JP6035121B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

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

  Crosslinked polyether-modified silicone has been used to improve the longevity and feel of use. For example, a cross-linked polyether-modified silicone and a powder are combined, and while the powder is highly blended, the water-in-oil emulsified cosmetic (Patent Document 1) has a light and fresh feeling of use, and a cross-linked polyether-modified silicone and A combination of silicone-treated powders and cosmetics that are excellent in makeup and have a good feel (Patent Document 2) have been studied.

JP 2010-116354 A JP 2012-17317 A

  The present inventors have found that the cross-linked polyether-modified silicone has excellent makeup durability and feeling of use, but when applied to the skin, it adheres to the skin crevice, resulting in uneven coating and powdering. I found a problem that it would be a crisp finish.

  The present inventors can obtain a water-in-oil emulsified cosmetic that solves the above problems by using a specific cross-linked polyether-modified silicone in combination with a specific fluorine-modified silicone and a fluorine compound-treated powder. I found.

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

(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.05 to 20% by mass of a crosslinked polyether-modified silicone represented by
(B) The following general formulas (2) and (3)

(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 an alkyl 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 the ratio of p and s 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
(C) A water-in-oil type containing a powder treated with tridecafluorooctyltriethoxysilane and having a mass ratio (A) / (B) of components (A) and (B) of 0.01 to 5 It relates to emulsified cosmetics.

  The water-in-oil emulsified cosmetic of the present invention uniformly adheres to the skin's skin crevice and hills, has good adhesion to the entire skin, prevents the skin from appearing rough, and has an inconspicuous finish. It is obtained and can make skin look brighter.

In an Example, it is a figure which shows the shape of the transparent polyurethane sheet | seat which has a wrinkle shape used for evaluation of the anti-shrink effect. In the examples, in the evaluation of the anti-shrinking effect, after applying oleic acid (artificial sebum), the makeup base and foundation of the example or comparative example to a transparent polyurethane sheet having a wrinkle shape, the sheet was bent It is a figure which shows a state. In an Example, it is the figure which extracted the image of the groove | channel part in which makeup | skinring arises in evaluation of the makeup | skin prevention effect. In an Example, it is a figure which shows the image analysis by (a) binarization and (b) standard deviation after the image extraction of the groove part where makeup twist occurs in evaluation of the makeup prevention effect.

The component (A) used in the present invention is a crosslinked polyether-modified silicone represented by the general formula (1).
In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group or acyl having 1 to 30 carbon atoms. Or a siloxane group having 1 to 30 silicon atoms, d is a number from 1 to 20, e and f are numbers from 0 to 200, and e and f are not 0 at the same time. The number of 0-30 is shown, h shows the number of 1-100, i shows the number of 10-2000, j shows the number of 1-1000, k shows the number of 1-1000.
Among them, in the formula, R ″ is preferably an alkyl group having 1 to 15 carbon atoms, g is a number from 0 to 15, h is a number from 1 to 40, i is a number from 10 to 200, j is A number of 1 to 50 and k is preferably a number of 1 to 50.

  The crosslinked polyether-modified silicone of component (A) can be produced, for example, by the method described in JP-A-4-272932.

As the component (A), dimethicone (PEG-10 / 15) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, and (PEG-10 / lauryl dimethicone) crosspolymer are preferable.
Examples of the component (A) include KSG-210, KSG-240 (dimethicone / (PEG-10 / 15)) crosspolymer); KSG-310, KSG-320, KSG-330 ((PEG-15 / Lauryl dimethicone) cross polymer); KSG-340 ((PEG-10 / lauryl dimethicone) cross polymer and (PEG-15 / lauryl dimethicone) cross polymer) (above, Shin-Etsu Chemical Co., Ltd.) can be used. .

