JP5930776B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic.

When only normal powder is blended in cosmetics, the powder becomes wet and mirror-finished due to sweat, sebum, etc. generated on the skin, and it is difficult to maintain the finish immediately after application. For this reason, various cosmetics that do not easily cause makeup loss and have a long makeup have been studied.
For example, cosmetics containing a fluorine compound-treated powder, a fluorine-based oil, fluorine-modified silicone, and the like have been studied (Patent Documents 1 and 2).

JP-A-4-91008 Japanese Patent Laid-Open No. 6-184212

The present inventor has found that a cosmetic containing a fluorinated oil has low affinity with the skin, tends to be uneven, and gives a feeling of tension after application. Furthermore, when used as a makeup base, the present inventors have found problems such as powder foundation, unevenness, and makeup paste.
It is an object of the present invention to provide a cosmetic material in which the feeling of stickiness and unevenness after application is suppressed and the cosmetic paste is excellent when applied as a makeup base and used with a powder foundation or when used alone. .

  The inventor can obtain a cosmetic that solves the above problems by using a combination of a fluorine compound-treated powder, a specific fluorine-modified silicone, fine zinc oxide having a specific surface area, and hyaluronic acid and / or a salt thereof. I found out that

The present invention includes the following components (A), (B), (C) and (D):
(A) The following general formulas (1) and (2)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ¹ , R ² and R ³ are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents a hydrocarbon group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and p and s (The ratio is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(B) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g,
(C) Hydrophobized powder excluding component (B),
(D) It provides hyaluronic acid and / or a salt thereof, and provides a cosmetic in which the mass ratio of components (A) and (D) is (A) / (D) = 30 to 2000.

The cosmetic composition of the present invention has a reduced feeling of tension and unevenness after application, and when applied as a makeup base and a powder foundation is used, or when the foundation is used alone, the cosmetic paste is excellent, and further familiar to the skin And a finish with a close feeling can be obtained.
Note that the familiarity with the skin means that when the cosmetic is spread on the skin, even with a single application, the makeup does not become uneven and a highly uniform appearance is obtained.

The fluorine-modified silicone of component (A) used in the present invention has a polysiloxane unit represented by the general formulas (1) and (2).
In the formula, examples of the hydrocarbon group represented by R ¹ , R ² and R ³ include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an isopropyl group, sec -Branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; and cyclic alkyl groups such as cyclopentyl and cyclohexyl.

Moreover, m shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. n shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.

  The ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (1) with respect to the total p + s of the polysiloxane units represented by the general formulas (1) and (2) is used. From the standpoint of excellent feeling and long-lasting makeup and less likely application unevenness, 0.66 ≦ p / (p + s) ≦ 0.9, and preferably 0.75 ≦ p / (p + s) ≦ 0.83.

The fluorine-modified silicone of component (A) can be produced, for example, according to the method described in JP-A-6-184212.
As a component (A), what is represented by following General formula (3) is preferable.

(Wherein p and s have the same meaning as described above, and q represents a number of 5)

  Ingredient (A) can be used alone or in combination of two or more, suppresses unevenness, has a good makeup paste, and has a lower limit of 0.01% by mass or more with respect to the entire cosmetic from the viewpoint of having a makeup. 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1 mass% or more is more preferable. Moreover, an upper limit is 50 mass% or less, 30 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is more preferable. When these viewpoints are combined, the content of the component (A) is 0.01 to 50% by mass, preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and a feeling of tension. From the point of suppression, it is more preferable to contain 1-10 mass%.

Particulate zinc oxide component (B) used in the present invention has a specific surface area be of 10 to 100 m ² / g, preferably from 15~95m ² / g. By using the fine particle zinc oxide having such a specific surface area, the cosmetic durability is excellent and a good feeling of use can be obtained.

  The finely divided zinc oxide of component (B) can be used as it is, but if necessary, it is subjected to water and / or oil repellent treatment with silicone, metal soap, lecithin, N-acylamino acid, fluorine compound, etc. Can also be used. From the standpoint of preventing makeup collapse and improving the dispersibility of the fine zinc oxide in the cosmetic, a silicone-treated one is preferred, and a silicone treatment using methylhydrogenpolysiloxane is more preferred. These processes can be performed by a normal method.

