JP6690947B2 - Water-in-oil skin cosmetics - Google Patents

Description

  The present invention relates to a water-in-oil type skin cosmetic.

As a technique for improving the appearance of the skin by using a cosmetic, there are those described in Patent Documents 1 and 2.
Patent Document 1 (JP 2001-172120 A) describes a cosmetic composition such as a makeup and / or care composition containing a soft focus filler and a fatty phase having a non-volatile fraction. ing. And in such a composition in which such composition contains at least one fluorescent substance and the weight ratio of the soft focus filler to the non-volatile fraction of the fatty phase is in a specific range, the composition is more homogeneous and more uniform, and the transparency is It is said to be bright and bright, and give a bright porcelain-like skin color.

  Further, Patent Document 2 (Japanese Patent Laid-Open No. 2007-518748) provides a composition having suitable optical properties for providing both soft focus and transparency effects in one system and providing excellent skin feel. As a technique for cross-linking silicone elastomers, zinc oxide or zirconium oxide having an average particle size of less than 300 nm, small disc-shaped light-reflecting inorganic material particles having an average particle size of 10,000 to 30,000 nm, and cosmetically acceptable Cosmetic compositions containing said carrier system are described.

  Patent Document 3 (Japanese Patent Laid-Open No. 5-117127) describes that a phosphor is mixed with cosmetics. According to the document, by adding an inorganic phosphor as a phosphor to be added to a fluorescent cosmetic, light resistance and safety are significantly improved.

JP 2001-172120 A Japanese Patent Publication No. 2007-518748 JP-A-5-117127

By the way, in recent years, people's consciousness for health and aesthetics have been increasing due to environmental changes such as global warming.
Further, there is a demand for cosmetics having an excellent ultraviolet protection effect, and the required properties thereof are increasing. However, further protection effects are desired against the recent highly required properties.

When the present inventors have studied from the viewpoint of the durability of the cosmetic effect, when the cosmetic is applied and used in various environments, the skin brightness may not be sufficiently ensured after use. It became clear. It was also revealed that increasing the content of the fluorescent pigment in order to maintain the brightness of the skin gives artificial texture.
Further, there is room for improvement in the dispersibility of powders such as fluorescent pigments in cosmetics and the balance of UV protection effect.

  As a result of examination by the present inventors, dispersion of powder in cosmetics was achieved by using fluorescent zinc oxide of a specific size, an ultraviolet absorber and a non-volatile oil which is liquid at 25 ° C. in a specific ratio. In addition to its excellent properties, it provides a well-balanced effect of protecting against UV rays and the effect of obtaining natural skin brightness regardless of the environment in which it is used. For example, natural skin after being exposed to sunlight and spraying soot. It was found that a water-in-oil type skin cosmetic having excellent environmental resistance such as brightness of can be obtained.

That is, according to the present invention, the following components (A) to (C):
(A) 1 to 25% by mass of fluorescent zinc oxide having a number average particle size of 1.6 to 4 μm,
(B) 1 to 15% by mass of ultraviolet absorber, and (C) 2 to 15% by mass of non-volatile oil which is liquid at 25 ° C. other than the component (B).
A water-in-oil type skin cosmetic containing
In the water-in-oil type skin cosmetic, the mass ratio of the total content of the components (B) and (C) to the content of the component (A) (((B) + (C)) / (A)) ) Is 0.3-10, The water-in-oil type skin cosmetics are provided.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the dispersibility of the powder in cosmetics, it is excellent in the balance of the ultraviolet protection effect and the effect of obtaining natural skin brightness regardless of the use environment. You can get a fee.

The water-in-oil (W / O) type skin cosmetics in the present embodiment is a composition containing the following components (A) to (C).
(A) Fluorescent zinc oxide having a number average particle size of 1.6 to 4 μm (B) UV absorber (C) Non-volatile oil which is liquid at 25 ° C. other than the component (B)

Hereinafter, each component will be described with reference to specific examples. In addition, each component can be contained in the cosmetic alone or in combination of two or more.
In the following, the “water-in-oil type skin cosmetics” in the present embodiment will also be simply referred to as “cosmetics” as appropriate.

(Component (A))
The component (A) is fluorescent zinc oxide having a number average particle size of 1.6 to 4 μm.
More specifically, the component (A) is a phosphor powder composed of zinc oxide, and is a particle having a number average particle diameter of 1.6 to 4 μm. The fluorescent zinc oxide as the component (A) may be any one that can be used in cosmetics. As the component (A), the surface of the surface of which is known by a known method, specifically, the surface of which is hydrophobized, may be contained in the cosmetic composition.

  Surface treatment methods include silicone treatment of methylhydrogenpolysiloxane, methylpolysiloxane, etc .; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol etc .; amino acid treatment with N-acyl glutamic acid etc .; octyltriethoxysilane, octyl Examples include treatment with alkylalkoxysilane such as trimethoxysilane; treatment with lecithin; treatment with metal soap; treatment with fatty acid; treatment with alkyl phosphate. Among fluorescent zinc oxides, zinc oxide treated with silicone is preferably used.

  The number average particle diameter of the component (A) is preferably 1.6 μm or more from the viewpoint of improving environmental resistance such as natural brightness of the skin after being exposed to sunlight and spraying soot, and preferably Is 2.0 μm or more, 4 μm or less, and preferably 3.5 μm or less.

  Here, the number average particle diameter of zinc oxide is, for example, a transmission electron microscope (TEM), the maximum minor axis of 100 particles in the image is measured under the condition of 2500 magnification, It is obtained by calculating the average value per Here, the maximum shortest diameter means the shortest diameter having the largest diameter among the shortest diameters orthogonal to the longest diameter.

In addition, as the fluorescence characteristic of the component (A), when a zinc oxide thin film having a film thickness of 2 to 10.0 μm is formed and a fluorescence spectrum is measured by a spectrofluorometer, the wavelength at which the fluorescence intensity is maximum is preferably It is within the range of 400 to 700 nm, more preferably within the range of 450 to 650 nm, and even more preferably within the range of 450 to 550 nm.
Further, the excitation wavelength in the fluorescent zinc oxide of the component (A) is preferably in the ultraviolet region, more preferably in the wavelength region of 300 to 400 nm.
The evaluation of the fluorescence characteristic of the component (A) can be performed according to the method described in JP-A-10-120419, for example.

