JP5705619B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic comprising a hydrophobized inorganic powder, a silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted on a siloxane main chain, silicone oil, triglyceride and astaxanthin. More particularly, the present invention relates to a water-in-oil emulsified cosmetic that is excellent in usability and astaxanthin stability over time even when powder is blended.

Ingredients used in cosmetics, such as polyphenols such as catechins and carotenoids such as astaxanthin, are useful for preventing skin aging such as prevention and improvement of wrinkles and tarmi, and for prevention and improvement of spots Although it is known to have an effect in nature, many of them are difficult to be stably blended into preparations because of their low oxidation stability.
Regarding carotenoids, since they are oxidized by light and heat and cause discoloration, measures to prevent discoloration such as the use of a light shielding container and the addition of an antioxidant have been taken, but they are not sufficient. Astaxanthin is a kind of red carotenoid and has high antioxidant power, but astaxanthins are also unstable to heat, oxygen, light, etc., and therefore methods for improving the stability have been studied. For example, a method of adding a phospholipid (for example, see Patent Document 1) or a method of adding a phospholipid or tocopherol in an oil-in-water emulsion cosmetic and controlling the particle size of the emulsion (for example, see Patent Document 2) Etc.

However, recently, it has been demanded that these medicinal ingredients are blended not only in skin care cosmetics such as skin lotions and creams but also in cosmetics such as sunscreen cosmetics and foundations. In addition, powders such as inorganic powders are raw materials blended in many cosmetics such as skin care cosmetics, makeup cosmetics, and hair cosmetics. In particular, makeup cosmetics such as foundations and base cosmetics often have a cosmetic effect by incorporating powder, so the interaction between medicinal ingredients and powder ingredients is a problem to be investigated. It was.
The action of powder on astaxanthin is based on the method of evaluating the solid catalyst activity of powder by the discoloration of carotenoid pigments such as astaxanthin (see, for example, Patent Document 3). In some cases, astaxanthin further deteriorated those unstable to heat, oxygen, light, and the like.
On the other hand, when astaxanthin is blended with a water-in-oil emulsified cosmetic, astaxanthin separates from the oil layer over time, and it is difficult to stably blend in the cosmetic.

JP 2007-254459 A JP 2007-326829 A JP 2009-222702 A

The method of adding phospholipids or adding tocopherol is effective for the storage stability of astaxanthin alone, but the effect is not sufficient in terms of stability in the presence of powder, and the particle size of the emulsion is reduced. The control method is a technique of oil-in-water emulsified cosmetics, which is effective when blending astaxanthin as the oil to be emulsified, but is applicable to water-in-oil emulsified cosmetics whose oil phase is the outer phase. It cannot be done.
In addition, in the method for evaluating the solid catalyst activity of the powder, the relevance to the stability of astaxanthin by the surface treatment of the powder is disclosed, but there is nothing about the stability and usability as an actual cosmetic. It was not mentioned, nor did it teach stability in water-in-oil emulsified cosmetics. Therefore, even when blended with powder, the spread is good, the usability such as a uniform finish of the cosmetic film is excellent, the stability of astaxanthin over time, and also stable in water-in-oil emulsified cosmetics. The development of cosmetics was desired.

  In view of this situation, the present inventors have conducted intensive studies, and as a result, obtained are a hydrophobized inorganic powder, a silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted on the siloxane main chain, silicone oil, triglyceride, and astaxanthin. It discovered that the water-in-oil type emulsified cosmetic which can solve the said subject was obtained by mix | blending, and came to complete this invention. Hydrophobic treatment of inorganic powder with high surface activity by suppressing the surface activity, and further using a silicone surfactant in which organopolysiloxane groups and hydrophilic groups are grafted to the siloxane main chain It became possible to improve the dispersibility in silicone oil, to prevent contact between astaxanthin and inorganic powder by selective adsorption, and to improve the stability of astaxanthin. Furthermore, it has been found that the triglyceride blending improves the compatibility of silicone oil and astaxanthin to an appropriate level, improving the stability and uniformity of the cosmetic film.

That is, the present invention
(1) the following components (a) to (e);
(A) Hydrophobized inorganic powder (b) Silicone surfactant in which organopolysiloxane group and hydrophilic group are grafted to siloxane main chain (c) Silicone oil (d) Triglyceride (e) Astaxanthin A water-in-oil emulsified cosmetic is provided.

  (2) In addition, the hydrophobized inorganic powder of component (a) is selected from dimethylpolysiloxane treatment, methylhydrogenpolysiloxane treatment, alkyltriethoxysilane treatment, metal soap treatment or acrylic-silicone graft copolymer treatment. The present invention provides a water-in-oil emulsified cosmetic according to (1), characterized in that the water-in-oil type emulsified cosmetic is (1) or more.

