JP6382099B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

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

The organic fine powder is excellent in that it imparts a transparent natural skin color when blended in cosmetics.
For example, Patent Document 1 discloses that a cosmetic containing a specific plate-like color pigment and a spherical powder can provide a bright finish with a transparent appearance without conspicuous unevenness of the skin and imparting a natural skin color. Have been described.

JP 2004-83423 A

  When the present inventors apply water-in-oil emulsified cosmetics containing organic fine powder to the skin, they tend to cause lumps, cause a feeling of catching at the initial stage of application, and cannot be used comfortably. We found a problem that the adhesion to the hill was bad and it could not be applied well to the skin.

  The present inventors have solved the above-mentioned problems by using a spherical organic resin powder having a specific particle diameter surface-treated with perfluoroalkylsilane and a fluorine-modified silicone oil that is liquid at 25 ° C. in a specific ratio. It was found that a water-in-oil emulsified cosmetic was obtained.

The present invention includes the following components (A), (B), (C) and (D):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 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 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) volatile oil,
(D) Water 1-70 mass%
And the mass ratio (A) / (B) of component (A) to component (B) is from 0.02 to 40.

The water-in-oil emulsified cosmetic of the present invention is excellent in spreadability, has little feeling of catching at the initial stage of application, and suppresses formation of lumps during application. In addition, the cosmetics being applied can be finished with a single application without slipping over the skin, improving the covering power of the skin dermis.
Here, finishing with a single application means that the cosmetic can be applied without reapplying the same part of the skin many times when spreading on the skin. The painted skin has excellent adhesion to the skin dermis and is applied neatly across the skin crevice and entire skin.

The organic resin powder of component (A) used in the present invention is spherical. The spherical shape may be a spherical powder or the like including a true sphere, a substantially spherical shape, and a spheroid and having irregularities on the surface.
Any spherical resin powder may be used as long as it is used in ordinary cosmetics. For example, polyamide resin, nylon resin, polyester resin, polyethylene resin, polytetrafluoroethylene resin, polypropylene resin, polystyrene resin, benzoguanamine Resin, Polymethylbenzoguanamine resin, Polyurethane resin, Vinyl resin, Fluorine resin, Acrylic resin, Melamine resin; Silicone elastomer such as silicone elastomer cross-linked with dimethyl silicone and polymethylsilsesquioxane; Butyl acrylate / vinyl acetate copolymer Cross-linked or non-cross-linked organic powders such as one or two or more polymers selected from styrene / acrylic acid copolymers and divinylbenzene / styrene copolymers or copolymer powders.
Among these, acrylic resin powder is preferable, and one or more polymers selected from acrylic acid ester, methacrylic acid ester, alkylene glycol acrylate, and alkylene glycol methacrylate are more preferable.

The spherical organic resin powder of component (A) is a surface treated with perfluoroalkylsilane. Of the perfluoroalkylsilanes, those surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula are preferred.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

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, and chloroform, and normal hexane, toluene, and xylene. Hydrocarbon organic solvents are suitable.

  The treatment amount of perfluoroalkylsilane varies depending on the powder, but it is less likely to catch at the initial stage of application, and 0.05% by mass with respect to the mass of the spherical organic resin powder from the viewpoint of suppressing the formation of lumps during application. The above is preferable, 0.1 mass% or more is more preferable, 0.5 mass% or more is further preferable, 50 mass% or less is preferable, 20 mass% or less is more preferable, and 8 mass% or less is further preferable. In addition, the treatment amount of perfluoroalkylsilane is preferably 0.05 to 50% by mass, more preferably 0.1 to 20% by mass, based on the mass of the spherical organic resin powder. More preferably, it is 5-8 mass%.

The powder of component (A) is less likely to catch at the initial stage of application, and has a particle diameter of 0.01 μm or more and 1.0 μm or less from the viewpoint of suppressing the formation of lumps during application. Preferably, 0.2 to 0.5 μm is more preferable.
In addition, the powder of component (A) is less likely to catch in the initial stage of application, and preferably has an average particle diameter of 0.1 to 0.5 μm from the viewpoint of suppressing the formation of lumps during application. -0.4 micrometer is more preferable.
In the present invention, the particle diameter of the component (A) refers to that measured in a state of being surface-treated with perfluoroalkylsilane, and the measurement method is observed with an electron microscope image, and in 100 measured particles. This is a particle size distribution based on the number obtained by measuring the number of particles and creating a histogram. Further, the average particle diameter is obtained from a median diameter (50% diameter) distribution of particle diameters based on the number.

