Silicone Acrylate”, “FA4001CM Silicone Acrylate” such as “FA4002ID Silicone Acrylate” are commercially available from Toray Dow Corning Co., Ltd., Shinetsu Chemical Industry Examples thereof include a copolymer (acrylic / dimethicone) marketed under the trade name “KP-545”.
Examples of the silicone-modified pullulan include pullulan tri (trimethylsiloxy) silylpropylcarbamate commercially available from Shin-Etsu Chemical Co., Ltd. under the trade name “TSPL-30-ID”.
Examples of the adhesive silicone include a cross-polymer (trimethylsiloxysilicate / dimethiconol) commercially available under the trade name such as “DOW CORNING 7-4411 Cosmetic Fluid” from Toray Dow Corning.
The fluorosilicone resin is commercially available from Momentive under the trade name “XS66-B8636” and is commercially available under the trade name “FR-5” (trifluoropropyldimethylsiloxy). / Trimethylsiloxy) silsesquioxane and the like.
Examples of the silicone-urethane coating agent include bishydroxypropyl dimethicone / SMDI copolymer commercially available from Siltech under the trade name “Silmer UR 5050”.
Other coating agents include isobutyl sucrose acetate marketed by Eastman Chemical Company under the name “Sustane SAIB”, dextrin isostearate marketed under the product name “Unifilmma HVY” by Chiba Flour Mills, Inc. A candelilla wax extract marketed under the trade name “Candelilla Resin E-1” by a commercial company is included.

A water-soluble polymer can be used as the thickener. Examples of the water-soluble polymer include gum arabic, carrageenan, caraya gum, gum tragacanth, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, locust bean gum, guar gum, tara gum, tamarind gum, glucomannan Natural polymers such as xylan, mannan, xanthan gum, agar, pectin, fucoidan, galactomannan, curdlan, gellan gum, fucogel, casein, collagen, starch, sodium hyaluronate, alkacilan (alkalinenes-producing polysaccharide); , Sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, methyl Semi-synthetic polymers such as droxypropylcellulose, hydroxypropylmethylcellulose stearoyl ester, propylene glycol alginate, cellulose dialkyldimethylammonium sulfate, PVA (polyvinyl alcohol), PVM (polyvinyl methyl ether), PVP (polyvinyl pyrrolidone), polyethylene oxide, _Examples thereof include synthetic polymers such as sodium polyacrylate, carboxyvinyl polymer, acrylate / C _10-30 alkyl acrylate crosspolymer, sodium polyacrylate, and the like.

  Moreover, you may use a clay mineral as a thickener. Examples thereof include clay minerals that provide an effect of thickening an aqueous phase such as bentonite, hectorite, AlMg silicate (beegum), and laponite.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

  Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, pentylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3 -Butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohols (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohols (eg, 1 , 2,6-hexanetriol, etc.); pentahydric alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipro) Ren glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, etc.); Divalent alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.); Divalent alcohol alkyl ethers (eg, diethylene glycol monomethyl, etc.) Ethers, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.); dihydric alcohol ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc.); glycerin monoalkyl ethers (eg, chimyl alcohol, ceralkyl alcohol) Sugar alcohol (eg, sorbitol, ma Chitoru, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitose, amylolytic sugar reducing alcohol) and the like.

  Examples of monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, etc.); pentose sugars (eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D) -Psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); heptacarbon (eg, aldoheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L Mannose, etc.]; amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D- Galacturonic acid, L-iduronic acid, etc.).

  Examples of the oligosaccharide include sucrose, lactose, maltose, trehalose, cellobiose, gentiobiose, umbilicin, raffinose, gentianose, maltotriose, melezitose, planteose, umbelliferose, stachyose, verbusose and the like.

  Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of the amino acid derivative include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

  Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. Is mentioned.

  Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

Examples of vitamins include vitamins A, B ₁ , B ₂ , B ₆ , C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

Examples of the antioxidant include ascorbic acid such as ascorbyl palmitate, ascorbyl tetraisopalmitate, glucoside ascorbyl, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl sorbate and derivatives thereof;
Tocopherol and its derivatives such as tocopherol acetate, tocopherol sorbate and other tocopherol esters; dibutylhydroxytoluene (BHT) and butylhydroxyanisole (BHA); gallic acid ester; phosphoric acid; citric acid; maleic acid; malonic acid; Acid; fumaric acid; kephalin; hexametaphosphate; phytic acid; ethylenediaminetetraacetic acid: and Irish moss (Rhodiola), hyperthermophilic bacteria, mate tea leaves, oak, kayu rape bark plant extracts such as rapet bark), cherry leaves, and ylang ylang leaves.