The content of the component (A) in the cosmetic is 1% by mass or more, preferably 1.5% by mass or more, and more preferably from the viewpoint of improving the ultraviolet protection effect of the cosmetic. It is 2% by mass or more and 25% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less.
From the viewpoint of improving the natural brightness of the skin, the content of the component (A) in the cosmetic is 1% by mass or more, preferably 1.0% by mass or more, based on the total amount of the cosmetic. It is preferably 5% by mass or more, more preferably 7% by mass or more, and 25% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

(Component (B))
The component (B) is an ultraviolet absorber.
As the component (B), known ones can be used, and examples thereof include salicylic acid-based ultraviolet absorbers such as homomenthyl salicylate, octyl salicylate, and triethanolamine salicylate;
2-Ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris. [4- (2-Ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (hereinafter, also referred to as “ethylhexyltriazone”. For example, Ubinal T150; manufactured by BASF), methyl bis (trimethyl) trimethoxycinnamate Siloxy) silyl isopentyl, isopropyl paracinnamate isopropyl / diisopropyl cinnamate mixture, p-methoxyhydrocinnamic acid diethanolamine salt, and other cinnamic acid-based UV absorbers;
Benzoylmethane-based UV absorption such as 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane (for example, Parasol 1789; manufactured by DSM Nutrition Japan). Agent;
Octocrylene (for example, Parasol 340; manufactured by DSM Nutrition Japan), 2-methoxyhexyl dimethoxybenzylidenedioxoimidazolidinepropionate (for example, soft shade DH; manufactured by Ajinomoto Co.), 1- (3,4-dimethoxyphenyl) -4, 4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 3- (4-methylbenzylidene) camphor, octyltriazone, hexyl diethylaminohydroxybenzoylbenzoate (for example, Ubinal Aplus; manufactured by BASF), Bisethylhexyloxyphenol methoxyphenyltriazine (for example, Tinosorb S; manufactured by BASF), methylenebisbenzotriazolyltetramethylbutylphenol (for example, Tinosorb M From BASF) can be mentioned may include one or more selected from these in cosmetics.

  Among these, 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), 2,4,6-tris [4- (2-ethylhexyl), from the viewpoint of improving the ultraviolet absorption effect of cosmetics. Oxycarbonyl) anilino] -1,3,5-triazine (for example, Ubinal T150; manufactured by BASF), 4-tert-butyl-4′-methoxydibenzoylmethane (for example, parasol 1789; manufactured by DSM Nutrition Japan), octocrylene (For example, Parasol 340; manufactured by DSM Nutrition Japan), 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (for example, soft shade DH; manufactured by Ajinomoto Co.), hexyl diethylaminohydroxybenzoyl benzoate (even For example, one selected from Ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyltriazine (for example, Tinosorb S; manufactured by BASF), and methylenebisbenzotriazolyltetramethylbutylphenol (for example, Tinosorb M; manufactured by BASF) or Two or more types are preferable, and 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,3. 5-triazine (for example, Ubinal T150; manufactured by BASF), hexyl diethylaminohydroxybenzoylbenzoate (for example, Ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyltriazine ( For example, one or more selected from Tinosorb S; manufactured by BASF) is more preferable, and it is further preferable to combine two or more thereof, and 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), Hexyl diethylaminohydroxybenzoylbenzoate (for example, Ubinal Aplus; manufactured by BASF) and bisethylhexyloxyphenol methoxyphenyltriazine (for example, Tinosorb S; manufactured by BASF) are more preferably one or more selected from two or more kinds. Even more preferred is the combination.

The content of the component (B) in the cosmetic is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass based on the total amount of the cosmetic, from the viewpoint of improving the ultraviolet protection effect of the cosmetic. % And 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.
Further, from the viewpoint of improving the natural brightness of the skin, the content of the component (B) in the cosmetic is 1% by mass or more, preferably 2% by mass or more, more preferably the total amount of the cosmetic. It is 3% by mass or more, more preferably 4% by mass or more, and 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less.

(Component (C))
The component (C) is a non-volatile oil which is liquid at 25 ° C. other than the component (B).
Here, the oil that is liquid at 25 ° C. is an oil agent having a melting point of 25 ° C. or less. That is, the component (C) is an oil agent having fluidity at 25 ° C. under 1 atm. The melting point is measured according to the third method described in the standard of cosmetic raw materials.
As the component (C), the viewpoint of improving the dispersibility of the powder, the viewpoint of improving the balance between the ultraviolet protection effect and the effect of obtaining natural skin brightness regardless of the use environment, and suppressing stickiness. From the viewpoint, the viscosity at 25 ° C. is preferably 500 mPa · s or less, more preferably 5 to 100 mPa · s, and further preferably 5 to 50 mPa · s.
The viscosity can be measured at 25 ° C. with a B-type viscometer (TOKI SANGYO VISCOMETER TVB-10M, manufactured by Toki Sangyo Co., Ltd.) and a rotor 1 under the conditions of 60 rpm and 1 minute.

Further, the non-volatile oil refers to one having an evaporation amount of less than 20% at 25 ° C. for 6 hours, which is measured by the following method.
That is, a 90 mm diameter filter paper is placed in a glass dish having a diameter of 120 mm, 1 g of the sample is placed on the filter paper, and the sample is stored in a 65% RH room (25 ° C.). Then, the residue of the sample after 6 hours is measured, and the evaporation amount is calculated.

  Specific examples of the component (C) are non-volatile oils other than the component (B) that are liquid at 25 ° C., such as ester oil, silicone oil, hydrocarbon oil, higher fatty acid having 12 to 22 carbon atoms, and carbon number. 12 to 22 higher alcohols may be mentioned.

  Among these, specific examples of the ester oil as the component (C) include isononyl isononanoate, isotridecyl isononanoate, octyldodecyl myristate, isopropyl myristate, isocetyl myristate, glyceryl tri-2-ethylhexanoate, di-2-sebacate. Ethylhexyl, diisopropyl sebacate, glyceryl tri (caprylic / capric acid), diisostearyl malate, alkyl benzoates such as alkyl benzoate (C12-C15), diethylene glycol dicaprate, neopentyl glycol dicaprate, di2-ethyl. One or more selected from the group consisting of neopentyl glycol hexanoate, isopropyl palmitate, ethylhexyl palmitate and 2-hexyldecyl palmitate may be mentioned. That.