  In addition, in the present invention, the feeling of catching at the initial stage of coating is small, and from the viewpoint of suppressing the formation of lumps during coating, 30% by mass or more of all spherical organic resin powders have a particle size of 0.01 μm or more and 1.0 μm. The following spherical organic resin powder is preferred, more preferably 50% by mass or more, and even more preferably 75% by mass or more.

  Component (A) can be used singly or in combination of two or more, and the content is 0.1 mass in the total composition from the viewpoint that the feeling of catching at the initial stage of coating is small and the formation of lumps is suppressed during coating. % Or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more, further preferably 1% by weight or more, 20% by weight or less, preferably 15% by weight or less, and 10% by weight or less. Is more preferable, and 8 mass% or less is still more preferable. Moreover, content of a component (A) is 0.1-20 mass% in all the compositions, 0.3-15 mass% is preferable, 0.5-10 mass% is more preferable, 1-8 mass % Is more preferable.

Component (B) is a fluorine-modified silicone having polysiloxane units represented by the general formulas (1) and (2).
The fluorine-modified silicone is preferably liquid at 25 ° C. Here, the liquid state has fluidity, and includes pastes.

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. 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.

These fluorine-modified silicones can be produced, for example, according to the method described in JP-A-6-184212.
The fluorine-modified silicone is more preferably a fluorine-modified silicone consisting only of the polysiloxane units represented by the general formulas (1) and (2), and more preferably one represented by the following general formula (3). .

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

  Component (B) can be used singly or in combination of two or more, is excellent in feeling of use and long-lasting, has little scratching feeling at the initial stage of application, and suppresses the formation of lumps during application. The total composition is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, 50% by mass or less, and 30% by mass. The following is preferable, 15 mass% or less is more preferable, and 9 mass% or less is further more preferable. Moreover, content of a component (B) is 0.01-50 mass% in the whole composition, 0.1-30 mass% is preferable, 0.5-15 mass% is more preferable, 1-9 mass % Is more preferable.

  In the present invention, the mass ratio (A) / (B) of the component (A) with respect to the component (B) is excellent in spreadability, less likely to be caught at the initial stage of application, excellent in makeup, and forms a lump during application. It is 0.02 or more, 0.03 or more is preferable, 0.04 or more is more preferable, and 0.04 or more is more preferable because the cosmetics being applied can be finished with a single application without slipping over the skin. 4 or more is more preferable, 40 or less, 20 or less is preferable, 10 or less is more preferable, and 4 or less is more preferable. Moreover, mass ratio (A) / (B) of the component (A) with respect to a component (B) is 0.02-40, 0.03-20 are preferable, 0.04-10 are more preferable, 0.04. 4-4 are more preferable.

As the volatile oil of component (C), volatile hydrocarbon oil and volatile silicone oil are preferable. Volatile has a flash point of 35-87 ° C.
Examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane and isododecane; cyclic paraffin hydrocarbons such as cyclodecane and cyclododecane. Oil. Of these, isoparaffinic hydrocarbon oil is preferable, and isododecane is more preferable.

Examples of the volatile silicone oil include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1.5 cs) and dimethylpolysiloxane (2cs); branched forms such as tris (trimethylsilyl) methylsilane and tetrakis (trimethylsilyl) silane. Siloxane; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like.
As the volatile oil of component (C), after applying water-in-oil emulsified cosmetics to the skin, the feeling of use after the volatilization of component (C) is good, and there is little catching feeling at the initial stage of application, and during application From the viewpoint of suppressing the formation of lumps, volatile silicone oil is preferable.

  Component (C) can be used singly or in combination of two or more, and after applying water-in-oil emulsified cosmetics to the skin, the feeling of use after component (C) volatilizes is good, The content is preferably 1% by mass or more, more preferably 7% by mass or more, more preferably 15% by mass or more, and further preferably 15% by mass or more, from the point of being less likely to be caught and suppressing the formation of lumps during coating. % Or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is more preferable. Moreover, 1-50 mass% is preferable in the whole composition, as for content of a component (C), 7-40 mass% is more preferable, 15-30 mass% is further more preferable.