  Examples of humectants include polyethylene glycol; propylene glycol; dipropylene glycol; glycerin; 1,3-butylene glycol; xylitol; sorbitol; maltitol; mucopolysaccharides such as chondroitin sulfate; hyaluronic acid; sodium hyaluronate; Sodium acetyl; mucoitin sulfate; caronic acid; atelocollagen; cholesteryl-12-hydroxystearate; bile salts; main components of NMF (natural moisturizing factor) such as pyrrolidone carboxylate and lactate; amino acids such as urea, cysteine and serine Short chain soluble collagen; Diglycerin (EO) PO adduct; 2-Methacryloyloxyethyl phosphorylcholine commercially available under the names “Lipidure HM” and “Lipidure PBM” from NOF Corporation Homopolymer or copolymer; Panthenol; Allantoin; PEG / PPG / polybutylene glycol-8 / 5/3 glycerin sold under the name of “Wilbride S 753” from NOF Corporation; “AMINOCOAT” from Asahi Kasei Chemicals Corporation Trimethylglycine marketed under the name of: Sweet chestnut (Castanea sativa) extract, hazelnut protein hydrolyzate, Polythethes tuberosa polysaccharide, Argania spinosa kernel oil, Maruzen Pharmaceutical Co., Ltd. Examples include various plant extracts such as conchiolin-containing pearl extract marketed under the name “pearl extract” (registered trademark).

  Examples of emollients include polyglyceryl methacrylate and methyl gluceth-20.

  Antiaging agents include, for example, acylamino acids (specifically, those marketed under the names “Maxilip”, “MatrixyL3000”, and “Biopeptide CL” from SEDERMA, and commercially available under the name “Sepilift” from SEPPIC. Peas extract; soy protein hydrolyzate; methyl silanol mannuronate; hydrolyzed peppo pumpkin seed oil lees; Senedesmus extract and the like.

  Examples of the anti-fouling agent include horseradish seed extract (specifically, commercially available under the name “Purisoft” from LSN); shea butter extract (specifically Is marketed by SILAB under the name “Detoxyl”, a blend of ivy extract, phytic acid and sunflower seed extract (for example, under the name “OSMOPUR” by SEDERMA) And the like are exemplified) and the like.

Examples of keratolytic agents include α-hydroxy acids (specifically, glycolic acid, lactic acid, citric acid, malic acid, mandelic acid, tartaric acid, etc.), β-hydroxy acids (specifically, and salicylic acid are exemplified), (specifically, the plant extract (specifically comprising lactic acid C _12-13 alkyl) and their hydroxy acids, Rozerisou (Hibiscus Sabdriffa) their esters such extracts is exemplified ) And the like.

  Examples of the anti-inflammatory agent include bisabolol, allantoin, tranexamic acid, zinc oxide, sulfur oxide and derivatives thereof, chondroitin sulfate, glycyrrhizic acid and derivatives thereof (such as glycyrrhizinate) and the like.

  The emulsion of the present invention may contain at least one whitening agent for the purpose of inhibiting the synthesis of structural proteins such as Pmel17, which is a melanocyte-specific protein contained in the melanogenesis mechanism (stage I). Examples of whitening agents include ferulic acid-containing site vectors (water, glycol, lecithin, ferulic acid, hydroxyethyl cellulose) marketed under the name “Cytovector” (registered trademark) by BASF.

  Furthermore, the emulsion of the present invention may contain at least one peptide described in International Publication No. 2009/010356 pamphlet.

  Furthermore, the emulsion of the present invention may contain a whitening agent having an inhibitory effect on melanin synthesis, microphthalmia-related transcription factor expression, anti-tyrosinase activity, and endothelin-1 synthesis. Examples thereof include licorice extract (Glycyrrhiza glabra extract) marketed under the name of “Licorice extract” (registered trademark) by Maruzen Pharmaceutical Co., Ltd.