  (3) Further, the present invention is characterized in that the blending amount of the inorganic powder not subjected to the hydrophobization treatment is 1% by mass (hereinafter simply referred to as “%”) or less (1) or (2) The water-in-oil emulsified cosmetic described in 1. is provided.

(4) The water-in-oil emulsified cosmetic according to any one of (1) to (3), wherein the silicone oil as component (c) has a viscosity of 20 mm ² / s or less at 25 ° C. Is to provide.

  (5) Component (a) 1-40%, Component (b) 0.5-10%, Component (c) 1-50%, Component (d) 0.1-15%, Component (e ) Is blended in an amount of 0.00001 to 0.1%. The water-in-oil emulsified cosmetic according to any one of (1) to (4) is provided.

  (6) The ratio (d) / (e) of the blending amount of the component (d) of the triglyceride to the astaxanthin of the component (e) is 50 to 10,000, and any of (1) to (5) The water-in-oil emulsified cosmetic according to claim 1 is provided.

  The water-in-oil emulsified cosmetic of the present invention has a water-in-oil type that is excellent in usability, such as good spread and uniform finish of the cosmetic film and stability of astaxanthin over time, even when blended with powder. It relates to emulsified cosmetics.

Hereinafter, the present invention will be described in detail.
The hydrophobized inorganic powder of component (a) used in the present invention is an inorganic powder that has been subjected to surface treatment to impart hydrophobicity.
The inorganic powder to be treated is usually a powder used in cosmetics, such as spherical, plate-like, needle-like shapes, fumes, fine particles, pigment grades, etc., porous, no It is not particularly limited by the particle structure such as porosity. Specifically, titanium oxide, black titanium oxide, conger, ultramarine, bengara, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, silicic anhydride, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide , Chromium hydroxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, boron nitride, bismuth oxychloride, titanium oxide coating Mica, iron oxide coated mica, iron oxide coated mica titanium, organic pigment coated mica titanium, titanium oxide coated glass powder, iron oxide titanium oxide coated glass powder, aluminum powder, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, Sulfate Um coated mica titanium, titanium oxide-containing silicic acid anhydride, zinc oxide containing anhydrous silicic acid and the like, can be used one or two or more in accordance with those on the intended use.

Examples of the treating agent for hydrophobizing the inorganic powder in component (a) include dimethylpolysiloxane, methylhydrogenpolysiloxane, high viscosity silicone, cross-linked silicone, fluorine-modified silicone, acrylic-silicone graft copolymer. Copolymers, silicone compounds such as silicone resins, anionic surfactants, cationic surfactants, surfactants such as nonionic surfactants, metal soaps such as zinc laurate and zinc stearate, polyisobutylene, wax, higher fatty acids, Oils such as higher alcohols, amino acid compounds such as N-acylamino acids, perfluoroalkyl phosphoric acid and salts thereof, perfluoropolyether, fluoroalkoxysilane, perfluoropolyetheralkyl phosphoric acid and salts thereof, perfluoroalkylsilane, etc. Fluorine compound , Polyvinyl pyrrolidone - polyvinylpyrrolidone modified polymer compound copolymers such as hexadecene and the like. From the viewpoint of improving the stability of astaxanthin by suppressing the powder surface activity, dimethylpolysiloxane treatment, methylhydrogenpolysiloxane treatment, alkyltriethoxysilane treatment, metal soap treatment, and acrylic-silicone graft copolymer treatment are particularly preferred. .
These surface treatments may be used alone or in combination of two or more, or may be combined treatments. These treated powders can be used singly or in combination.

  In the component (a), the method for treating the powder with the treating agent is usually a known method and is not particularly limited. For example, a wet method using a solvent, a gas phase method, a mechanochemical Law. Further, the treatment ratio of the treating agent and the powder in the component (a) is preferably 0.1 to 20: 99.9 to 80 as a mass ratio.

  Further, in the acrylic-silicone graft copolymer treatment, a chip-forming treatment can be performed in which powder is kneaded into the acrylic-silicone graft copolymer. By performing the chip forming treatment, the surface activity suppression effect and dispersibility of the powder are further improved. The chip-forming treatment can be performed by the method described in JP-A-06-009332. For example, the acryl-silicone graft copolymer is mixed with the powder and heated under a high shear force condition. More preferably, the powder is mixed with a solution in which an acrylic-silicone graft copolymer is dissolved in a volatile solvent, and the mixture is kneaded under high shearing force under heating to volatilize the volatile solvent. There is a way. The kneading under high shear force conditions can be carried out using, for example, a roll mill. The blending ratio of the acrylic-silicone graft copolymer and the powder in the case of chipping treatment is 5 to 70% of the acrylic-silicone graft copolymer, 30 to 95% of the powder, especially the acrylic-silicone graft copolymer. The polymer content is preferably 10 to 50% and the powder content 50 to 90%.