  Further, as an ester oil as the component (C), it is contained in the cosmetic together with the components (A) and (B), and from the viewpoint of improving the ultraviolet protection effect and the natural brightness of the skin, it has 12 to 18 carbon atoms. Monoester of fatty acid and branched alcohol having 14 to 22 carbon atoms, triester of branched fatty acid having 6 to 18 carbon atoms and glycerin, diester of dicarboxylic acid having 2 to 18 carbon atoms and branched alcohol having 2 to 18 carbon atoms , Alkyl benzoate (C12-C15) (for example, Finsolve TN; manufactured by Innospec Active Chemicals LLC) and the like are preferable, and specifically, octyldodecyl myristate, isocetyl myristate, glyceryl tri-2-ethylhexanoate, diisopropyl sebacate, Di-2-ethylhexyl sebacate, neopentyl glycol di2-ethylhexanoate, dica One or more selected from neopentyl glycol phosphate, alkyl benzoate (C12 to C15), and diisostearyl malate are more preferable, and in addition to the above viewpoints, compatibility with ultraviolet absorbers in cosmetics From the viewpoint of improving the UV protection effect and improving the ultraviolet protection effect, one or more selected from neopentyl glycol dicaprate and alkyl benzoate (C12 to C15) are more preferable.

In addition, since the cosmetic contains silicone oil as the component (C), excellent dispersibility of the powder in the cosmetic, an effect of protecting ultraviolet rays, and an effect of obtaining natural skin brightness regardless of the use environment It is possible to further improve the balance with and the non-stickiness.
As a specific example of the silicone oil as the component (C), dimethylpolysiloxane is preferable from the same viewpoint, and dimethylpolysiloxane having a viscosity at 25 ° C. of 20 mPa · s or less is more preferable.

  Examples of the hydrocarbon oil as the component (C) include liquid paraffin, liquid isoparaffin such as hydrogenated polyisobutene, heavy liquid isoparaffin, liquid ozokerite, squalane, pristane, squalene and isohexadecane, and preferably isohexadecane and liquid isoparaffin. It is one or more selected from, and more preferably one or more selected from branched aliphatic hydrocarbon oils such as isohexadecane and hydrogenated polyisobutene.

  Examples of the higher fatty acid having 12 to 22 carbon atoms as the component (C) include a nonvolatile fatty acid having 12 to 22 carbon atoms and being liquid at 25 ° C. More specifically, oleic acid and isostearine. Acid, linoleic acid, and linoleic acid are mentioned.

Examples of the higher alcohol having 12 to 22 carbon atoms as the component (C) include oleyl alcohol, 2-decyltetradecinol, dodecanol, isostearyl alcohol, and octyldodecanol.
Further, the component (C) may be a naturally-derived one such as olive oil.

  Further, it is contained in the cosmetic together with the components (A) and (B) to enhance the UV protection effect and enhance the environmental resistance such as the natural brightness of the skin after being exposed to sunlight and after being sprayed with soot. From the viewpoint, the component (C) preferably contains one or more non-volatile oils which are liquid at 25 ° C. selected from ester oils, hydrocarbon oils and silicone oils, and more preferably benzoic acid. It contains one or more selected from the group consisting of alkyl (C12-15), neopentyl glycol dicaprate, isohexadecane, hydrogenated polyisobutene and dimethylpolysiloxane.

The content of the component (C) in the cosmetic is 2% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass based on the total amount of the cosmetic, from the viewpoint of improving the ultraviolet protection effect of the cosmetic. % And 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less.
Further, from the viewpoint of improving the natural brightness of the skin, the content of the component (C) in the cosmetic is 2 mass% or more, preferably 3 mass% or more, and more preferably the mass of the cosmetic. It is 5% by mass or more and 15% by mass or less, preferably 10% by mass or less, and more preferably 7% by mass or less.

In addition, the total content ((B) + (C)) of the components (B) and (C) in the cosmetic is preferably from the viewpoint of improving the ultraviolet protection effect of the cosmetic, with respect to the entire cosmetic. 3% by mass or more, more preferably 10% by mass or more, further preferably 12% by mass or more, and preferably 20% by mass or less, more preferably 19% by mass or less, further preferably 17% by mass. It is the following.
From the viewpoint of improving the natural brightness of the skin, the total content ((B) + (C)) of the components (B) and (C) in the cosmetic is preferably based on the total amount of the cosmetic. 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, even more preferably 9% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. % Or less, more preferably 10% by mass or less.

In the cosmetic, the mass ratio (((B) + (C)) / (A)) of the total content of the components (B) and (C) to the content of the component (A) is From the viewpoint of improving the ultraviolet protection effect, it is 0.3 or more, preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and 10 or less, preferably 8 or less.
From the viewpoint of improving the natural brightness of the skin, the total mass ratio of the contents of the components (B) and (C) to the content of the component (A) in the cosmetic (((B) + (C )) / (A)) is 0.3 or more, preferably 0.5 or more, more preferably 0.7 or more, and 10 or less, preferably 5 or less, more preferably 3 or less. , And more preferably 1.5 or less.

  In the present embodiment, the water-in-oil type skin cosmetic contains a specific amount of components (A) to (C), and more specifically, the specific size of the component (A) is fluorescent. It contains zinc oxide, an ultraviolet absorber of component (B) and a non-volatile oil which is liquid at 25 ° C. of component (C) in a specific ratio. With such components and proportions, the cosmetic material according to the present embodiment has an excellent ultraviolet protection effect as well as a soft focus effect by fluorescence. For this reason, it is excellent in environmental resistance such as being able to maintain the natural brightness of the skin even after being exposed to sunlight and the natural brightness of the skin after being sprayed with soot. In addition, the cosmetic of the present embodiment has excellent dispersibility of the powder in the cosmetic.

In the present embodiment, the cosmetic may contain components other than the above-mentioned components (A) to (C).
For example, the cosmetic in the present embodiment may contain water, and the content of water can be the balance excluding components other than water in the cosmetic. The content of water in the cosmetic is preferably less than 50% by mass, more preferably 43% by mass or less, based on the total amount of the cosmetic.

Further, in the present embodiment, the cosmetic preferably further contains a film-forming polymer (component (D)) from the viewpoint of enhancing the ultraviolet protection effect and the effect of maintaining natural skin brightness.
The film-forming polymer as the component (D) is one having film-forming properties when dried. When the cosmetic contains a film-forming polymer, for example, it is possible to form a film on the surface of the skin, so that the UV protection effect and the natural skin brightness can be maintained, and the environmental resistance is further enhanced. be able to.