  Furthermore, the emulsion of the present invention may contain a whitening agent having an antioxidant action such as a vitamin C compound. Examples include ascorbate, fatty acid or sorbic acid ascorbyl ester, and other ascorbic acid derivatives. Specifically, ascorbyl phosphate salt (ascorbyl magnesium phosphate, ascorbyl sodium phosphate, etc.), saccharide ester of ascorbic acid (ascorbyl-2-glucoside, 2-O-α-D-glucopyranosyl L-ascorbic acid, 6- O-β-D-galactopyranosyl L-ascorbic acid and the like). This type of active ingredient is commercially available from DKSH under the name “Ascorbyl glucoside” ®.

  Furthermore, the emulsion of the present invention may contain other whitening agents. For example, plant extracts (extracts such as bosaki narcissus), cetyl tranexamic acid (manufactured by Nikko Chemicals, product name “NIKKOL TXC”), arbutin, kojic acid, ellagic acid, cysteine, 4-thioresorcin, resorcinol or Pigmentation inhibitors such as lucinol or derivatives thereof, glycyrrhizic acid and hydroquinone-β-glucoside may be included.

The emulsion of the present invention may further contain an organic sunscreen agent and / or an inorganic sunscreen agent.
Organic sunscreen agents include dibenzoylmethane derivatives such as butylmethoxydibenzoylmethane (such as those sold under the name “Parsol 1789” from HOFFMANN LA ROCHE); cinnamic acid derivatives such as octyl methoxycinnamate (HOFFMANN LA Such as those commercially available from ROCHE under the name “Parsol MCX”); salicylates; paraaminobenzoic acids; β, β′-diphenyl acrylate derivatives; benzophenone derivatives; benzylidene camphor derivatives such as terephthalylidene dicamphor sulfonic acid; Examples thereof include benzimidazole derivatives; triazine derivatives; phenylbenzotriazole derivatives; anthranilic acid derivatives. These may be coated or encapsulated.
Examples of inorganic sunscreen agents include nanopigments that are optionally coated with pigments or metal oxides. Examples of nanopigments include titanium oxide, iron oxide, zinc oxide, zirconium oxide, and cerium oxide. All of these compounds are well known as UV photoprotective agents.

  Examples of the preservative include paraoxybenzoic acid esters (methyl paraben, propyl paraben, etc.), phenoxyethanol and the like.

Other optional ingredients used in the emulsion of the present invention are listed in the “International Cosmetic Ingredient Dictionary and Handbook” (13th edition, 2010) published by the Personal Care Products Council. You can use what you have.
The amount of these optional components is not particularly limited as long as it does not impair the object of the present invention.

The emulsion of the present invention is based on the total mass of the emulsion.
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
It can manufacture by mix | blending.

The components (A) to (E) may be uniformly stirred and mixed by an ordinary method without requiring a special apparatus.
Although there is no restriction | limiting in particular in the order which mixes each component, In the preferable aspect of this invention, first, component (B), (C) and (D) is mixed, it stirs until it becomes uniform, and contains a microparticles | fine-particles. An oil phase is formed, and then component (A) is added to the oil phase and stirred until uniform, and component (E) is further added to the resulting mixture and stirred until uniform, so that A (F + W) / O type emulsion in which a phase containing a fluorinated oil and an aqueous phase are more uniformly dispersed in an oil phase containing an oil that is incompatible with the oil can be obtained.
As described above, according to the method of the present invention, a (F + W) / O type emulsion can be formed by a normal stirring operation.
In addition, an oil-soluble or water-soluble optional component may be added in advance to each of the oil phase and the water phase containing an oil agent that is incompatible with the fluorinated oil agent on the condition that the emulsion stability of the emulsion is not inhibited.

  The emulsion of the present invention is excellent in emulsification stability, has a high persistence in cosmetic effects such as a makeup effect and a skin care effect, and can give a fresh feeling when applied to the skin. (Including medicinal cosmetic compositions), particularly as a cosmetic composition for skin care or makeup. By applying the cosmetic composition of the present invention to the skin, skin care or make-up excellent in durability of the cosmetic effect can be applied. That is, the present invention also provides a cosmetic method for skin care or makeup, which comprises applying the cosmetic composition of the present invention to the skin. In the present specification, “cosmetic effect” includes not only a makeup effect but also a skin care effect.