  Ingredient (A) can be used singly or in combination of two or more, adheres uniformly to the skin's crevice and skin, prevents skin from appearing rough, The content is 0.05% by mass or more, preferably 0.1% by mass or more, and more preferably 0.3% by mass or more from the viewpoint that a finish with an inconspicuous feeling can be obtained. And it adheres evenly to the skin crevice and skin hill, adheres well to the whole skin, prevents the skin from appearing rough, and gives a finish with an inconspicuous feel of powder. Yes, 10 mass% or less is preferable, and 7 mass% or less is more preferable. Moreover, content of a component (A) is 0.05-20 mass% in the whole composition, 0.1-10 mass% is preferable, and 0.3-7 mass% is more preferable.

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

  Further, the ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (2) with respect to the total p + s of the polysiloxane units represented by the general formulas (2) and (3) is used. 0.66 ≦ p / (p + s) ≦ 0.9, and 0.75 ≦ from the viewpoint that it is excellent in feeling and makeup, is less likely to cause uneven appearance, and is less likely to cause uneven application after the cosmetic is applied. p / (p + s) ≦ 0.83 is preferable.

The fluorine-modified silicone as component (B) can be produced, for example, according to the method described in JP-A-6-184212.
As a component (B), what is represented by following General formula (4) is preferable.

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

  Ingredient (B) can be used alone or in combination of two or more, has excellent makeup, adheres evenly to the skin's skin crevice and dermis, and has good adhesion to the entire skin. It is 0.01 mass% or more in all compositions, 0.1 mass% or more is preferable and 0.5 mass% or more is more preferable. And it is 50 mass% or less from the point which adheres to the skin crevice and skin hill of skin uniformly, and the sticking to the whole skin is preferable, 30 mass% or less is preferable, and 20 mass% or less is more preferable. Moreover, content of a component (B) is 0.01-50 mass%, 0.1-30 mass% is preferable and 0.5-20 mass% is more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) adheres uniformly to the skin's skin crevice and skin hill, has good adhesion to the entire skin, and the skin looks rough. From the viewpoint of preventing this and obtaining a finish with an inconspicuous feeling of powder, it is 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, 5 or less, and preferably 3 or less, 1 .5 or less is more preferable. Moreover, mass ratio (A) / (B) of component (A) and (B) is 0.01-5, 0.05-3 are preferable and 0.1-1.5 are more preferable.

The powder of component (C) used in the present invention has been surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
Among the fluorine compounds that surface-treat the powder, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, it is possible to suppress uneven skin and obtain a natural finish. 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, 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, oxidation Inorganic powders such as chromium, chromium hydroxide, calamine and carbon black, and composites thereof; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine Resin, Epoxy Organic powders such as 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; A composite powder of inorganic powder and organic powder can be used.

As a method of surface-treating the powder with tridecafluorooctyltriethoxysilane, for example, tridecafluorooctyltriethoxysilane is dropped or added in a mixer and mixed with the powder, followed by heat treatment, and if necessary And a method in which an organic solvent liquid in which tridecafluorooctyltriethoxysilane is dissolved or dispersed and a powder are mixed, the organic solvent is removed, and the mixture is crushed after drying.
Among them, tridecafluorooctyltriethoxysilane is dissolved or dispersed in an organic solvent, and while mixing the powder and the mixer in the mixer, the mixer is heated under reduced pressure to remove the organic solvent. A production method for crushing 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, chloroform, and normal hexane, toluene, xylene, and the like. Hydrocarbon organic solvents are suitable.

  The treatment amount of tridecafluorooctyltriethoxysilane varies depending on the powder, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 50% by mass with respect to the mass of the powder of the component (C). % Or less is preferable, and 20% by mass or less is more preferable. Moreover, it is preferable that it is 0.05-50 mass%, and it is more preferable to process 0.1-20 mass%. This treatment amount is preferable because water repellency and oil repellency are sufficiently exhibited, and feel and fluidity are good.

Component (C) preferably has an average particle size of 0.01 to 20 μm, more preferably 0.01 to 10 μm, from the standpoint of powderiness and finish at the time of application.
In the present invention, the particle size 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.