  The content of water of component (D) is 1% by mass or more, preferably 15% by mass or more, more preferably 25% by mass or more, and more preferably 70% by mass in the total composition from the viewpoint of excellent usability and stability. It is below, 45 mass% or less is preferable, and 40 mass% or less is more preferable. Moreover, content of a component (D) is 1-70 mass% in the whole composition, 15-45 mass% is preferable and 25-40 mass% is more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain ester oil that is liquid at 25 ° C. as the component (E), and can suppress roughness and roughness during application. Here, the liquid state has fluidity, and includes pastes.
Any ester oil that is liquid at 25 ° C. may be used as long as it is used in ordinary cosmetics. For example, avocado oil, macadamia nut oil, olive oil, rapeseed oil, sesame oil, wheat germ oil, linseed oil, cottonseed oil, large oil Bean oil, palm oil. Palm oil, castor oil, jojoba oil, sunflower oil, camellia oil, corn oil, isopropyl myristate, octyldodecyl myristate, isopropyl isostearate, isononyl isononanoate, isotridecyl isononanoate, butyl stearate, oleyl oleate, octyl ricinoleate Dodecyl, octyl hydroxystearate, 2-ethylhexyl paramethoxycinnamate, neopentyl glycol dicaprate, diisostearyl malate, polyglyceryl diisostearate, polyglyceryl triisostearate, glyceryl diisostearate, glyceryl triisostearate, tri (capryl Capric acid) glyceryl, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate Trimethylolpropane triisostearate, and the like. In addition, lanolin, trilanolin fatty acid glyceryl, soft lanolin fatty acid, petrolatum, branched or hydroxylated fatty acid cholesteryl, dipentaerythritol fatty acid ester (hexaoxystearic acid dipentaerythritol etc.), isostearic acid cured as cream or paste Castor oil, monohydroxystearic acid hydrogenated castor oil, tri (capryl / caprin / myristin / stearic acid) glyceride, myristyl lactate, dimerlinoleic acid hydrogenated castor oil, dimerlinoleic acid (phytorteryl / isostearyl / cetyl / stearyl / Behenyl), phytosteryl oleate, and N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl).

Among them, jojoba oil, octyldodecyl myristate, isopropyl isostearate, isotridecyl isononanoate, 2-ethylhexyl paramethoxycinnamate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl diisostearate, glyceryl triisostearate, N -Lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl) is preferred.
Further, isotridecyl isononanoate, 2-ethylhexyl paramethoxycinnamate, neopentyl glycol dicaprate, and diisostearyl malate are more preferred, and 2-ethylhexyl paramethoxycinnamate is more preferred.
These ester oils can be used alone or in combination of two or more.

  The ester oil that is liquid at 25 ° C. of component (E) can be used singly or in combination, has a good feeling of use, and suppresses the formation of lumps during coating. 0.1 mass% or more is preferable, 1 mass% or more is more preferable, 2 mass% or more is further more preferable, 15 mass% or less is preferable, 7 mass% or less is more preferable, and 5 mass% or less is further more preferable. Further, the content of the ester oil that is liquid at 25 ° C. of the component (E) is preferably 0.1 to 15% by mass, more preferably 1 to 7% by mass, and further preferably 2 to 5% by mass in the total composition. .

  In the present invention, the mass ratio (A) / (E) of the component (A) to the component (E) is preferably 0.03 or more from the viewpoint of good usability and suppressing formation of lumps during coating. 0.05 or more is more preferable, 0.1 or more is more preferable, 20 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable. Moreover, 0.03-20 are preferable, as for the mass ratio (A) / (E) of the component (A) with respect to a component (E), 0.05-5 are more preferable, and 0.1-3 are more preferable.

  The water-in-oil emulsified cosmetics of the present invention are components other than the above-mentioned components and used in ordinary cosmetics, for example, powders other than the component (A), oily components other than the above, surfactants, pigments, water-soluble And oil-soluble polymers, ethanol, polyhydric alcohol, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, UV absorbers, moisturizers, blood circulation promoters, cooling sensates, antiperspirants, Bactericides, skin activators, moisturizers and the like can be included.

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and the dosage form can be a liquid, emulsion, paste, cream, gel, etc. An emulsion or cream is 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.
The water-in-oil emulsified cosmetic of the present invention can be used in the case of using only a single product, or in the case of overlaying powder cosmetics such as liquid foundation, powder foundation, and white powder.

The water-in-oil emulsified cosmetic of the present invention preferably has a viscosity at 25 ° C. of 2000 to 200000 mPa · s, more preferably 3000 to 100000 mPa · s, from the viewpoint of blending stability, usability, and feeling of use. 3500-15000 mPa · s is more preferable.
Here, the viscosity is measured at 25 ° C. with a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVB-10 type viscometer, rotational speed 6 r / min, rotor No. M3, 1 min).
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B), (C) and (D):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 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 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) volatile oil,
(D) Water 1-70 mass%
The water-in-oil type emulsified cosmetics whose mass ratio (A) / (B) of the component (A) with respect to a component (B) is 0.02-40.