  The amount of component (a) used in the present invention is preferably 1 to 40%, more preferably 3 to 35%. Within this range, the decomposition of astaxanthin due to the surface activity of the powder is suppressed and stable, and it is preferable because it is excellent in usability such as being able to obtain a uniform cosmetic film with good dispersion in silicone oil.

  Further, the inorganic powder that has not been subjected to the hydrophobizing treatment in the present invention can be blended to such an extent that the effect is not impaired, but when blending the inorganic powder, it is 1% or less from the viewpoint of astaxanthin stability. Preferably there is.

  The hydrophilic group of the silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted to the siloxane main chain of the component (b) used in the present invention is not particularly limited, but is a polyoxyalkylene group or a polyglyceryl group Are preferable, and organopolysiloxane graft polyoxyalkylene-modified silicone, organopolysiloxane graft polyglycerin-modified silicone and the like can be mentioned.

As a silicone-based surfactant in which an organopolysiloxane group and a hydrophilic group are grafted to the siloxane main chain of component (b) (hereinafter sometimes simply referred to as “specific organopolysiloxane group-grafted silicone surfactant”). Particularly preferred are those represented by the following general formula (1).
R ¹ _a R ² _b R ³ _c SiO _{(4-a-b-c) / 2} (1)
Specific examples of R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Hexadecyl, octadecyl, eicosyl and other alkyl groups, cyclopentyl, cyclohexyl and other cycloalkyl groups, phenyl, tolyl and other aryl groups, benzyl and phenethyl and other aralkyl groups, trifluoropropyl and hepta Fluorine-substituted alkyl groups such as decafluorodecyl group, amino-substituted alkyl groups such as 3-aminopropyl and 3-[(2-aminoethyl) amino] propyl groups, carboxy-substituted alkyl groups such as 3-carboxypropyl group, etc. It is done.

A part of R ¹ is represented by the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 (2)
An organic group represented by Here, R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁵ — (CO) —, and R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms. m is an integer of 0 ≦ m ≦ 15, and d and e are integers of 0 ≦ d ≦ 50 and 0 ≦ e ≦ 50, respectively. A part of this R ⁵ is an alcohol residue or an alkenyl addition type residue.
When m = 0
_{-O- (C 2 H 4 O)} d (C 3 H 6 O) e -R 4
In this case, if d = 0 and e = 0, an alkoxy group having 4 to 30 carbon atoms, for example, a lower alkoxy group such as a butoxy group to a higher alkoxy such as an oleyloxy group such as cetyl alcohol, oleyl alcohol, and stearyl alcohol, and a stearoxy group Or fatty acid residues such as acetic acid, lactic acid, butyric acid, oleic acid, stearic acid, and behenic acid. Further, if d> 1 and e> 1, it becomes an alcohol residue of an alkylene oxide adduct of higher alcohol (terminal is a hydroxyl group).
When m ≧ 1 and d = e = 0, d is preferably 3, 5 or 11, in which case it is an allyl ether, pentenyl ether, or undecenyl ether residue, for example allyl stearyl depending on the substituent of R ⁴ Examples include ether residues, pentenyl behenyl ether residues, undecenyl oleyl ether residues, and the like. When d or e is not 0, an alkoxy group or an ester group is present via polyoxyalkylene. Whatever d and e are, when m = 0, the hydrolysis resistance may be inferior. When d is 15 or more, the oily odor is strong.

R ² represents the following general formula (3)
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 6 (3)
Or an organic group having a polyoxyalkylene group represented by the following general formula (4)
-QOX (4)
(In the formula, Q represents a C 3-20 divalent hydrocarbon group which may contain at least one of an ether bond and an ester bond, and X represents a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups. And the same or different organic groups selected from organic groups represented by
R ⁶ in the general formula (4) is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an organic group represented by R ⁵ — (CO) —, and R ⁵ is a carbon atom having 1 to 30 carbon atoms. It is a hydrogen group. f is an integer of 2 to 200, preferably 5 to 100, g is an integer of 0 to 200, preferably 0 to 100, and f + g is 3 to 200, preferably 5 to 100, and f / g ≧ 1. It is preferable that In addition, when the polyoxyalkylene group shown by General formula (3) consists of both an ethylene oxide unit and a propylene oxide unit, any of the block polymer of these both units and a random polymer may be sufficient.
The Q in the general formula _{(5), - (CH 2} ) 2 -, - (CH 2) 3 -, - CH 2 CH (CH 3) CH 2 -, - (CH 2) 4 -, - (CH 2 ) ₆ -,-(CH ₂ ) ₇ -,-(CH ₂ ) ₈ -,-(CH ₂ ) ₂ -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ -CH (CH ₂ CH ₃ )- , — (CH ₂ ) ₃ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— CH ₂ CH (CH ₃ ) —, —CH ₂ —CH (CH ₃ ) —COO (CH ₂ ) ₂ — and the like can be exemplified. X is a polyhydric alcohol-substituted hydrocarbon group having at least two hydroxyl groups, and is preferably a hydrocarbon group selected from glycerin.