  Specific examples of the component (D) include N-acylalkylenes such as poly (N-formylethyleneimine) organopolysiloxane, poly (N-acetylethyleneimine) organopolysiloxane, poly (N-propionylethyleneimine) organopolysiloxane. Polymers having a hydrophilic segment having an imine as a repeating unit and an organopolysiloxane segment as structural units; polyvinylpyrrolidone / hexadecene copolymer such as antalon V-216 (manufactured by ISP); antalon V-220 (manufactured by ISP) Polyvinylpyrrolidone / eicosene copolymer; tricontanyl PVP such as Antalon WP-660 (manufactured by ISP); U. R. Polyurethane-1 such as (manufactured by BASF); Polyurethane-1 such as Bicusan C1000 and C1001 (manufactured by Bayer MaterialScience); Polyurethane-32 such as Bicusan 1003 (manufactured by Bayer MaterialScience); Bicusan 1004 (manufactured by Bayer MaterialScience) Polyurethane-35 such as)); polyvinyl caprolactam such as rubiscol plus (manufactured by BASF); alkyl acrylate copolymers such as Rubimer 100P and 30E (above, manufactured by BASF).

  Among the above film-forming polymers, from the viewpoint of enhancing the ultraviolet protection effect and the effect of maintaining the natural skin brightness, a hydrophilic segment containing N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as constituent units. The polymer, polyvinylpyrrolidone / hexadecene copolymer, polyvinylpyrrolidone / eicosene copolymer, and one or more selected from the group consisting of tricontanyl PVP are preferable.

  Among them, a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a structural unit is preferable from the viewpoint of enhancing the ultraviolet protection effect and the effect of improving natural skin brightness.

Hereinafter, the structure of a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a structural unit will be described more specifically.
In a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a constituent unit, the mass ratio of the organopolysiloxane segment to the hydrophilic segment having N-acylalkyleneimine as a repeating unit ( The organopolysiloxane segment a / hydrophilic segment b) having N-acylalkyleneimine as a repeating unit is, for example, a / b = from the viewpoint of improving the balance between the durability of the ultraviolet protection effect of the cosmetic and the suppression of stickiness. 45/55 or more, preferably 65/35 or more, more preferably 85/15 or more, and for example 94/6 or less, preferably 92/8 or less, more preferably 90/10 or less. .
Specific examples of the polymer having such a mass ratio include those represented by the general formula (4) described later.

In a polymer having a hydrophilic segment having an N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a constituent unit, the weight average molecular weight of the organopolysiloxane segment improves the durability of the UV protection effect of cosmetics. From the viewpoint of suppressing stickiness, improving the spreadability of cosmetics, and improving the compatibility with ultraviolet absorbers, for example, 1 × 10 ⁴ or more, preferably 2 × 10 ⁴ or more, and further It is preferably 3.5 × 10 ⁴ or more, and for example, 3 × 10 ⁵ or less, preferably 2 × 10 ⁵ or less, more preferably 1.5 × 10 ⁵ or less.
The weight average molecular weight of the organopolysiloxane segment is measured by gel permeation chromatography (GPC) according to the method described in JP2009-256367A.

Further, in a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a constituent unit, the number average molecular weight of the poly (N-acylalkyleneimine) segment is From the viewpoints of improving the sustainability of effects, suppressing stickiness, improving the spreadability of cosmetics, increasing compatibility with UV absorbers, and flexibility of cosmetic film and dissolution in solvent From the viewpoint of enhancing the property, it is, for example, 5 × 10 ² or more, preferably 7 × 10 ² or more, more preferably 8 × 10 ² or more, and, for example, 4 × 10 ³ or less, preferably 3.5. It is not more than × 10 ³ , and more preferably not more than 3 × 10 ³ .
The number average molecular weight of the poly (N-acylalkyleneimine) segment can be measured by the method calculated from the molecular weight of the N-acylalkyleneimine unit and the degree of polymerization, or by the GPC measurement method described above. In the form, it refers to the number average molecular weight measured by the GPC measurement method.

  Specific examples of the polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a structural unit include those represented by the following general formula (4).

(In the general formula (4), w represents a number of 1 to 5, R ²¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, v represents the degree of polymerization of the monomer, and is 1 to 1000. Z3 represents an average of 10 to 2000, z1 represents an average of 0 to 20, z2 represents an average of 1 to 20, X ⁻ represents a counter ion of a quaternary ammonium ion, ethyl sulfate ion, and methyl ion. A sulfate ion, a chloride ion, an iodine ion, a sulfate ion, a p-toluenesulfonate ion, or a perchlorate ion is shown, in which a polymerization initiator residue is bonded to the N terminal of the repeating unit of N-acylalkyleneimine. .)

  As a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as a constituent unit, an N-propionyl polyethyleneimine / methylpolysiloxane copolymer is preferable. As the N-propionyl polyethyleneimine / methyl polysiloxane copolymer, for example, those described in JP2009-256367A can be included. The properties of the N-propionyl polyethyleneimine / methyl polysiloxane copolymer are also measured according to the description of the publication.

  The content of the component (D) in the cosmetic is preferably 0.1 mass with respect to the total amount of the cosmetic, from the viewpoint of improving the ultraviolet protection effect of the cosmetic and improving the brightness of natural skin. % Or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, preferably 2% by mass or less, more preferably 1.5% by mass or less, further preferably Is 1 mass% or less.

Further, in the present embodiment, from the viewpoint of improving the dispersibility of powder in the cosmetic and improving the brightness of natural skin, the cosmetic preferably further contains a surfactant as the component (E). .
As the surfactant of component (E), known anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be contained, but they improve the dispersibility of powder in cosmetics. From the viewpoint and from the viewpoint of improving environment resistance such as natural skin brightness after spraying soot, it is preferable to contain a nonionic surfactant.

As the nonionic surfactant, for example, ethylene glycol fatty acid ester such as ethylene glycol monostearate ester;
Polyethylene glycol (2) polyethylene glycol fatty acid ester such as monostearate ester;
Polyethylene glycol (5) polyethylene glycol alkyl ether such as decyl pentadecyl ether;
Polyethylene glycol (5) hydrogenated castor oil polyethylene glycol hydrogenated castor oil such as monoisolaurate;
Propylene glycol fatty acid ester;
Monoglycerin monofatty acid ester such as glycerin monoisostearate;
Monoglycerin difatty acid esters such as glycerin distearate, glycerin dilaurate, etc .;
Glycerin alkyl ether such as glycerin monoisostearyl ether;
Sorbitan fatty acid esters such as sorbitan monostearate and sorbitan oleate;
Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan oleate;
Fatty acid alkanolamides;
Of fatty acid dialkanolamides such as lauric acid diethanolamide, monofatty acid glyceryl ethers such as stearyl glyceryl ether, and silicone-based surfactants, excluding the non-volatile silicone oil which is liquid at 25 ° C. of the aforementioned component (C) And so on.