<2> The organic resin powder of component (A) is preferably an acrylic resin powder, and one or two kinds selected from acrylic acid esters, methacrylic acid esters, alkylene glycol acrylates, and alkylene glycol methacrylates The water-in-oil emulsified cosmetic according to <1>, wherein the above polymer is more preferable.
<3> The water-in-oil emulsion cosmetic according to <1> or <2>, wherein the spherical organic resin powder of component (A) is preferably surface-treated with tridecafluorooctyltriethoxysilane .
In the spherical organic resin powder of <4> component (A), the treatment amount of perfluoroalkylsilane is preferably 0.05% by mass or more based on the mass of the acrylic resin powder, and 0.1% Any of the above <1> to <3>, more preferably at least 0.5% by mass, more preferably at least 0.5% by mass, more preferably at most 50% by mass, more preferably at most 20% by mass, and even more preferably at most 8% by mass. 1. A water-in-oil emulsified cosmetic according to 1.

<5> The powder of component (A) is preferably any one of the above items <1> to <4>, preferably having a particle size of 0.1 to 0.7 μm and more preferably 0.2 to 0.5 μm. The water-in-oil emulsified cosmetic described.
<6> The powder of component (A) is preferably any one of the above items <1> to <5>, preferably having an average particle size of 0.1 to 0.5 μm and more preferably 0.3 to 0.4 μm 1. A water-in-oil emulsified cosmetic according to 1.
<7> 30% by mass or more of all spherical organic resin powders are preferably spherical organic resin powders having a particle size of 0.01 μm or more and 1.0 μm or less, more preferably 50% by mass or more, and 75% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <6>, wherein the above is more preferable.
The content of <8> component (A) is preferably 0.3% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 15% by mass. The water-in-oil emulsion cosmetic according to any one of the above items <1> to <7>, preferably 10% by mass or less, more preferably 8% by mass or less.
<9> The fluorine-modified silicone oil of the component (B) is preferably a fluorine-modified silicone composed only of polysiloxane units represented by the general formulas (1) and (2), which has the following general formula (3 )

(Wherein p and s have the same meaning as described above, and q represents a number of 5)
The water-in-oil emulsified cosmetic according to any one of <1> to <8>, wherein the fluorine-modified silicone represented by
The content of <10> component (B) is preferably 0.1% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 30% by mass. The water-in-oil emulsified compound according to any one of <1> to <9>, wherein the following is preferable, 15% by mass or less is more preferable, and 9% by mass or less is further preferable.
<11> The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.03 or more, more preferably 0.04 or more, and further preferably 0.4 or more. 20 or less is preferable, 10 or less is more preferable, and 4 or less is more preferable. The water-in-oil emulsion cosmetic according to any one of <1> to <10>.

<12> The volatile oil of component (C) is preferably a volatile hydrocarbon oil or a volatile silicone oil, and more preferably a volatile silicone oil. Water-in-oil emulsified cosmetic.
The content of <13> component (C) is preferably 1% by mass or more in the total composition, more preferably 7% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, 40 mass% or less is more preferable, and 30 mass% or less is still more preferable.
The water content of <14> component (D) is preferably 15% by mass or more, more preferably 25% by mass or more, preferably 45% by mass or less, and more preferably 40% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of the above items <1> to <13>.

<15> Further, as component (E), an ester oil which is liquid at 25 ° C. can be contained, and ester oil which is liquid at 25 ° C. is preferably jojoba oil, octyldodecyl myristate, isopropyl isostearate, isononane Isotridecyl acid, 2-ethylhexyl paramethoxycinnamate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl diisostearate, glyceryl triisostearate, di-N-lauroyl-L-glutamate (phytosteryl behenyl 2-octyldodecyl) And is more preferably isotridecyl isononanoate, 2-ethylhexyl paramethoxycinnamate, neopentyl glycol dicaprate, diisostearyl malate, and 2-ethylhexyl paramethoxycinnamate is further Masui the <1> to <14> or 1 water-in-oil type emulsified cosmetic according to.
<16> The content of the ester oil which is liquid at 25 ° C. of the component (E) is preferably 0.1% by mass or more in the total composition, more preferably 1% by mass or more, and more preferably 2% by mass or more. More preferably, 15 mass% or less is preferable, 7 mass% or less is more preferable, and 5 mass% or less is further more preferable, The water-in-oil type emulsion cosmetic in any one of said <1>-<15>.