  Component (B) can be used singly or in combination of two or more, and the lower limit is preferably 0.1% by weight or more, preferably 1% by weight, based on the feeling of use, makeup paste, and makeup retention. The above is more preferable, and 5% by mass or more is more preferable. Further, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. When these viewpoints are put together, 0.1 to 20% by mass is preferable, 1 to 15% by mass is more preferable, and 5 to 12% by mass is more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) suppresses the feeling of firmness and unevenness of the skin, and the lower limit is 0.05 or more from the viewpoint of long makeup persistence. Is preferable, and 0.1 or more is more preferable. Further, the upper limit is preferably 3 or less, and more preferably 1.5 or less. When these viewpoints are put together, it is preferable that (A) / (B) = 0.05 to 3, more preferably 0.1 to 1.5.

  Component (C) used in the present invention is a hydrophobized powder excluding component (B). The hydrophobizing treatment is not limited as long as it is a treatment applied to normal cosmetic powders. Silicone treatment, fatty acid treatment, lauroyllysine treatment, lecithin treatment, N-acylamino acid treatment, metal soap treatment, fluorine Compound treatment and the like can be mentioned. Of these, fluorine compound treatment and silicone treatment are preferred, and fluorine compound treatment and silicone treatment may be used in combination. In that case, the lower limit of the powder treated with the fluorine compound is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, with respect to the whole component (C). Even more preferably,

The component (C) powder used in the present invention is preferably treated with a fluorine compound.
Examples of the fluorine compound used to treat the powder include perfluoroalkyl group-containing phosphate esters (US Pat. No. 3,632,744), monoesters and diesters of fluoroalkyl phosphate diethanolamine salts (JP-A-62). No.-250074), a resin having a perfluoroalkyl group (Japanese Patent Laid-Open No. 55-167209), a tetrafluoroethylene resin, a perfluoroalcohol, a perfluoroepoxy compound, a sulfoamide type fluorophosphoric acid, a perfluorosulfate, Examples thereof include perfluorocarboxylates, perfluoroalkylsilanes (JP-A-2-218603), compounds having a perfluoropolyether group (JP-A-8-33928), and perfluoroalkylsilanes are preferred.

As the fluorine compound, tridecafluorooctyltriethoxysilane represented by the following formula is preferable.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
Among the fluorine compounds that surface-treat powder, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, it has excellent stability, good skin fit, moisturizing feeling and unevenness, and moist Can be used. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

  The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, Bengala, clay, bentonite, mica, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine , Inorganic powders such as chromium oxide, chromium hydroxide, calamine, carbon black, and composites thereof; polyamide, nylon, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, Acrylic resin, melami Organic powders such as resins, epoxy resins, polycarbonate resins, divinylbenzene / styrene copolymers, silk powder, cellulose, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and complexes thereof; Furthermore, the composite powder of the said inorganic powder and organic powder etc. are mentioned.

Examples of a method for surface-treating powder with a fluorine compound include, for example, a method in which a fluorine compound is dropped or added in a mixer and mixed with the powder, followed by heat treatment and pulverization as necessary. Examples include a method in which a dissolved or dispersed organic solvent liquid and powder are mixed, the organic solvent is removed, and the powder is dried and crushed.
Among them, a manufacturing method in which a fluorine compound is dissolved or dispersed in an organic solvent, mixed with the powder in the mixer, heated under reduced pressure to remove the organic solvent, and then heat-treated and crushed as necessary. Is preferred. Examples of the organic solvent used here include polar organic solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, dichloromethane, and chloroform, and normal hexane, toluene, and xylene. Hydrocarbon organic solvents are suitable.

  Although the treatment amount of the fluorine compound varies depending on the powder, the lower limit is preferably 0.05% by mass or more and more preferably 0.1% by mass or more with respect to 100% by mass of the fluorine-treated powder of the component (C). Moreover, 50 mass% or less is preferable and, as for an upper limit, 20 mass% or less is more preferable. If these viewpoints are put together, it is preferable that it is 0.05-50 mass%, and it is more preferable to process 0.1-20 mass%. If it is this processing amount, since water repellency and oil repellency will fully express and a touch is also favorable, it is preferable.