  Examples of glycerin include compounds represented by the following general formulas (A) to (C).

  Here, Q in the above formulas (A) to (C) is the same as Q in the general formula (4), and l and m are integers of 1 to 20. In addition, a part of the hydroxyl group in the compound may be substituted with an alkoxy group or an ester group.

R ³ represents the following general formula (5)

  It is the organopolysiloxane shown by these. Here, h is 1 to 500, preferably an integer of 1 to 50. n is an integer of 1 to 5, and when synthesizing from a reaction between a vinyl group and hydrogen siloxane, n is 2. If h is greater than 500, problems such as poor reactivity with the main chain hydrogen siloxane may occur.

In the component (b) exemplified in the general formula (1) in the present invention, a is 1.0 to 2.5, preferably 1.2 to 2.3. When a is less than 1.0, the compatibility with the oil is poor, and when it is greater than 2.5, the hydrophilicity is poor. b is 0.001 to 1.5, preferably 0.05 to 1.0. If b is less than 0.001, the hydrophilicity will be poor, and if it is more than 1.5, the hydrophilicity will be too high. c is 0.001 to 1.5, preferably 0.05 to 1.0. When c is less than 0.001, the compatibility with silicone oil is poor, and when it is greater than 1.5, the hydrophilicity is poor.
Although the weight average molecular weight of the component (b) illustrated by the said General formula (1) used by this invention is not specifically limited, 500-200000 are preferable, More preferably, it is 1000-100000.

  As a commercial item of the component (b) in this invention, organopolysiloxane graft | grafting polyoxyalkylene modified silicone is KF-6028 (The Shin-Etsu Chemical Co., Ltd. make, display name; PEG-9 polydimethylsiloxyethyl dimethicone), KF-6038. (Shin-Etsu Chemical Co., Ltd., display name; lauryl PEG-9 polydimethylsiloxyethyl dimethicone), organopolysiloxane grafted polyglycerin-modified silicone is KF-6104 (Shin-Etsu Chemical Co., Ltd., display name; polyglyceryl-3 polydimethylsiloxy) Ethyl dimethicone), KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd., display name; lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone), and the like, among which KF-6028 is particularly preferable.

  The blending amount of the component (b) used in the present invention is preferably 0.5 to 10%, more preferably 1 to 8%. Within this range, astaxanthin is preferable because it is excellent in stability, good spread and usability such as uniformity of the decorative film.

  The silicone oil of component (c) used in the present invention is not particularly limited, but is preferably liquid at 25 ° C., and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane. , Octamethyltrisiloxane, decamethyltetrasiloxane, methyltrimethicone, caprylyltrimethicone, dimethylpolysiloxane, methylphenylpolysiloxane, and the like, and one or more of these can be used.

The viscosity of the silicone oil of component (c) used in the present invention is preferably 20 mm ² / s or less at 25 ° C., more preferably 10 mm ² / s or less.

  The blending amount of the component (c) used in the present invention is preferably 1 to 50%, more preferably 5 to 40%. Within this range, astaxanthin is excellent in stability and usability, which is preferable.

  The triglyceride of component (d) used in the present invention is not particularly limited, but is preferably liquid at 25 ° C., glyceryl tri-2-ethylhexanoate, glyceryl tri (capryl / capric acid), glyceryl triisostearate, tripalm oil fatty acid Examples thereof include glyceryl and trimacadamia nut oil fatty acid glyceryl, and one or more of them can be used.

  The blending amount of component (d) used in the present invention is preferably 0.1 to 15%, more preferably 0.5 to 10%. Within this range, astaxanthin is excellent in stability and usability, which is preferable.

  The astaxanthin as the component (e) used in the present invention may be a chemically synthesized product or one extracted from natural products such as krill, salmon, trout, fussa, red yeast, hematococcus, etc. Can be preferably used. That is, an extraction solvent is added to Krill family krill (Euphasia similis G.O., etc.) and extracted, and astaxanthin extract extract obtained by filtering this extract, or the extract solvent is further distilled off from this extract, if necessary. Then, after performing a chemical reaction such as hydrogenation or hydrolysis, purified astaxanthin that has been deodorized and purified using means such as molecular distillation or column chromatography or high performance liquid chromatography (HPLC) can be used. As said extraction solvent, organic solvents, such as acetone, ether, chloroform, alcohol (ethanol, methanol, etc.), can also be used, and these mixed solutions can also be used. Alternatively, supercritical carbon dioxide may be used.