  The component (E) is preferably a sorbitan fatty acid from the viewpoint of improving the dispersibility of the powder in the cosmetic and from the viewpoint of improving environmental resistance such as natural skin brightness after spraying soot. Containing one or more selected from the group consisting of ester and polyoxyethylene sorbitan fatty acid ester, more preferably sorbitan monostearate, sorbitan oleate, polyoxyethylene sorbitan monostearate and polyoxyethylene oleate. It includes one or more selected from the group consisting of sorbitan.

Further, from the viewpoint of improving the dispersibility of the powder in the cosmetic and the environment resistance such as the natural brightness of the skin after spraying soot, the component (E) is a silicone-based surfactant. It is also preferable to include an agent.
As a specific example of the silicone-based surfactant, among the polyether-modified silicones represented by the following general formulas (1) to (3), the above-mentioned component (C), a non-volatile silicone oil which is liquid at 25 ° C., is used. Excludes things.

(In the general formula (1), R ¹ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ² represents a formula — (CH ₂ ) _r —O— (C ₂ H ₄ O) _s — (C ₃ H ₆ O) _t -R ⁵ (R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, r is a number of 1 to 5, s is a number of 1 to 50, and t is a number of 0 to 30. .), R ³ and R ⁴ represent the same group as any one of R ^{1 and} R ² , and p represents a number of 5 to 300 and q represents a number of 1 to 50. However, not all R ¹ will be phenyl groups.)

(In the general formula (2), R ¹ , R ² , p and q are the same as R ¹ , R ² , p and q in the general formula (1), respectively, and R ⁶ has 2 to 2 carbon atoms. 20 represents an alkyl group, R ⁷ and R ⁸ represent the same group as any one of R ¹ , R ^{2 and} R ⁶ , and u represents a number of 1 to 30, provided that all of R ¹ are It does not become a phenyl group.)

(In the formula (3), R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents a formula —Q ¹ —O— (C ₂ H ₄ O) _x — (C ₃ H ₆ O) _y R ¹⁴ (Q ¹ is a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁴ is a hydrogen atom, an alkyl group or an acetyl group having 1 to 4 carbon atoms, x is a number of 1 or more, and y is a number of 0 or more. R ¹¹ is a group represented by the formula: —Q ² —O—R ¹⁵ (Q ² is a hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁵ is a hydrocarbon group having 8 to 30 carbon atoms. R ¹² and R ¹³ are the same groups as any one of R ⁹ , R ¹⁰ or R ¹¹ , α is a number of 0 or more, and β and γ are independent. And indicates a number of 1 or more.)

  The polyether-modified silicones represented by the general formulas (1) to (3) may have a branched structure in the silicone chain or a functional group other than polyether depending on the effect required for cosmetics. It may be co-modified.

Examples of the compound represented by the general formula (1) include KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH-3772C (manufactured by Toray Dow Corning) and SH-3775M (manufactured by Toray Dow Corning). To be
The compound represented by the general formula (2) is referred to as an alkyl polyether-modified silicone, and examples thereof include Abil WE-09 (manufactured by Gold Schmidt) and KF6038 (manufactured by Shin-Etsu Silicone).
The compound represented by the general formula (3) is referred to as polyoxyalkylene alkyl ether co-modified organopolysiloxane, and for example, methyl hydrogen polysiloxane is co-modified with polyoxyalkylene allyl ether and allyl alkyl ether. By doing so, it can be easily manufactured.

  Among these silicone-based surfactants, the polyether-modified silicone represented by the general formula (1) is preferable from the viewpoint of improving the dispersibility of the powder in the cosmetic and the feel when the cosmetic is applied.

  The content of the component (E) in the cosmetic is from the viewpoint of improving the dispersibility of the powder in the cosmetic, and from the viewpoint of improving environmental resistance such as natural skin brightness after spraying soot. Therefore, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and preferably 2% by mass or less, based on the entire cosmetic. Yes, more preferably 1.5% by mass or less, further preferably 1.2% by mass or less.

In addition, from the viewpoint of improving the dispersibility of powder, improving the balance between the ultraviolet protection effect and the effect of obtaining natural skin brightness regardless of the environment of use, and the dry feeling of the part to which the cosmetic is applied. From the viewpoint of increasing the level, it is preferable that the cosmetic further contains, as the component (F), a volatile oil that is liquid at 25 ° C. other than the component (B).
Component (F) is preferably a volatile silicone oil, more preferably a linear or cyclic organopolysiloxane which is liquid at 25 ° C. and is volatile.
Here, the volatile oil means an oil having an evaporation amount of 20% or more at 25 ° C. for 6 hours, which is measured by the following method.
That is, a 90 mm diameter filter paper is placed in a glass dish having a diameter of 120 mm, 1 g of the sample is placed on the filter paper, and the sample is stored in a 65% RH room (25 ° C.). Then, the residue of the sample after 6 hours is measured, and the evaporation amount is calculated.

  Among the volatile silicone oils, specific examples of linear organopolysiloxanes include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1,1,1,3,5,5,5-heptamethyl- 3-[(trimethylsilyl) oxy] -trisiloxane may be mentioned.

  Among the volatile silicone oils, examples of the cyclic organopolysiloxane include 4- to 6-membered cyclic siloxanes having an alkyl group having 1 to 5 carbon atoms as a substituent, and specific examples thereof include octamethylcyclotetrasiloxane. Examples thereof include decamethylcyclopentasiloxane.