Component (C) has an average particle size of preferably 0.1 to 20 μm, more preferably 0.1 to 15 μm, and more preferably 1 to 10 μm from the viewpoint of powderiness and finish at the time of application. preferable.
In the present invention, the particle diameter of the component (C) is measured with an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

The powder of component (C) preferably has a spherical shape. The spherical shape refers to a powder having a substantially spherical shape, and may be a spheroid, a spherical powder having irregularities on the surface, or the like, and does not need to be a perfect sphere.
The spherical powder of component (C) is not particularly limited as long as it is used in ordinary cosmetics. For example, polyamide powder, nylon powder, polyester powder, polyethylene powder, polytetrafluoroethylene powder, polypropylene powder , Polystyrene powder, benzoguanamine powder, polymethylbenzoguanamine powder, polymethyl methacrylate powder, polyurethane powder, vinyl resin, fluorine resin, acrylic resin, melamine resin; Silicone powder;
Poly (meth) acrylic acid, such as butyl acrylate / vinyl acetate copolymer, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, (lauryl methacrylate / ethylene glycol dimethacrylate) copolymer, Cross-linked or non-crosslinked type such as powder of one or more kinds of polymers or copolymers selected from sodium poly (meth) acrylate, poly (meth) acrylic ester, poly (meth) acrylate alkylene glycol The organic spherical powder is mentioned.

  Component (C) can be used singly or in combination of two or more, and the lower limit is preferably 0.1% by mass or more with respect to the total cosmetics in terms of the feeling of use, makeup paste and longevity. More preferably, 5 mass% or more is more preferable, 1 mass% or more is further more preferable, and 2 mass% or more is further more preferable. Moreover, 30 mass% or less is preferable, as for an upper limit, 25 mass% or less is more preferable, 20 mass% or less is more preferable, and 15 mass% or less is more preferable. If these viewpoints are put together, it is preferable to contain 0.1-30 mass%, 0.5-25 mass% is more preferable, 1-20 mass% is further more preferable, and 2-15 mass% is contained. Is even more preferable.

  In the present invention, the mass ratio (A) / (C) of the components (A) and (C) is preferably 0.01 or more, preferably 0.1 or more, from the viewpoint of feeling of use, makeup paste and makeup retention. Is more preferable, and 0.2 or more is more preferable. The upper limit is preferably 50 or less, more preferably 10 or less, and still more preferably 5 or less. Taking these viewpoints together, (A) / (C) = 0.01 to 50 is preferable, 0.1 to 10 is more preferable, and 0.2 to 5 is even more preferable.

The component (D) hyaluronic acid used in the present invention is a kind of acidic mucosaccharide, which is a chained polysaccharide in which β-DN-acetylglucosamine and β-D-glucuronic acid are alternately bonded, When dissolved in, a highly transparent solution can be obtained. Examples of the salt include sodium and potassium, and sodium is preferable.
As hyaluronic acid and its salt, commercially available products can be used, and those extracted from animal tissues and those produced by fermentation by culturing microorganisms can also be used. Examples of the fermentation method include a method using Streptococcus zooepidemic-us, a kind of streptococci.

The molecular weight of hyaluronic acid and its salt is preferably 30,000 to 3,000,000, preferably from 30,000 to 3,000,000 from the viewpoint of suppressing the feeling of tightness of the skin, improving the adhesion between the powder and the skin, and suppressing unevenness. More preferably, those of 750,000 to 2 million are more preferred. Hydrolyzed hyaluronic acid and hyaluronic acid salts can also be used.
Although the measuring method of molecular weight is not limited, For example, the intrinsic viscosity is calculated | required from dynamic viscosity, The method of converting this intrinsic viscosity into molecular weight, the simple measuring method by a liquid chromatography, etc. are mentioned.
Of hyaluronic acid and hyaluronate, sodium hyaluronate is preferable from the viewpoints of solubility in water, feeling of use on the skin, and the like.

  Ingredient (D) can be used alone or in combination of two or more, from the point of suppressing the feeling of tightness of the skin, improving the adhesion between the powder and the skin, suppressing unevenness, and improving the makeup paste, 0.001 mass% or more is preferable with respect to the whole cosmetics, 0.002 mass% or more is more preferable, 0.003 mass% or more is further more preferable. Moreover, 0.1 mass% or less is preferable, as for an upper limit, 0.06 mass% or less is more preferable, and 0.05 mass% or less is further more preferable. When these viewpoints are combined, 0.001 to 0.1% by mass is preferable, 0.002 to 0.06% by mass is more preferable, and 0.003 to 0.05% by mass is further included. preferable.