  The amount of component (e) used in the present invention is preferably 0.00001 to 0.1%, more preferably 0.0001 to 0.01%. Within this range, this effect of astaxanthin is sufficiently obtained, which is preferable.

  As for the ratio of the amount of components (d) and (e) used in the present invention, (d) / (e) is preferably 50 to 10,000. Within this range, the solubility of astaxanthin in the oil layer is moderate, and the effect of improving the stability over time is excellent.

  The blending amount of water in the water-in-oil emulsified cosmetic of the present invention depends on the blending amounts of the components (a) to (e), but is preferably 10 to 80%.

  In addition to the above components, the water-in-oil emulsified cosmetic of the present invention usually includes components used in cosmetics, powders other than component (a), surfactants other than component (b), and components ( c) Oils other than (d) and (e), oil gelling agents, ultraviolet absorbers, aqueous components such as water-soluble polymers and alcohols, oil-soluble film forming agents such as trimethylsiloxysilicic acid, paraoxybenzoic acid derivatives, phenoxyethanol Such preservatives, vitamins, cosmetic ingredients, fragrances and the like can be appropriately blended within a range not impairing the effects of the present invention.

  Examples of powders other than component (a) include organic powders and pigments, such as nylon powder, polymethyl methacrylate powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, polyethylene powder. , Polystyrene powder, organopolysiloxane elastomer powder, polymethylsilsesquioxane powder, polyurethane powder, wool powder, silk powder, crystalline cellulose powder, organic powder such as N-acyl lysine powder, organic tar pigment, organic dye A lake pigment etc. are mentioned, These can use 1 type, or 2 or more types.

  Surfactants other than component (b) are those used for the purpose of dispersing agents, emulsifying aids, feel modifiers, etc., and include glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid esters and alkylene glycols thereof. Adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, polyoxyalkylene-modified silicone, polyoxyalkylene Nonionic surfactants such as alkyl co-modified silicone, alkylbenzene sulfate, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate Acid salt, α-sulfonated fatty acid salt, acylmethyl taurine salt, N-methyl-N-alkyl taurine salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl Anionic surfactants such as ether phosphates, polyoxyethylene alkylphenyl ether phosphates, N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, alkylamine salts, polyamines and alkanoylamine fatty acid derivatives, alkyls Cationic surfactants such as ammonium salts and alicyclic ammonium salts, amphoteric surfactants such as lecithin and N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, and the like are listed. Or by using two or more That.

  Examples of oils other than components (c), (d), and (e) include, for example, paraffin wax, ceresin wax, ozokerite, microcrystalline wax, montan wax, fisher trops wax, polyethylene wax, liquid paraffin, squalane, petrolatum, polyisobutylene. , Hydrocarbons such as polybutene, natural waxes such as carnauba wax, beeswax, lanolin wax, candelilla, pentaerythritol ester of rosin acid, cetyl isooctanoate, isopropyl myristate, diglyceryl triisostearate, dipentaerythritol fatty acid ester Esters other than triglycerides, stearic acid, behenic acid, fatty acids such as 12-hydroxystearic acid, cetanol, stearyl alcohol, behenyl alcohol Higher alcohols, lanolin derivatives such as lanolin fatty acid isopropyl and lanolin alcohol, amino acid derivatives such as di-cholesteryl, behenyl, octyldodecyl, N-lauroyl L-glutamate, perfluoropolyether, perfluorodecane, perfluorooctane Fluorine-based oils, etc., etc. are mentioned, These can use 1 type, or 2 or more types.

  As the oil gelling agent, any one can be used as long as it is usually used in cosmetics. Examples thereof include dextrin fatty acid ester, sucrose fatty acid ester, starch fatty acid ester, hydroxystearic acid, calcium stearate, and the like. Or 2 or more types can be used.

  As the ultraviolet absorber, any one usually used in cosmetics may be used. For example, 2-hydroxy-4-methoxybenzophenone, 2,4,6-trianilino-para- (carbo-2′-ethylhexyl- 1′-oxy) -1,3,5-triazine, 2,4-bis [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl)-(1 , 3,5) -triazine, 2-2′-methylene-bis- {6- (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol} and the like Benzophenone series, salicylic acid series such as 2-ethylhexyl salicylate, ethyl paradihydroxypropylbenzoate, 2- {4- (diethylamino) -2-hydroxybenzoyl} hexyl benzoate, etc. PABA, cinnamic acid such as paramethoxycinnamic acid-2-ethylhexyl, dibenzoylmethane such as 4-tert-4'-methoxydibenzoylmethane, 2-2'-methylene-bis- {6- (2H-benzo Triazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol} and the like, and one or more of them can be used.

