JP6209442B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

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

Conventionally, zinc oxide and trimethylsiloxysilicic acid have been used in order to obtain cosmetics that are less likely to lose makeup and have a long lasting makeup. However, when these are used, the skin feels dry and tight after application. There was a problem that.
In order to improve this, various studies have been made. For example, in Patent Document 1, a cosmetic containing fluorine-modified silicone having a specific modification rate, fine-particle zinc oxide, hydrophobized powder, and trimethylsiloxysilicic acid is applied. It is described that the feeling of subsequent tension and unevenness is suppressed, and it is excellent in makeup. Patent Document 2 discloses that cosmetics containing trimethylsiloxysilicic acid, fine-particle zinc oxide, hyaluronic acid and / or a salt thereof are smooth and uniform on the skin because the dryness and tension of the skin after application are suppressed. It is described that it can be applied.

JP 2013-181007 A JP 2013-181209 A

  Cosmetics containing zinc oxide and trimethylsiloxysilicic acid are excellent in longevity. However, recent foundations are not only effective in maintaining makeup and making the skin look beautiful, but there is a growing need for clearing skin problems, and there is a need for a foundation that has no noticeable wrinkles in the finished skin after application. .

  The present inventors have used trimethylsiloxysilicic acid and fine particle zinc oxide together with a specific fluorosilicone resin and specific silica in spite of containing trimethylsiloxysilicic acid which is a film forming agent. While suppressing stickiness, the time from application to skin is fast, the finish of the makeup is fast, and when used as a makeup base, drying of the skin after overlaying the powder foundation is suppressed, and finely powdered It has been found that a water-in-oil emulsified cosmetic can be obtained that has a finish that does not accumulate, and that is also excellent in suppressing makeup collapse, stickiness, and providing a smooth feeling after application for a long time. It was.

The present invention includes the following components (A), (B), (C) and (D):
(A) Trimethylsiloxysilicic acid 0.01 to 20% by mass,
(B) The following general formula (1)
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8, which is arbitrarily selected from a functional group having a hydroxyl group and a general formula —R ² —Rf as essential, and a is an average number of 1.0 ≦ a ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g,
(D) Spherical silica having an average particle diameter of ^{2 to} 10 μm, a specific surface area of 50 to 400 m ² / g, and an oil absorption of 200 mL / 100 g or less 0.1 to 15% by mass
The present invention relates to a water-in-oil emulsified cosmetic containing

  Although the water-in-oil emulsified cosmetic of the present invention contains trimethylsiloxysilicic acid, which is a film-forming agent, the time from application to skin is fast while suppressing stickiness, The finish is fast. Moreover, when used as a makeup base, drying of the skin after the powder foundation is overlaid is suppressed, and a finish in which fine powder does not accumulate is obtained. Furthermore, the water-in-oil emulsified cosmetic of the present invention is excellent in terms of suppressing makeup collapse, stickiness, and imparting a feeling of smoothness after a long time has elapsed after application.

The trimethylsiloxysilicic acid of the component (A) used in the present invention is not limited as long as it is usually used in cosmetics, and any compound can be used, and it is a compound having a crosslinked structure with a siloxane structure as the main skeleton. , [(CH ₃ ) ₃ SiO _1/2 ] _X [SiO ₂ ] _Y (X is 1 to 3, Y is 0.5 to 8).
Moreover, trimethylsiloxysilicic acid has a weight average molecular weight of preferably 1000 to 10,000, more preferably 2000 to 9000, and still more preferably 3000 to 6000, from the viewpoint of feeling of use and longevity. In addition, the property may be any of liquid, gum, paste, solid, etc. at 25 ° C., but from the viewpoint of long-lasting makeup, a solid product is preferred. Further, from the viewpoint of compoundability, it is preferably a solution or dispersion diluted with a solvent, or a solution or dispersion obtained by mixing in advance. As the solvent for diluting or dispersing the component (A), one or more selected from dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and isododecane are preferable. Volatile dimethylpolysiloxane, deca More preferred is methylcyclopentasiloxane. In addition, volatility has a flash point of 35-90 degreeC.
As a commercial item of a component (A), KF-7312T, KF-7312J, KF-7312K (above, Shin-Etsu Chemical Co., Ltd. product) etc. which were previously melt | dissolved in the solvent can be used conveniently.