  The product form of the cosmetic composition of the present invention is not particularly limited and can be arbitrarily selected. For example, facial cosmetics such as face wash, lotion, beauty liquid, milky lotion, cream, pack; makeup cosmetics such as foundation, lipstick, eye shadow, sunscreen, makeup base; body cosmetics; aromatic cosmetics; body Cleaning agent; can be used for hand cream and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. Unless otherwise specified, the composition ratio is based on a mass ratio (mass%).

[Examples 1 to 6 and Comparative Examples 1 to 4]
Cosmetic compositions having the compositions shown in Tables 1 and 2 were prepared as follows.
1. Components (1) to (3) were mixed and stirred until homogeneous to prepare an oil phase (mixture 1).
2. Next, component (4) fluorinated oil was added to mixture 1 as the oil phase and stirred until uniform (mixture 2).
3. Then, the purified water which is a component (5) was added to the said mixture 2, and it stirred until it became uniform.

[Appearance of the cosmetic composition after preparation]
After preparation, the appearance of each cosmetic composition after standing at room temperature overnight was confirmed by visual observation, and further microscopic observation was performed in order to confirm the state of the emulsion. Moreover, the cosmetic compositions of Examples 1 to 6 were evaluated by microscopic observation of the stability of the emulsion after standing at 40 ° C. for 1 month.
The appearance of the cosmetic compositions of Examples 1 to 6 and the state of the emulsion by microscopic observation confirmed visually are shown in Table 3, the appearance of the cosmetic compositions of Comparative Examples 1 to 4 and the state of the emulsion by microscopic observation. Are shown in Table 4. Moreover, the microscope observation image of the cosmetic composition of Example 2 after standing for one month is shown in FIG.

As shown in Table 3, in Examples 1 to 6, a cosmetic composition in a uniform dispersion state could be obtained. Moreover, as shown in FIG. 1, when the cosmetic composition of Example 2 was observed with a microscope, two types of droplets having different sizes (7 to 8 μm and 15 to 20 μm) were dispersed in the oil phase. It was confirmed that From this observation image, it is presumed that the fluorinated oil agent and the aqueous phase component are separately dispersed in an oil phase containing an oil agent that is incompatible with the fluorinated oil agent, and the emulsion of the present invention is (F + W) / It turns out that it is an O-type emulsion.
On the other hand, as shown in Table 4, it was found that in Comparative Examples 1 to 4 not containing the organically modified clay mineral or the fluorine compound-treated powder, the liquid was separated on the same day. When the cosmetic compositions of Comparative Examples 1 and 2 were observed with a microscope, it was confirmed that only droplets of about 7 to 8 μm were dispersed in the oil phase. Further, when the cosmetic compositions of Comparative Examples 3 and 4 were observed with a microscope, it was confirmed that only droplets of about 15 to 20 μm were dispersed in the oil phase. From the emulsified state by microscopic observation, it is presumed that in Comparative Examples 1 and 2, only the fluorinated oil droplets are dispersed, and in Comparative Examples 3 and 4, only the water phase component droplets are dispersed.

[Examples 7 and 8 and Comparative Examples 5 and 6]
A cosmetic composition which is a liquid foundation having the composition shown in Table 5 was prepared as follows.
1. Components 1-22 were mixed and stirred until homogeneous to prepare an oil phase (mixture 1).
2. On the other hand, components 25 to 28 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, component 23 or 24 was added to the oil phase as mixture 1 and stirred until uniform (mixture 3).
4). The mixture 2 was added to the obtained mixture 3 and stirred until it became uniform to obtain a cosmetic composition.

[Evaluation of makeup effect durability and feeling of use]
The persistence and feeling of use of the makeup effect of the liquid foundation after preparation were evaluated based on the following evaluation criteria. The results are shown in Table 6.
Evaluation criteria for makeup effect persistence:
10 panelists used the liquid foundation after preparation,
A: More than 8 out of 10 felt that makeup was good.
B: 7 out of 10 felt that they had good makeup.
C: 4 to 6 out of 10 felt that makeup was good.
D: Less than 3 out of 10 felt that makeup was good.

Evaluation criteria for fresh feeling:
10 panelists used the liquid foundation after preparation,
A: Eight or more out of 10 felt that the feeling of use during application was fresh.
B: Seven out of ten people felt that the feeling of use during application was fresh.
C: 4 to 6 out of 10 felt that the feeling of use during application was fresh.
D: 3 or less out of 10 felt that the feeling of use at the time of application was fresh.