<17> The mass ratio (A) / (E) of the component (A) to the component (E) is preferably 0.03 or more, more preferably 0.05 or more, and further preferably 0.1 or more. 20 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
<18> The viscosity at 25 ° C. is preferably 2000 to 200000 mPa · s, more preferably 3000 to 100000 mPa · s, and further preferably 3500 to 15000 mPa · s, and any one of the above <1> to <17> The water-in-oil emulsified cosmetic described.

Synthesis Example 1 (Synthesis 1 of fluorine-modified silicone)

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 2 of fluorine-modified silicone)

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%).

Examples 1-9 and Comparative Examples 1-3
Manufactures water-in-oil emulsified cosmetics (foundations) with the composition shown in Table 1, spreadability on the skin, no catching at the initial stage of application, difficulty of lumps during application, and difficulty of slipping during application And the point which can be finished with one coat was evaluated. The results are also shown in Table 1.

(Manufacturing method)
The powder phase component was mixed and ground, added to the separately mixed oil phase component, and dispersed with a disper. Then, the water phase component was added, dispersed with a disper, and then stirred with a homomixer to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
(I) When 10 expert evaluators applied each water-in-oil type emulsified cosmetic to the skin, the spreadability on the skin, the lack of catching at the initial stage of application, the difficulty of applying lumps during application, The difficulty of slipping was evaluated by sensory evaluation according to the following criteria. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.

(1) Spreadability on the skin:
5; The spread on the skin is very fast.
4; Good spread on the skin.
3; Slightly spreading on the skin.
2: The spread on the skin is not so good.
1: The spread on the skin is not good.

(2) No catch at the beginning of application:
5: Feels not caught in the initial stage of application.
4; Almost no initial catching feeling.
3; A slight feeling of catching at the initial stage of application is felt.
2; Feeling a catch at the initial stage of application.
1; A feeling of catching at the initial stage of application is considerably felt.

(3) Difficulty of lumps during application:
5; No lumps.
4; Slight lumps are seen.
3; Dama is slightly noticeable.
2; Dama stands out.
1; Dama is quite noticeable.

(4) Difficult to slide up during application:
5; Cosmetics do not slide on the skin.
4; Cosmetics do not slide too much on the skin.
3; The cosmetic slips slightly on the skin.
2; Cosmetics slide up on the skin.
1; Cosmetics slide considerably up on the skin.

(II) When 10 expert evaluators spread each water-in-oil emulsified cosmetic on the skin, can they apply the cosmetic without re-applying the same part of the skin many times? Sensory evaluation was performed according to the following criteria from the viewpoint of “finished by coating”. In addition, the evaluation result in a table | surface was sensory-evaluated by 10 expert evaluators in the following five steps, and was shown by the total score of 10 people.
(5) Finished with a single coat:
5: There is no re-coating during application, and it is quickly finished with a single application.
4; There is almost no re-coating during application, and it is finished with a single application.
3: Finished while partially repainting during application.
2: Finishing over time and the number of times of application while recoating during application.
1; Application cannot be performed well, and application time and frequency are very long.

Claims (5)

The following components (A), (B), (C) and (D):
(A) 0.1-20% by mass of a spherical organic resin powder having a particle size of 0.01 μm or more and 1.0 μm or less, which is surface-treated with perfluoroalkylsilane,
(B) 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 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) volatile oil,
(D) Water 1-70 mass%
The water-in-oil type emulsified cosmetics whose mass ratio (A) / (B) of the component (A) with respect to a component (B) is 0.02-40.   The water-in-oil emulsified cosmetic according to claim 1, wherein the component (A) is a spherical acrylic resin powder.   The water-in-oil emulsion makeup according to claim 1 or 2, wherein component (A) is one or more polymers selected from acrylic esters, methacrylic esters, alkylene glycol acrylates and alkylene glycol methacrylates. Fee.   The cosmetic according to any one of claims 1 to 3, wherein the surface treatment of the component (A) is a tridecafluorooctyltriethoxysilane treatment.   The water-in-oil emulsion makeup according to any one of claims 1 to 4, wherein 30% by mass or more of all spherical organic resin powders are spherical organic resin powders having a particle diameter of 0.01 µm to 1.0 µm. Fee.