  The aqueous component may be any component that is soluble in water, for example, lower alcohols such as ethyl alcohol and propyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol. , Glycerols such as glycerin, diglycerin, polyglycerin, plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, rose, etc., and water-soluble polymers include methylcellulose, hydroxymethylcellulose, Cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, sodium alginate, carrageenan, quince seed gum, cold Natural polymers such as gelatin, xanthan gum, locust bean gum, pectin, gellan gum, polyvinyl alcohol, carboxyl vinyl polymer, alkyl-added carboxyl vinyl polymer, polyacrylic acid soda, polymethacrylic acid soda, polyacrylic acid glycerin ester, Examples thereof include synthetic polymers such as polyvinyl pyrrolidone, and one or more of these can be used.

  The water-in-oil emulsified cosmetic of the present invention is one in which the oil agent forms the outer phase of the emulsion as a continuous phase, and can be prepared by a conventional method in combination with other components as necessary. It can be carried out in various forms such as liquid, emulsion, cream, solid, gel, and paste. The water-in-oil emulsified cosmetic of the present invention can be applied to products such as emulsions and creams, sunscreens, makeup foundations, foundations, concealers, blushers, eye shadows, lipsticks, and particularly emulsions, creams, Those used for the entire face such as sunscreen, makeup base, foundation and the like are preferred.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

Examples 1 to 13 and Comparative Examples 1 to 5: Water-in-oil type emulsified foundations Water-in-oil type emulsified foundations having the compositions shown in Tables 1 and 2 were prepared by the following production method. Each of the items of film uniformity and astaxanthin stability was evaluated and determined by the following evaluation methods and criteria, and the results are shown in Tables 1 and 2.

* 1: 20 parts of KP-540 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 80 parts of MT-500SA (manufactured by Teika) were kneaded in isopropanol and chipped.
* 2: High call K-230 (manufactured by Kaneda)
* 3: The blending amount is described in terms of pure astaxanthin.
* 4: SH200C FLUID 6CS (Toray Dow Corning)
* 5: KF-6028P (PEG-9 polydimethylsiloxyethyl dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 6: KF-6105 (Laurylpolyglyceryl-3polydimethylsiloxyethyl dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd.))
* 7: KF6019 (PEG-10 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 15 to 25 are mixed.
B: Components 1 to 14 are added to A and mixed.
C: Components 26 to 30 are mixed and dissolved.
D: C was added to A, emulsified, and filled into a container to obtain a water-in-oil emulsion foundation.

[Evaluation Method 1]
20 panelists specializing in cosmetics evaluation use the water-in-oil emulsified foundations of the examples and comparative examples described in Tables 1 and 2 to determine “goodness of elongation” and “uniformity of cosmetic film”. Each item was evaluated on a five-point scale according to the following evaluation criteria, given a score for each foundation, and the average score of all panels was determined according to the following criteria.
Evaluation criteria:
[Evaluation Result]: [Score]
Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Judgment criteria:
[Average score]: [Judgment]
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

[Evaluation Method 2]
Astaxanthin has an absorption peak at 476 nm, and it is known that the peak disappears upon decomposition. Therefore, the stability of astaxanthin was evaluated based on the findings as follows.
For the water-in-oil emulsified foundations of Examples and Comparative Examples shown in Tables 1 and 2, the absorbance at 476 nm of the supernatant obtained by centrifuging (15000 rpm, 10 minutes) and removing the powder and aqueous components was immediately after production. The stability of astaxanthin over time was evaluated by measuring each of the samples after storage at 50 ° C. for 1 month and observing the rate of decrease in absorbance. Judgment was made according to the following criteria.
Judgment criteria:
[Average score]: [Decision] 0 to 5% decrease in absorbance after 1 month at 50 ° C. with respect to immediately after production: ◎
The rate of decrease in absorbance after 1 month at 50 ° C. immediately after production is 5 to 20%: ○
The rate of decrease in absorbance after 1 month at 50 ° C. with respect to immediately after production is 20 to 50%: Δ
The rate of decrease in absorbance after 1 month at 50 ° C. with respect to immediately after production is 50 to 100%: ×