  As specific examples of commercially available volatile silicone oils, volatile silicones include KF-96A-1cs (Shin-Etsu Chemical Co., Ltd., octamethyltrisiloxane), KF-96A-1.5cs (Shin-Etsu Chemical Co., Ltd., Decamethyltetrasiloxane), KF-96A-2cs (Shin-Etsu Chemical Co., Ltd., dodecamethylpentasiloxane), KF-995 (Shin-Etsu Chemical Co., Ltd., decamethylcyclopentasiloxane), TMF-1.5 (Shin-Etsu Chemical Co., Ltd.) 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl) oxy] -trisiloxane), SH200C Fluid 1cs (Toray Dow Corning octamethyltrisiloxane), SH200C Fluid 1.5cs (Toray Dow Corning decamethyltetrasiloxane), S 200C Fluid 2cs (Toray Dow Corning, dodecamethylpentasiloxane), SH245 Fluid (Toray Dow Corning, decamethylcyclopentasiloxane), TSF405A (Momentive Performance Materials, decamethylcyclopentasiloxane) ) Is mentioned.

  The content of the component (F) in the cosmetic is from the viewpoint of improving the dispersibility of the powder in the cosmetic, and from the viewpoint of improving environmental resistance such as natural skin brightness after spraying soot. Therefore, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 70% by mass, based on the whole cosmetic. % Or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

  In addition, the cosmetic of the present embodiment includes components other than the components described above, for example, an ultraviolet light scattering agent, an oily component other than components (B), (C) and (F), a fragrance, a moisturizer, an antiperspirant, Among the components used in cosmetic ingredients, medicinal ingredients, oil gelling agents, bactericides, pH adjusters, antioxidants, preservatives, alcohols having 1 to 5 carbon atoms and other ordinary cosmetics, those mentioned above Other than the above may be contained. In addition, these components are not limited to the use as each agent, but may be used for other purposes depending on the purpose, for example, a perfume as an antiperspirant.

For example, in the present embodiment, from the viewpoint of further enhancing the ultraviolet protection effect of the cosmetic, an ultraviolet scattering agent may be contained, and preferably an ultraviolet scattering agent composed of an inorganic powder may be contained. Further, two or more kinds of ultraviolet scattering agents may be used in combination.
Examples of the material of the ultraviolet scattering agent include titanium oxide, zinc oxide other than the component (A), iron oxide, zirconium oxide, aluminum oxide and the like. Further, examples of the ultraviolet scattering agent include fine particles of these materials and composite materials. The ultraviolet scattering agent preferably contains one kind or two or more kinds selected from titanium oxide and zinc oxide other than the component (A).

  The titanium oxide and zinc oxide used as the ultraviolet scattering agent may be titanium oxide and zinc oxide usually used in cosmetics. It is preferable that the cosmetic composition has a more excellent dispersibility, for example, a surface of which is subjected to a surface treatment by a known method, specifically, a hydrophobic treatment if necessary.

  Surface treatment methods include silicone treatment of methylhydrogenpolysiloxane, methylpolysiloxane, etc .; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol etc .; amino acid treatment with N-acyl glutamic acid etc .; octyltriethoxysilane, octyl Examples include treatment with alkylalkoxysilane such as trimethoxysilane; treatment with lecithin; treatment with metal soap; treatment with fatty acid; treatment with alkyl phosphate. Among them, zinc oxide whose surface is treated with silicone is preferably used.

  The silicone used for the surface treatment is not limited, and examples thereof include methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and octadecamethylcyclohexasiloxane. Methyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (Polyoxypropylene) siloxane copolymer, dimethyl siloxane / methyl cetyloxy siloxane copolymer, dimethyl siloxane It can include various silicone oils such as pulse stearoyl carboxymethyl copolymer. Preferred are methyl hydrogen polysiloxane and methyl polysiloxane.

  As the zinc oxide, a commercially available product may be used, and if a specific example is shown, FINEX-50-LPTM (dimethicone treatment, Sakai Chemical Industry Co., Ltd.), MZ-300 (no surface treatment, Teika Co., Ltd.), MZ- 504R3M (hydrogen dimethicone treatment, manufactured by Teika), MZY-303S (hydrogen dimethicone treatment, manufactured by Teika), MZ-306X (triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone treatment, manufactured by Teika), MZ-200 (surface treatment). None, manufactured by Teika), MZY-203S (hydrogen dimethicone treatment, manufactured by Teika), MZ-150 (no surface treatment, manufactured by Teika), MZY-153S (hydrogen dimethicone treated, manufactured by Teika), FINEX-25 ( No surface treatment, Sakai Chemical Industry Co., Ltd., FINEX-25LP (Jime Con treatment, and manufactured by Sakai Chemical Industry Co., Ltd.) and the like. However, it is not limited to these examples.

  As the titanium oxide, a commercially available product may be used, and if a specific example is shown, fine particle titanium oxide MT-100TV (alumina, stearic acid treatment, manufactured by Teika), fine particle titanium oxide MTY-110M3S (alumina, silica, Hydrogen dimethicone treatment, manufactured by Teika) and the like.

  Further, when the titanium oxide or zinc oxide is in the form of particles, the number average particle diameter is, for example, 1 nm or more, preferably 5 nm or more, more preferably 8 nm or more, further preferably 10 nm or more. Further, it is, for example, 500 nm or less, preferably 300 nm or less, more preferably 100 nm or less, and further preferably 60 nm or less.

  Here, the number average particle diameter of titanium oxide or zinc oxide is, for example, a transmission electron microscope (TEM), and the maximum short diameter of 300 particles in an image is measured under a condition of 50,000 magnification. Then, it is obtained by calculating the average value per number. Here, the maximum shortest diameter means the shortest diameter having the largest diameter among the shortest diameters orthogonal to the longest diameter. For example, the number average particle diameter of MZ-504R3M measured by such a method is about 25 nm, and the number average particle diameter of particulate titanium oxide MT-100TV measured by such a method is about 15 nm.

The total content of titanium oxide, the component (A) and the other zinc oxide in the cosmetic composition improves the dispersibility of the powder in the cosmetic composition, suppresses the skin from becoming too white, and the cosmetic composition. From the viewpoint of reducing the oiliness of the cosmetic, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 18% by mass or less, based on the whole cosmetic. Is.
Further, from the viewpoint of improving the ultraviolet protection effect of the cosmetic, the total content of titanium oxide, component (A) and other zinc oxide in the cosmetic is preferably 5% by mass or more with respect to the entire cosmetic. Yes, and more preferably 9% by mass or more. Further, from the viewpoint of obtaining the brightness of the skin, especially the brightness of the natural skin, it is preferably 20% by mass or less, and more preferably 15% by mass or less.
Further, from the viewpoint of obtaining natural skin brightness, the content of iron oxide in the cosmetic is preferably 3% or less, preferably 1% or less, more preferably 0.5% or less, and substantially 0%. More preferable.