  Ingredient (C) can be used alone or in combination of two or more, adheres uniformly to the skin's skin crevice and dermis, adheres well to the entire skin, and in terms of finish and stability, the content is The total composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. And it adheres uniformly to the skin crevice and skin hill, adheres to the whole skin, and is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 15% by mass or less from the viewpoint of finish and stability. Is more preferable. Moreover, 0.1-40 mass% is preferable in the whole composition, as for content of a component (C), 0.5-30 mass% is more preferable, and 1-15 mass% is further more preferable.

  In the present invention, the mass proportions (A) / (C) of the components (A) and (C) are uniformly attached to the skin crevice and dermis, have good adhesion to the whole skin, and the skin looks rough. From the viewpoint of preventing this and obtaining a finish with an unnoticeable texture, 0.02 or more is preferable, 0.04 or more is more preferable, 0.1 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable 2 or less is more preferable. Moreover, 0.02-10 are preferable, as for mass ratio (A) / (C) of component (A) and (C), 0.04-5 are more preferable, and 0.1-2 are still more preferable.

The water-in-oil emulsified cosmetic of the present invention may further contain (D) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, preferably 15 to 95 m 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 fine particle zinc oxide of component (D) 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 or the like. 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 (D) can be used singly or in combination of two or more, and the content is preferably 0.1% by mass or more in the total composition from the viewpoint that the entire skin is bright and the skin is brightened. 0.5 mass% or more is more preferable, 1 mass% or more is further more preferable, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 8 mass% or less is still more preferable. Moreover, 0.1-20 mass% is preferable in the whole composition, content of a component (D) has more preferable 0.5-10 mass%, and 1-8 mass% is still more preferable.

  The content of water used in the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 60% by mass or less, and 50% by mass in the total composition from the viewpoint of usability and storage stability. % Or less is more preferable. Moreover, it is preferable to contain 10-60 mass% of water in the whole composition, and 15-50 mass% is more preferable.

In addition, the oil used in the present invention may be liquid at 20 ° C. 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, 10 mass% or more is preferable in the whole composition, as for content of the oil agent used for this invention, 20 mass% or more is more preferable, 50 mass% or less is preferable, and 45 mass% or less is more preferable. Moreover, it is preferable to contain 10-50 mass% of oil agents in the whole composition, and 20-45 mass% is more preferable.

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 components (A), (B), and (C), the HLB value is preferably 1 or more and 7 or less, and the HLB value is more preferably 2 or more and 6 or less.
The content of the nonionic surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 8% by mass or less, and more preferably 6% by mass or less in the total composition. Moreover, it is preferable to contain 0.1-8 mass% of surfactant in the whole composition, and 0.2-6 mass% is more preferable.

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 water-in-oil emulsified cosmetic of the present invention is a component used in ordinary cosmetics in addition to the above components, for example, solid oils such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax; And oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling sensations Agents, antiperspirants, bactericides, skin activators, and the like.

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method. Examples of the dosage form include liquid, emulsion, cream, and gel, and emulsion and cream are preferred.
Further, the water-in-oil emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as UV protection cosmetics such as sunscreen cream. Among these, a makeup base, a liquid foundation, and a concealer are more preferable, and a makeup base is more preferable.

The water-in-oil emulsified cosmetic of the present invention preferably has a viscosity at 25 ° C. of 500 to 200,000 mPa · s, preferably 1,000 to 100,000 mPa · s, from the viewpoint of blending stability, usability, and feeling of use. Is more preferable, and it is still more preferable that it is 2000-50,000 mPa * s. Here, the viscosity is measured with a B-type viscometer.
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B) and (C):
(A) The following general formula (1)

(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.05 to 20% by mass of a crosslinked polyether-modified silicone represented by
(B) The following general formulas (2) and (3)

(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 an alkyl 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 the ratio of p and s 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
(C) A water-in-oil type containing a powder treated with tridecafluorooctyltriethoxysilane and having a mass ratio (A) / (B) of components (A) and (B) of 0.01 to 5 Emulsified cosmetic.