As is apparent from the results of Tables 1 and 2, the water-in-oil type emulsion foundations of Examples 1 to 13 of the present invention have “good spread”, “uniformity of cosmetic film”, “stability of astaxanthin”. It was a water-in-oil emulsified cosmetic excellent in all items.
In contrast, Comparative Example 1 in which an untreated powder was blended instead of the hydrophobized inorganic powder of component (a) was markedly inferior in “staxanthin stability”, such as a marked discoloration of astaxanthin. There was an aggregate of pigments, which was inferior in “uniformity of the decorative film”.
In Comparative Examples 2 and 3 in which a silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted to the siloxane main chain of component (b) is not blended, a part of astaxanthin is obtained from the cosmetic one month after production. It was inferior in "staxanthin stability" as it was separated into the supernatant and a fading color was observed. Furthermore, in Comparative Example 2, the elongation was heavy and the finish was uneven, and in Comparative Example 3, it was inferior in “good spread” and “uniformity of the decorative film”.
Furthermore, the comparative example 4 which did not mix | blend the silicone oil of a component (c) became unstable in an emulsified state, and the oil layer and the water layer were isolate | separated immediately after manufacture. Furthermore, in that state, all of “stability of astaxanthin”, “good spread”, and “uniformity of cosmetic film” were significantly inferior.
In Comparative Example 5 in which the triglyceride of the component (d) was not blended, astaxanthin was remarkably separated from the cosmetics, and the discoloration was also noticeable, so that “astaxanthin stability” was particularly inferior.

Example 14: Water-in-oil type emulsified base (component) (%)
1. Titanium oxide treated with zinc stearoyl glutamate (3%) 5
2. Red 226 0.15
3. Stearic acid (5%) treated yellow iron oxide 0.5
4). Methyltrimethicone 20
5. Organopolysiloxane graft polyoxyalkylene modified silicone * 8 3
6). 2-Ethylhexyl paramethoxycinnamate 5
7). Diethylaminohydroxybenzoyl hexyl benzoate 1
8). Bisethylhexyloxyphenol methoxyphenyl triazine 1
9. Glyceryl triisostearate 5
10. Astaxanthin * 3 0.005
11. Silicone composite spherical powder * 9 3
12 Methyl methacrylate cross polymer * 10 3
13. Dimethyl distearyl ammonium hectorite 1
14 Methylparaben 0.1
15. Ethyl alcohol 5
16. Glycerin 3
17. Rosemary extract 0.1
18. Purified water remaining amount 19. Perfume proper amount20. Sodium chloride 1
21. Methylenebisbenzotriazolyltetramethylbutylphenol 2
* 8: KF-6038 (Shin-Etsu Chemical Co., Ltd.)
* 9: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 10: Matsumoto Microsphere M-305 (Matsumoto Yushi Seiyaku Co., Ltd.)

(Production method)
A: Components 4 to 9 are heated to 80 ° C. and mixed and dissolved.
B: Components 1 to 3 and 10 to 13 are dispersed in A and cooled to room temperature.
C: Components 14 to 20 are mixed and dissolved.
D: Component 21 is dispersed in C.
E: D was added to B, emulsified, and filled into a container to obtain a water-in-oil base.
The water-in-oil type emulsified base of Example 14 of the present invention was excellent in all items of “goodness of spread”, “uniformity of cosmetic film”, and “stability of astaxanthin”.

Example 15: Water-in-oil type emulsion sunscreen (component) (%)
1. Isopropyl stearate triisostearate (4%)
Treated zinc oxide 20
2. Dimethylpolysiloxane * 11 15
3. Organopolysiloxane graft polyoxyalkylene modified silicone * 52
4). Isododecane 10
5. Tri (capryl / capric) glyceryl 3
6). Astaxanthin * 3 0.001
7). 2-Ethylhexyl paramethoxycinnamate 5
8). Sorbitan sesquiisostearate 0.5
9. Phospholipid 0.3
10. Phenoxyethanol 0.3
11. Ethyl alcohol 10
12 Phenylbenzimidazolesulfonic acid 2
13. Triethanolamine 1
14 Purified water remaining amount * 11: KF-96 (2CS) (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 1 to 3 are bead-milled and mixed uniformly.
B: Components 4 to 9 are mixed with A.
C: Components 10 to 14 are mixed and dissolved.
D: C was added to B and emulsified, and filled into a container to obtain a water-in-oil sunscreen.
The water-in-oil type emulsion sunscreen of Example 15 of the present invention was excellent in all items of “goodness of spread”, “uniformity of cosmetic film”, and “stability of astaxanthin”.