Specific examples of oily components other than the components (B), (C) and (F) include solid alcohols having 12 to 22 carbon atoms such as cetanol, stearyl alcohol and behenyl alcohol at 25 ° C. and other 25 ° C. Solid oil agents can be mentioned.
Here, the solid oil agent at 25 ° C. means an oil agent having a melting point higher than 25 ° C. The melting point is measured according to the third method described in the standard of cosmetic raw materials.

  Specific examples of the moisturizer include glycerin, 1,3-butylene glycol, hyaluronic acid and salts thereof.

Ethanol is preferred as the alcohol having 1 to 5 carbon atoms from the viewpoint of improving the dispersibility of the powder in the cosmetic.
The content of the alcohol having 1 to 5 carbon atoms in the cosmetic is preferably 1 to 20% by mass and more preferably the total amount of the cosmetic from the viewpoint of improving the dispersibility of the powder in the cosmetic. Is 2 to 15% by mass, more preferably 3 to 12% by mass.

Moreover, the cosmetics in the present embodiment may include powders other than the above-mentioned components, and specific examples thereof include inorganic powders and resin powders.
Specific examples of the material of the inorganic powder include silica, phlogopite, mica, composite powder of titanium oxide and mica, talc, borosilicate (Ca / Al), and the like.
Specific examples of the resin powder material include silicone resins such as (vinyl dimethicone / methicone silsesquioxane) crosspolymer.

The cosmetic according to the present embodiment can be manufactured according to a conventional method for manufacturing a water-in-oil type emulsion cosmetic.
Specifically, the cosmetic according to this embodiment is obtained by the following procedure. That is, the components (B) and (C) and other oily components are appropriately mixed at a temperature of about 80 ° C. to prepare an oil phase. Subsequently, the component (A) and the appropriate component (D) are added to the oil phase and mixed well. On the other hand, water and other aqueous components are appropriately added and mixed to prepare an aqueous phase. A cosmetic is obtained by adding the aqueous phase to the oil phase and stirring.
Note that some of the component (B) may be solid as a simple substance, but in the cosmetic of the present embodiment, it is considered that the component (B) is in a liquid state by being heated, for example, in the manufacturing process.

  Further, the cosmetics obtained by the present embodiment include makeup bases, sunscreen cosmetics such as sunscreen cream, and the like. The dosage form may be, for example, emulsions, creams and the like.

In the present embodiment, the specific components (A) to (C) are contained in a specific amount, and the mass ratio (((B) + (C)) / (A)) is set in a specific range, so that makeup Excellent dispersibility of the powder in the powder, and a good balance between the UV protection effect and the effect of obtaining natural skin brightness regardless of the environment of use. For example, after soaking in the sun and spraying soot It is possible to obtain a water-in-oil type skin cosmetic having excellent environment resistance such as natural skin brightness after application.
Therefore, by using the cosmetic of the present embodiment, for example, it is possible to give the skin a natural brightness and effectively protect the skin from ultraviolet rays.
In addition, by using the cosmetic of the present embodiment, it becomes possible to suppress the stickiness of the skin, for example.
In addition, the cosmetic material according to the present embodiment can be configured to have excellent redispersibility of the powder component, for example, excellent dispersibility of the powder after storage at a low temperature of about 5 ° C. Therefore, for example, the uneven distribution of the components in the cosmetic applied to the skin is suppressed, and it is possible to stably improve the ultraviolet protection effect and the natural skin brightness improving effect.

  The cosmetic of the present embodiment can be used by applying, preferably applying to the skin, especially the skin excluding the hair, preferably the face, body, limbs and the like. For example, by applying, preferably applying, the cosmetic of the present embodiment to the skin, it is possible to protect the ultraviolet rays while giving the skin a natural and preferable brightness, and it is also possible to suppress the stickiness of the skin. Become.

  Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Production Example 1 (Production 1 of N-propionyl polyethyleneimine / methyl polysiloxane copolymer)
Poly (N-propionylethyleneimine) having a number average molecular weight of 2700 was obtained from 0.8 g (0.005 mol) of diethyl sulfate, 12.8 g (0.14 mol) of 2-ethyl-2-oxazoline, and 29 g of dehydrated ethyl acetate. Obtained. Further, 100 g of a side chain primary aminopropyl modified polydimethylsiloxane (weight average molecular weight 100,000, amine equivalent 20,000) was used to prepare an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (111 g, yield 98). %). The content of the organopolysiloxane segment in the final product was 88% by mass (a / b = 88/12), and the weight average molecular weight of the organopolysiloxane was 114,000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained.

  In the following examples, according to the amount of components contained in the raw material, each raw material is blended so that the content of each component in the resulting composition is as described in each table, and water-in-oil skin A cosmetic composition was obtained.

(Examples 1 to 6 and Comparative Examples 1 to 6)
The water-in-oil type skin cosmetics having the compositions shown in Tables 1 and 2 were produced by the method described below, and the method described below was applied to the skin after exposure to sunlight for 1 hour as a UV protection effect and environment resistance test. The appearance, the appearance of the skin after spraying soot, and the dispersibility of the powder were evaluated. The results are also shown in Tables 1 and 2.

(Method of manufacturing cosmetics)
At a temperature of 80 ° C., the components (B), (C), (E) and other oily components were appropriately added and mixed to prepare an oil phase. Then, the component (A) and an appropriate component (D) were added to the oil phase and mixed well. On the other hand, water and other appropriate aqueous components were added and mixed to prepare an aqueous phase. The water phase thus obtained was added to the oil phase and stirred to obtain the water-in-oil type skin cosmetics described in each table.

(Evaluation methods)
(UV protection effect)
28.5 mg of each cosmetic was uniformly applied to a size of 5 cm × 5 cm of a polymethylmethacrylate (PMMA) plate (Helioplate HD6, manufactured by Helioscreen; roughness 6 μm), and dried in a dark room for 30 minutes. Then, the transmittance at a wavelength of 300 nm was measured with UV-2000S (manufactured by Labsphere). Three plates were measured for one cosmetic, and the average transmittance was calculated at 15 points on each plate, totaling 15 points, and evaluated according to the following criteria.
5: Average transmittance less than 10% 4: Average transmittance 10% or more, less than 20% 3: Average transmittance 20% or more, less than 30% 2: Average transmittance 30% or more, less than 50% 1: Average transmittance 50 %that's all

(Environmental resistance test: How the skin looks after being exposed to sunlight for 1 hour)
Five professional panelists applied 50 mg of the cosmetic material obtained in each example to the size of 5 cm × 5 cm on their forearms and dried for 15 minutes. Then, the appearance of the skin after exposing the arm to sunlight for 1 hour was evaluated on a scale of 5 with 5 being a very bright skin color and 1 being a very dark skin color. The average of 5 professional panelists was calculated, and the value rounded to the first decimal place was used for evaluation.