  In this invention, it is mass ratio (A) / (D) = 30-2000 of component (A) and (D). From the point of suppressing skin tightness, improving the adhesion between the powder and skin, suppressing unevenness, and improving makeup, the lower limit is preferably 60 or more, from the point of improving familiarity with the skin, 100 or more is more preferable. Further, the upper limit is preferably 1500 or less, and more preferably 1400 or less. When these viewpoints are put together, (A) / (D) = 60-1500 is preferable, and it is more preferable that it is 100-1400.

  The content of water used in the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and the upper limit is 70% with respect to the entire cosmetic from the viewpoint of usability and storage stability. The mass% or less is preferable, and 60 mass% or less is more preferable. When these viewpoints are put together, 10-70 mass% is preferable, and it is more preferable to contain 20-60 mass%.

The oil used in the present invention is preferably liquid at 20 ° C., and when a solid or paste oil is used, it is preferably used after being dissolved in another oil or solvent.
Examples of the oil used in the present invention include silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils (including fats and oils), ether oils, mineral oils, etc. Ester oil is more preferable, and silicone oil is more preferable. Of these, dimethylpolysiloxane and cyclopolysiloxane are more preferable.
These oil agents can be used alone or in combination of two or more.
Moreover, as for content of the oil agent used for this invention, 10 mass% or more is preferable with respect to the whole cosmetics, and 20 mass% or more is more preferable. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. If these viewpoints are put together, 10-50 mass% is preferable, and it is more preferable to contain 20-40 mass% from the point of use feeling and storage stability.

  Examples of the surfactant used in the present invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, nonionic surfactants are preferable, and polyether-modified silicones are more preferable. From the viewpoint of stably emulsifying the aqueous phase in the oil phase containing the component (A) and other oil agent, the HLB value is preferably 1 or more and 7 or less, and the HLB value is preferably 2 or more and 6 or less.

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lypophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant. For nonionic surfactants, Griffin ( Griffin).
The HLB of the mixed surfactant composed of two or more kinds of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is obtained by averaging the HLB values of the nonionic surfactants based on the blending ratio.

Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

  The lower limit of the surfactant content is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, with respect to the entire cosmetic. The upper limit is preferably 6% by mass or less, and more preferably 3% by mass or less. If these viewpoints are put together, 0.1-6 mass% or less is preferable, and it is more preferable to contain 0.2-3 mass%.

  The cosmetics of the present invention include, in addition to the above components, components used in ordinary cosmetics, such as water-soluble and oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, It can contain a pigment, a thickener, a pH adjuster, a fragrance, an ultraviolet absorber, a moisturizer, a blood circulation promoter, a cooling agent, an antiperspirant, a disinfectant, a skin activator, and the like.

  The cosmetic of the present invention can be produced according to a usual method, and may be any emulsion type such as a water-in-oil type, an oil-in-water type, or a two-layer separation type. Of these, water-in-oil emulsified cosmetics are preferable from the viewpoint of usability. Furthermore, examples of the dosage form include liquid, emulsion, cream, and gel, and emulsion is preferred.

  The cosmetics of the present invention can be produced according to ordinary methods, and make-up cosmetics such as makeup foundations, liquid foundations, oily foundations, powder foundations, lipsticks, blushers, eye shadows; sunscreen emulsions and sunscreen creams UV protective cosmetics such as Of these, a makeup base and a liquid foundation are preferable.

Synthesis Example 1 (Synthesis of Compound A1)

Synthesis of _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).

  To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and 8 cm made of Teflon (registered trademark) under a nitrogen atmosphere. The mixture was stirred at 200 rpm with a crescent blade, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (Compound A1) (yield 89%).

Synthesis Example 2 (Synthesis of Compound A2)

In the same manner as in Synthesis Example 1, C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ was synthesized.
To a 300 mL four-necked flask equipped with a thermometer, 21.29 g (51 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and 8 cm made of Teflon (registered trademark) under a nitrogen atmosphere. The mixture was stirred at 200 rpm with a crescent blade, 2 mass% chloroplatinic acid hexahydrate / 0.26 g of isopropyl alcohol was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 78.71 g (195 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 78.9 g of the target compound (Compound A2) (yield 85%).