As shown in Table 6, the liquid foundations of Examples 7 and 8 could be felt to have good makeup.
Further, in the liquid foundations of Examples 7 and 8, the aqueous phase component can be stably blended without the need for a surfactant, so that it was possible to give a fresh feeling when applied to the skin. In addition, in the liquid foundations of Examples 7 and 8, it is possible to use a small amount of surfactant in combination as long as the fresh feeling of use is not significantly impaired.
On the other hand, the liquid foundations of Comparative Examples 5 and 7 were in a state of uneven color and uneven skin color. In Comparative Example 6, the skin color was in a uniform state, but the durability of the makeup effect and the fresh feeling of use were not sufficiently obtained.

[Evaluation of water resistance and oil resistance]
The liquid foundations prepared in Example 8 and Comparative Example 7 were each applied to a bio skin plate (“P001-001” manufactured by Beaulux) and dried at room temperature for 10 minutes. Thereafter, 0.05 g of purified water and 0.03 g of squalane were respectively dropped onto each liquid foundation. The state after standing for 1 hour is shown in FIG. As shown in FIG. 2, neither the purified water dropped on the foundation of Example 8 nor the state of squalane changed. On the other hand, although the state of the purified water dropped on the foundation of Comparative Example 7 did not change, it was confirmed that squalane penetrates into the applied foundation and spreads, and the oil resistance is insufficient.

[Example 9, cream foundation]
A cream foundation formulation having the composition shown in Table 7 was prepared as follows.
1. Components 1 to 21 were mixed and stirred until uniform to prepare an oil phase (mixture 1).
2. On the other hand, components 23 to 27 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, component 22 was added to the oil phase, which was mixture 1, and stirred until uniform (mixture 3).
4). Then, the mixture 2 was added to the mixture 3, and it stirred until it became uniform, and the cream foundation formulation was obtained.

The prepared cream foundation was allowed to stand at 40 ° C. for 1 month and then visually checked for separation. As a result, it was evaluated that the skin color was uniform and the makeup effect was highly durable. Further, as a result of microscopic observation, as shown in FIG. 3, it was confirmed that two types of droplets (7 to 8 μm and 2 to 3 μm) having different sizes were dispersed in the oil phase. From this result, it was confirmed that the fluorine compound-coated powder was a small amount of 2% by mass, and a good dispersion state could be obtained even in combination with other hydrophobically treated powder. Furthermore, the combined use of the surfactant allows the size of the fluorinated oil droplet in the oil phase to be 7 to 8 μm, which is the same as in Example 2 (FIG. 1), but the water phase component in the oil phase. It can be seen that the size of the droplet is 2 to 3 μm, which is smaller than that in the case of Example 2 (FIG. 1).

[Example 10, sunscreen]
A sunscreen formulation having the composition shown in Table 8 was prepared as follows.
1. Components 1 to 11 were mixed and stirred until uniform to prepare an oil phase (mixture 1).
2. On the other hand, ingredients 13 to 17 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, component 12 was added to the oil phase as mixture 1 and stirred until uniform (mixture 3).
4). Then, the mixture 2 was added to the mixture 3, and it stirred until it became uniform, and obtained the sunscreen formulation.

  The prepared sunscreen preparation was allowed to stand at 40 ° C. for 1 month and then visually checked for the presence or absence of separation. As a result, it was evaluated that the white color was in a uniform state and the durability of the cosmetic effect was high. Moreover, it was evaluated that a fresh feeling of use was obtained.

[Example 11, makeup base]
A cosmetic base preparation having the composition shown in Table 9 was prepared as follows.
1. Components 1 to 15 were mixed and stirred until homogeneous to prepare an oil phase (mixture 1).
2. On the other hand, components 17 to 21 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, component 16 was added to the oil phase as mixture 1 and stirred until uniform (mixture 3).
4). Thereafter, the mixture 2 was added to the mixture 3 and stirred until uniform to obtain a cosmetic base preparation.

  After leaving the prepared makeup base at 40 ° C. for 1 month, the presence or absence of separation was confirmed by visual inspection. As a result, the white color was in a uniform state, the makeup effect was highly durable, and a fresh feeling of use was obtained. It was evaluated.