(Environmental resistance test: Natural appearance of skin after spraying soot)
40 mg of the cosmetic material obtained in each example was uniformly applied to 5 cm × 4 cm white artificial leather and dried until the next day. After that, the artificial leather was placed in a closed dirt chamber, and the appearance of the artificial leather after spraying soot by burning the filter paper was evaluated by the following criteria by five expert panelists. For each evaluation, 3 pieces of artificial leather were used for each cosmetic, the average of 5 professional panelists was calculated, and the value rounded to the first decimal place was used for the evaluation.
3: There is no change before and after spraying soot 2: It looks slightly dark after spraying soot 1: It looks very dark after spraying soot

(Powder dispersibility)
50 g of the cosmetic material obtained in each example and one stirring ball having a diameter of 5 mm were placed in a glass bottle (wide-mouth standard bottle, PS-No. 6, manufactured by Tokyo Glass Co., Ltd.) and stored at 5 ° C. for 1 month. After storage, one professional panelist holds the glass bottle by hand so that the long axis of the glass bottle is vertical to the ground, shakes it at a height of 30 cm up and down once a second, and then visually. The evaluation was performed according to the following criteria.
The powder is evenly dispersed by shaking less than 3:10 times. The powder is uniformly dispersed by shaking 2:10 times or more and the shaking less than 20 times. Disperse, or the powder is not evenly dispersed

Details of the components described in Table 1 and Table 2 are shown below.
* 1 Silicone-treated fluorescent zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd. (number average particle size 2.5 μm)
* 2-Ethylhexyl paramethoxycinnamate: BASF, Ubinal MC80
* 3 Alkyl benzoate (C12-15): Finnosolv TN, manufactured by Innospec Active Chemicals LLC
* 4 Silicone-treated zinc oxide: MZ-504R3M (number average particle diameter 25 nm) manufactured by Teika.
* 5 Polyoxyethylene / methylpolysiloxane copolymer: Silicone SH3775M, manufactured by Toray Dow Corning
* 6 Decamethylcyclopentasiloxane: Silicone TSF405A manufactured by Momentive Performance Materials Japan, Inc.

  From Table 1 and Table 2, the cosmetics of each Example include the components (A) to (C) in a specific amount, and the mass ratio (((B) + (C)) / (A)) is specific. Since it is in the range, it has excellent dispersibility of powder after storing at 5 ° C and ultraviolet ray protection effect, and also has a natural skin after being exposed to sunlight for 1 hour and soot. It was excellent in environment resistance such as brightness, and was excellent in balance of each effect as compared with those of each comparative example.

(Prescription examples 1 to 3)
Table 3 shows a prescription example of the water-in-oil type skin cosmetic.

Details of components other than those described above among the components shown in Table 3 are shown below.
* 7 Hexyl diethylaminohydroxybenzoyl benzoate: BASF, Ubinal A Plus
* 8 Ethylhexyltriazone: BASF, Ubinal T-150
* 9 Bisethylhexyloxyphenol methoxyphenyl triazine: BASF, Tinosorb S
* 10 Neopentyl glycol dicaprate: Nisshin Oillio Group, Estemol N-01
* 11 Hydrogenated polyisobutene: Pearl Oil EX manufactured by NOF Corporation
* 12 Dimethyl polysiloxane: manufactured by Shin-Etsu Chemical Co., Ltd., Silicone KF-96A-6CS.
* 13 Silicone-treated titanium oxide: SI-Titanium CR50 manufactured by Ishihara Sangyo Kaisha, Ltd.
* 14 Stearic acid-treated titanium oxide: MT-100TV manufactured by Teika.
* 15 Silicone-treated talc: SI-talc JA-46R, manufactured by Miyoshi Kasei Co., Ltd.
* 16 Silicone treated iron oxide: manufactured by Miyoshi Kasei Co., Ltd., SI-Bengara Cloisonne * 17 Silicone treated iron oxide: manufactured by Miyoshi Kasei Co., Ltd., SI-yellow * 18 Silicone treated iron oxide: manufactured by Miyoshi Kasei Co., Ltd., SI-black * 19 Silica: Sunsphere H-121, manufactured by AGC SITEC
* 20 Silicone treated synthetic phlogopite: PDM-20L (S) manufactured by Topy Industries, Ltd.
* 21 (Vinyl dimethicone / methicone silsesquioxane) cross polymer: KSP-100 manufactured by Shin-Etsu Chemical Co., Ltd.
* 22 Silicone treated borosilicate (Ca / Al): Nippon Sheet Glass Co., Ltd., Silky Flake FTD010FY-F01
* 23 Composite powder of titanium oxide and mica: made by BASF, flamenco sparkle blue

Claims (4)

The following components (A) to ( F ):
(A) 1 to 25% by mass of fluorescent zinc oxide having a number average particle size of 1.6 to 4 μm,
(B) 1 to 15% by mass of ultraviolet absorber, and (C) 2 to 15% by mass of non-volatile oil which is liquid at 25 ° C. other than the component (B).
(D) Film-forming polymer
(E) Surfactant
(F) A water-in-oil type skin cosmetic containing a volatile oil which is liquid at 25 ° C. other than the component (B) ,
In the water-in-oil type skin cosmetic, the mass ratio of the total content of the components (B) and (C) to the content of the component (A) (((B) + (C)) / (A)) ) Is 0.3-10, water-in-oil type skin cosmetics.   The total content ((B) + (C)) of the components (B) and (C) in the water-in-oil type skin cosmetic is 3 to 20 with respect to the whole water-in-oil type skin cosmetic. The water-in-oil type skin cosmetic according to claim 1, which is a mass%. The water-in-oil type skin cosmetic according to claim 1 or 2 , wherein the component (E) contains a silicone-based surfactant. The total content of titanium oxide, the component (A) and other zinc oxide in the water-in-oil skin cosmetic is 20% by mass or less with respect to the entire water-in-oil skin cosmetic. Item 1. A water-in-oil type skin cosmetic according to any one of items 1 to 3 .