<2> The oil according to <1>, wherein the content of the component (A) is 0.05 to 20% by mass, preferably 0.1 to 10% by mass, and more preferably 0.3 to 7% by mass. Water-in-water emulsified cosmetic.
<3> The content of the component (B) is 0.01 to 50% by mass, preferably 0.1 to 30% by mass, and more preferably 0.5 to 20% by mass <1> or <2 > Water-in-oil emulsified cosmetics as described.
<4> The mass ratio (A) / (B) of the components (A) and (B) is 0.01 to 5, preferably 0.05 to 3, and more preferably 0.1 to 1.5. The water-in-oil emulsified cosmetic according to any one of <1> to <3>.

<5> The content of the component (C) is 0.1 to 40% by mass, preferably 0.5 to 30% by mass, and more preferably 1 to 15% by mass. The water-in-oil emulsion cosmetic according to any one of the above.
<6> The mass ratio (A) / (C) of the components (A) and (C) is 0.02 to 10, preferably 0.04 to 5, and more preferably 0.1 to 2. The water-in-oil emulsified cosmetic according to any one of 1> to <5>.
<7> Further, (D) 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably, fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, preferably 15 to 95 m ² / g. The water-in-oil emulsified cosmetic according to any one of <1> to <6>, wherein 1 to 8% by mass is contained.

Synthesis Example 1 (Synthesis of Compound B1)

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 (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 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 B2)

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.
21.29 g (51 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added to a 300 mL four-necked flask equipped with a thermometer, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.26 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 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 B3)

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 (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a 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 B4)

In a 100 mL two-necked flask equipped with a condenser and a magnetic stirrer, 20 mL of toluene and 8.0 g (18.6 mmol) of hydrogen polysiloxane (MD ₂ D ₂ ^MH ) (manufactured by Toshiba Silicone) under a nitrogen atmosphere , C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 18.0 g (44.7 mmol), 2% isopropyl alcohol solution of chloroplatinic acid in 29 μL (0.89 × 10 ⁻³ mmol) was added. , And stirred at 110 ° C. for 4 hours. The reaction mixture was cooled to room temperature, and 1.0 g of activated carbon was added and stirred at room temperature for 1 hour. The activated carbon was filtered off, and the solvent was distilled off. Unreacted compound was distilled off under reduced pressure to obtain 20.3 g of the objective compound (Compound A4) as a colorless and transparent oil (yield 87%).

Synthesis Example 5 (Synthesis of Compound B5)

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. The unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective compound (Compound A5) as a colorless and transparent oil (yield 78%).

Examples 1-12 and Comparative Examples 1-5
A W / O makeup base having the composition shown in Table 1 was manufactured and applied to the skin immediately after application, the brightness of the skin immediately after application, the inconspicuous feeling of powder immediately after application, the dispersion state, and the makeup The prevention effect was evaluated. The results are also shown in Table 1.

(Production method)
After roughly mixing the powder components, the powder components were mixed and pulverized using an Admizer pulverizer (Fuji Paudal). The oil phase component was mixed, and the pulverized powder component was added and dispersed with a disper. Furthermore, the water phase component was mixed and added to the oil phase and powder mixture to emulsify. Thereafter, the viscosity was adjusted with a homomixer to obtain a W / O makeup base.

(Evaluation method)
(1) Good skin contact immediately after application:
Five professional panelists evaluated the “goodness on the skin” immediately after each cosmetic was applied to the skin according to the following criteria. The results are shown as a total of 5 people.
5; Very good skin contact.
4; Good skin contact.
3; Slightly good skin contact.
2; The skin is not very good.
1; Skin is not good.

(2) Skin brightness immediately after application:
Five professional panelists evaluated the “brightness of the finished skin” immediately after each cosmetic was applied to the skin according to the following criteria. The results are shown as a total of 5 people.
5: The finish of the skin is very bright.
4; The skin finish is bright.
3; The skin finish is slightly bright.
2: The skin finish is not so bright.
1: The skin finish is not bright.