[Example 12, face cream]
A face cream formulation having the composition shown in Table 10 was prepared as follows.
1. Components 1 to 12 were mixed and stirred until uniform to prepare an oil phase (mixture 1).
2. On the other hand, components 14 to 19 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, component 13 was added to the oil phase as mixture 1 and stirred until uniform (mixture 3).
4). Then, the mixture 2 was added to the mixture 3, and it stirred until it became uniform, and the face cream formulation was obtained.

  The prepared face cream was allowed to stand at 40 ° C. for 1 month and then visually checked for separation, and it was confirmed to be a uniform white cream state. In addition, it was evaluated that the makeup effect was highly durable and a fresh feeling of use was obtained.

[Example 13, hand cream]
A hand cream formulation having the composition shown in Table 11 was prepared as follows.
1. Components 1 to 11 were mixed and stirred until uniform to prepare an oil phase (mixture 1).
2. On the other hand, components 14 to 18 were mixed and stirred until uniform to prepare an aqueous phase (mixture 2).
3. Next, components 12 and 13 were added to the oil phase, which was mixture 1, and stirred until uniform (mixture 3).
4). Then, the mixture 2 was added to the mixture 3, and it stirred until it became uniform, and the hand cream formulation was obtained.

  The prepared hand cream was allowed to stand overnight at room temperature (25 to 30 ° C.) and then visually checked for the presence or absence of separation. As a result, it was confirmed to be a uniform white cream state. Moreover, it was evaluated that the durability of the water resistance effect was high and a fresh feeling of use was obtained.

[Example 14, mascara]
Mascara preparations having the compositions shown in Table 12 were prepared as follows.
1. Components 1 to 13 were uniformly mixed and dispersed while heating at 80 ° C. (mixture 1).
2. Ingredient 14 was heated to 80 ° C. and then stirred while being added to mixture 1 (mixture 2).
3. The ingredients 15 to 17 which had been heated and dissolved uniformly were added to the mixture 2 and stirred until uniform.
4). After cooling and defoaming, a mascara preparation was obtained.
The prepared mascara was allowed to stand at 40 ° C. for one month and then visually checked for separation, and it was confirmed that the mascara was in a uniform black cream state. In addition, it was easy to apply, and after application, sweat, tears, and sebum did not cause mascara to bleed and adhere to the lower eyelid.

  The emulsion of the present invention is suitably used as a cosmetic composition, particularly as a cosmetic composition for skin care or makeup. According to a preferred embodiment of the present invention, the emulsion of the present invention is excellent in emulsification stability, has a long cosmetic effect, and can provide a fresh feeling of use.

Claims (9)

In an oil phase containing an oil agent that is incompatible with the fluorine oil agent, a phase containing a fluorine oil agent and an aqueous phase are dispersed (F + W) / O type emulsion, with respect to the total mass of the emulsion,
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
An emulsion.   The emulsion according to claim 1, wherein component (A) is at least one selected from the group consisting of perfluoropolyethers and fluorosilicone oils.   The emulsion according to claim 1 or 2, wherein the fluorine compound in component (B) is at least one selected from the group consisting of perfluoroalkyl phosphate esters and perfluoroalkylalkoxysilanes.   The emulsion as described in any one of Claims 1-3 in which a component (C) contains silicone oil.   The emulsion according to any one of claims 1 to 4, wherein the component (D) is a water-swellable clay mineral treated with a quaternary ammonium compound.   A cosmetic composition comprising the emulsion according to any one of claims 1 to 5.   Use of the composition according to claim 6 for skin care or makeup.   A cosmetic method for skin care or makeup comprising applying the composition of claim 6 to the skin. A method for producing an (F + W) / O type emulsion, in which a phase containing an fluorinated oil and an aqueous phase are dispersed in an oil phase containing an oil that is incompatible with the fluorinated oil, with respect to the total mass of the emulsion And
(A) 1 to 40% by mass of a fluorinated oil,
(B) 0.1-30% by mass of a powder coated with a compound containing a fluorine compound,
(C) 10 to 70% by mass of an oil agent that is incompatible with component (A),
(D) 0.1-5% by mass of organically modified clay mineral, and (E) 1-60% by mass of aqueous phase component
Combining the method.