Synthesis Example 3 (Synthesis of Compound A3)

In the same manner as in Synthesis Example 1, C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ was synthesized.
To a 300 mL four-necked flask equipped with a thermometer, 17.61 g (33 mmol) of hydrogen polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and 8 cm made of Teflon (registered trademark) under a nitrogen atmosphere. The mixture was stirred with a crescent blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.27 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 82.39 g (206 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 75.8 g of the target compound (Compound A3) (yield 82%).

Synthesis Example 4 (Synthesis of Compound A4)

In a 100 mL two-necked flask equipped with a condenser and a magnetic stirrer, 19.0 g (44.1 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ M) (manufactured by Toshiba Silicone) under a nitrogen atmosphere, C ₈ F ₁₇ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 53.3 g (105.8 mmol) was charged. Next, after raising the temperature in the flask to 80 ° C., 174.5 μL of a 2% isopropyl alcohol solution of chloroplatinic acid was added and stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, 50 mL of hexane and 2.2 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off and the solvent was distilled off. Unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective compound (Compound A4) as a colorless and transparent oil (yield 78%).

Examples 1-7, Comparative Examples 1-5
W / O makeup bases having the compositions shown in Table 1 were manufactured, and “goodness of familiarity”, “no stickiness after application”, “no stickiness after application” immediately after applying each makeup base, and “ “No unevenness after application” was evaluated. Next, after applying each makeup base, a powder foundation was applied, and “improved finish of powder foundation” and “good foundation of powder foundation” were evaluated immediately after. The results are also shown in Table 1.

(Production method)
About Examples 1-7 and Comparative Examples 1-5, the whole quantity is measured with a scale of 100 g. The oil phase (containing the active agent) containing the component (A) is preliminarily dispersed using a disper (500 r / min, 5 minutes). Next, the powder phase containing the components (B) and (C) is dispersed in the oil phase (1500 r / min, 10 minutes), and it is confirmed that the powder phase is uniformly dispersed. Using an oil phase in which the powder phase is uniform, gradually add an aqueous phase while stirring with a disper (450 r / min), then add an ethanol phase to emulsify and hold the emulsification, and then a homomixer The viscosity was adjusted (3000 r / min) and defoamed to obtain a W / O makeup base.

(Evaluation method)
Five professional panelists “Familiarity” immediately after applying each W / O makeup base to the skin with their fingers, “No stickiness after application”, “No feeling of tension after application” and “ Evaluate “no unevenness after application” according to the following criteria, and then apply each makeup base and then apply a powder foundation (Sophina Fine Fit Powder Foundation UV, manufactured by Kao Corporation) “Finish with a close feeling of foundation” and “Good foundation of powder foundation” were evaluated according to the following criteria. A result is shown by the integrated value of 5 persons.
4: I think so.
3: I think so.
2: I think so.
1: I don't think so.

Example 8
A liquid foundation having the composition shown in Table 2 was produced in the same manner as in Examples 1 to 7, and “goodness of familiarity” immediately after application with a sponge, “no stickiness after application”, “feeling of tension after application” “Non-uniformity”, “Non-uniformity after application”, “Finish with good adhesion” and “Good makeup” were evaluated. The results are shown in Table 2.

Claims (5)

The following components (A), (B), (C) and (D):
(A) The following general formula (3)

(In the formula, p represents a number of 3 to 10, s represents a number of 1 to 3, and the ratio of p and s is 0.66 ≦ p / (p + s) ≦ 0.9. Q is 5) Indicates the number of
0.01 to 50% by mass of a fluorine-modified silicone represented by
(B) Fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, 0.1 to 20% by mass ,
(C) Hydrophobized powder of 0.1 to 30% by mass excluding component (B)
(D) Hyaluronic acid and / or its salt 0.001-0.1 mass%
And a mass proportion of components (A) and (D) is (A) / (D) = 30-2000. Component (C), and a fluorine compound and / or cosmetic composition according to claim 1, wherein the treated powder with a silicone. The cosmetic according to claim 1 or 2 , wherein the component (D) has an average molecular weight of 30,000 to 3,000,000. The cosmetic according to any one of claims 1 to 3 , wherein the mass ratio of the components (A) and (B) is (A) / (B) = 0.05-3. The cosmetic according to any one of claims 1 to 4 , wherein the mass ratio of the components (A) and (C) is (A) / (C) = 0.01 to 50.