(3) No noticeable texture immediately after application:
Five expert panelists performed sensory evaluation on the following criteria based on the “not noticeable texture of the skin” immediately after each cosmetic was applied to the skin. The results are shown as a total of 5 people.
5: The powdery texture of the skin is not noticeable.
4; The powdery texture of the skin is not so noticeable.
3; The powdery texture of the skin is slightly noticeable.
2: The powdery texture of the skin is conspicuous.
1: The powdery texture of the skin is very conspicuous.

(4) Distributed state:
Each cosmetic was applied to artificial leather to a thickness of 25 μm using an applicator and dried at 37 ° C. for 3 hours using a hot plate. Five specialist panelists visually evaluated the dispersion state of the powder in the obtained cosmetic coating film according to the following criteria. The results are shown as a total of 5 people.
4: The powder is not agglomerated and applied uniformly.
3: The powder is less agglomerated and applied uniformly.
2: There is agglomeration of the powder and it is applied unevenly.
1; Clearly there is agglomeration of the powder and it is applied unevenly.

(5) Anti-makeup effect:
0.005 g of oleic acid (artificial sebum) was applied to a transparent polyurethane sheet having a wrinkle shape (FIG. 1). On top of that, 0.025 g of each makeup base (Table 1) was applied and dried on a 37 ° C. hot plate for 30 minutes. Further, 0.01 g of a solid foundation (Japanese Patent Laid-Open No. 2001-158717, product 1 of the present invention 1 (Table A)) of Example 1 was applied on a makeup base using a sponge. Then, it dried at room temperature for 30 minutes and obtained the sheet-like test article.
A polyurethane sheet coated with each test product is placed on a black plate, and a magnified image is taken (condition: 40 times) by DSA (direct skin analyzer). Next, after the sheet is bent 30 times along the groove of the polyurethane sheet, an enlarged image of the same part is taken (FIG. 2). By image analysis of Adobe Photoshop Elements3.0, the difference between each data of binarization and standard deviation was obtained from the captured images before and after the bending operation. Table 1 shows the binarization and standard deviation. It can be seen that if the binarization difference is large, the foundation has a large difference, and if the standard deviation is large, the makeup has become uneven.

Moreover, about the polyurethane sheet after bending, five special panelists evaluated the application | coating state visually according to the following reference | standard. The results are shown as a total of 5 people.
3; there is no aggregation of the powder and there is no peeling of the powder.
2: There is no aggregation of the powder and the powder is less peeled.
1; There is agglomeration of the powder, and the powder is peeled off to cause makeup.

Example 13 (Liquid Foundation)
A liquid foundation having the composition shown in Table 2 was produced by a conventional method.
The obtained foundation adheres evenly to the skin crevice and skin hill, adheres well to the entire skin, gives a finish that is not noticeable to the powder, and makes the skin appear brighter.

Example 14 (Concealer)
A concealer having the composition shown in Table 3 was produced by a conventional method.
The resulting concealer uniformly adheres to the skin's skin crevice and skin hills, has good adhesion to the entire skin, gives an unobtrusive finish, and makes the skin look brighter.

Claims (4)

The following components (A), (B) and (C):
(A) The following general formula (1)
(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group having 1 to 30 carbon atoms or An acyl group or a siloxane group having a silicon atom of 1 to 30. d represents a number of 1 to 20, e and f represent a number of 0 to 200, and e and f are not simultaneously 0. g Represents a number from 0 to 30, h represents a number from 1 to 100, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
0.05 to 20% by mass of a crosslinked polyether-modified silicone represented by
(B) The following general formula (4)
(In the formula, p represents a number of 3 to 50, s represents a number of 1 to 5, 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
(C) A water-in-oil type containing a powder treated with tridecafluorooctyltriethoxysilane and having a mass ratio (A) / (B) of components (A) and (B) of 0.01 to 5 Emulsified cosmetic.   The water-in-oil emulsified cosmetic according to claim 1, comprising 0.1 to 40% by mass of component (C).   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (C) of the components (A) and (C) is 0.02 to 10. The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, further comprising (D) 0.1 to 20% by mass of finely divided zinc oxide having a specific surface area of 10 to 100 m ² / g.