Example 16: Water-in-oil solid emulsion foundation (component) (%)
1. Dimethylpolysiloxane treatment (3%) Titanium oxide 12
2. Dimethylpolysiloxane treatment (3%) Bengala 1.2
3. Dimethylpolysiloxane treatment (3%) Yellow iron oxide 2.8
4). Dimethylpolysiloxane treatment (3%) Black iron oxide 0.7
5. Methylphenyl polysiloxane * 12 5
6). Organopolysiloxane grafted polyoxyalkylene modified silicone * 62
7). Decamethylcyclopentasiloxane 5
8). Cross-linked methylpolysiloxane /
Decamethylcyclopentasiloxane mixture * 13 10
9. Astaxanthin * 14 0.05
10. Isotridecyl isononanoate 5
11. Glyceryl tri-2-ethylhexanoate 10
12 2-Ethylhexyl paramethoxycinnamate 3
13. Diglyceryl diisostearate 2
14 Cetyl polyether-modified silicone * 15 4
15. Phospholipid 0.5
16. Microcrystalline wax 3
17. Carnauba wax * 16 2
18. Nylon powder 3
19. Silicone-treated mica titanium * 17 2
20. Methylparaben 0.2
21.1,3-butylene glycol 5
22. Glycerin 2
23. Purified water remaining * 12: SH556 (manufactured by Dow Corning Toray)
* 13: KSG-15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 14: Astaxanthin solution containing 5% astaxanthin * 15: ABIL EM-90 (manufactured by Goldschmidt)
* 16: Refined carnauba wax No. 1 (manufactured by Nippon Natural Products)
* 17: SA-Timilon Super Gold (manufactured by Miyoshi Kasei Kogyo Co., Ltd.)

(Production method)
A: Components 1 to 6 are roller-processed and mixed uniformly.
B: Components 10 to 17 are heated and dissolved at 90 ° C.
C: A and components 7 to 9, 18, and 19 are mixed with B.
D: Components 20 to 23 are mixed and dissolved.
E: D is added to C and emulsified.
F: E was dissolved at 80 ° C., poured into a metal pan and filled to obtain a water-in-oil solid foundation.
The water-in-oil type emulsified solid foundation of Example 16 of the present invention was excellent in all items of “goodness of spread”, “uniformity of cosmetic film”, and “stability of astaxanthin”.

Example 17: Water-in-oil emulsified blusher (component) (%)
1. Amodimethicone (3%) treated titanium oxide 3
2. Red No. 226 0.35
3. Yellow No. 4 0.3
4). Dimethylpolysiloxane (3%) treated synthetic phlogopite 3.35
5. Organopolysiloxane graft polyoxyalkylene modified silicone * 8 3
6). Di-2-ethylhexyl malate 5
7). Di-2-ethylhexanoic acid neopentyl glycol 3
8). Decamethylcyclopentasiloxane 15
9. Tripalm oil fatty acid glyceryl 5
10. Astaxanthin * 3 0.001
11. Zinc stearate (2%) treated synthetic phlogopite titanium * 185
12 Nylon powder * 19 3
13. Dimethyl distearyl ammonium hectorite 1
14 Methylparaben 0.2
15. Ethyl alcohol 5
16. Glycerin 5
17. Purified water remaining amount 18. Perfume proper amount19. Sodium chloride 0.3
* 18: Processed by HELIOS R100 (Topy Industries, Ltd.) * 19: SP-500 (Toray Industries, Inc.)

(Production method)
A: Components 1 to 6 are roller-processed and mixed uniformly.
B: Components 7 to 13 are mixed with A.
C: Components 14 to 19 are mixed and dissolved.
D: C was added to B and emulsified, and filled into a container to obtain a water-in-oil emulsified blusher.
The water-in-oil type emulsified blusher of Example 17 of the present invention was excellent in all items of “goodness of spreading”, “uniformity of cosmetic film”, and “stability of astaxanthin”.

Claims (7)

The following components (a) to (e);
(A) Hydrophobized inorganic powder 1-40% by mass
(B) 0.5-10% by mass of a silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted to the siloxane main chain
(C) Silicone oil 1-50 mass%
(D) 0.1-15 % by mass of triglyceride
(E) Astaxanthin 0.0001 to 0.1% by mass
A water-in-oil emulsified cosmetic characterized by comprising   One or two hydrophobized inorganic powders of component (a) are selected from dimethylpolysiloxane treatment, methylhydrogenpolysiloxane treatment, alkyltriethoxysilane treatment, metal soap treatment or acrylic-silicone graft copolymer treatment. The water-in-oil emulsified cosmetic according to claim 1, wherein the powder is treated with at least seeds.   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the amount of the inorganic powder not subjected to the hydrophobization treatment is 1% by mass or less. The silicone surfactant in which an organopolysiloxane group and a hydrophilic group are grafted to the siloxane main chain of the component (b) is an organopolysiloxane graft polyoxyalkylene-modified silicone or an organopolysiloxane graft polyglycerin-modified silicone. The water-in-oil emulsified cosmetic according to any one of claims 1 to 3. Water-in-oil emulsified cosmetic according to claim 1, wherein the silicone oil is a viscosity of less 20 mm 2 / ^s at 25 ° C. of component (c). The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, wherein the triglyceride of component (d) is a triglyceride that is liquid at 25 ° C. The mass ratio (d) / (e) of the blending amount of the triglyceride of the component (d) to the astaxanthin of the component (e) is 50 to 10,000, in oil according to any one of claims 1 to 6 Water-type emulsified cosmetic.