  Component (A) can be used singly or in combination of two or more, and the content is 0.01% by mass or more and 0.5% by mass or more in the total composition from the viewpoint of feeling of use and makeup. 2 mass% or more is more preferable, 20 mass% or less is preferable, 10 mass% or less is preferable, and 6 mass% or less is more preferable. Moreover, content of a component (A) is 0.01-20 mass% in the whole composition, 0.5-10 mass% is preferable, and 2-6 mass% is more preferable.

The component (B) fluorine-modified silicone resin used in the present invention has a structure represented by the general formula (1), and contains a hydroxyl group and a general formula —R ² —Rf as essential functional groups in the molecule. It is a waste.
The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to skin and powder, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass with respect to the resin mass. Of 0.5 to 5% by mass is more preferable.

  The fluorine-modified silicone resin is solid at 25 ° C. From the standpoint of the obtained cosmetic durability and blendability, it is preferably a solution or dispersion diluted with a solvent, or a solution or dispersion obtained by mixing in advance. As the solvent for diluting or dispersing the component (B), one or more selected from dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and isododecane are preferable. Volatile dimethylpolysiloxane, deca More preferred is methylcyclopentasiloxane. In addition, volatility has a flash point of 35-90 degreeC.

  As such a fluorine-modified silicone resin, INCI names “Trifluoropropyldimethyl / Trimethylsiloxysilicate”, XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive Performance Materials) Commercially available products such as those manufactured by the company) can be used.

  The component (B) can be used alone or in combination of two or more, and the content is 0.01% by mass or more and 0.2% by mass or more in the total composition from the point of use feeling and longevity. 1 mass% or more is more preferable, 20 mass% or less is preferable, 10 mass% or less is preferable, and 4 mass% or less is more preferable. Moreover, content of a component (B) is 0.01-20 mass% in the whole composition, 0.2-10 mass% is preferable, and 1-4 mass% is more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) is such that even after 6 hours have passed since the application, makeup collapse and stickiness are suppressed, and the feeling of smooth use is maintained. 0.05 or more, 0.2 or more is more preferable, 0.6 or more is more preferable, 30 or less is preferable, 10 or less is more preferable, and 4 or less is more preferable. Moreover, 0.05-30 are preferable, as for the mass ratio (A) / (B) of a component (A) and (B), 0.2-10 are more preferable, and 0.6-4 are more preferable.

Particulate zinc oxide component (C) 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 fine particle zinc oxide of component (C) 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 (C) 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 of excellent cosmetic durability and good usability. More preferably, 5 mass% or more is more preferable, 1 mass% or more is more preferable, 20 mass% or less is preferable, 12 mass% or less is more preferable, and 8 mass% or less is further more preferable. In addition, the content of the component (C) is preferably 0.1 to 20% by mass, more preferably 0.5 to 12% by mass, and further preferably 1 to 8% by mass in the entire composition.

The component (D) silica used in the present invention is a spherical silica having an average particle diameter of ^{2 to} 10 μm, a specific surface area of 50 to 400 m ² / g, and an oil absorption of 200 mL / 100 g or less, and is preferably porous. By using such a silica, it is excellent in long-lasting makeup sustainability and a smooth feeling can be obtained.
Here, 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 average particle size of the component (D) is preferably from 3 to 9 μm, more preferably from 4 to 8 μm from the viewpoint that makeup collapse and stickiness are suppressed even after a lapse of time after application and the feeling of smooth use is maintained.
The specific surface area of the component (D) is such that, even after a lapse of time after application, makeup collapse and stickiness are suppressed, the feeling of smoothness is maintained, the skin after applying the powder foundation repeatedly does not dry, terms nor the powder accumulation, preferably ^{75~260m 2 / g, 100~200m 2 /} g is more preferable.
Furthermore, the amount of oil absorption of the component (D) is such that even after a lapse of time after application, makeup collapse and stickiness are suppressed, the feeling of smooth use is maintained, and the skin after applying the powder foundation repeatedly does not dry, 10 to 150 mL / 100 g is preferable, and 40 to 100 mL / 100 g is more preferable from the viewpoint that fine powder does not accumulate.

  In addition, the spherical silica of component (D), even after a lapse of time after application, makeup collapse, stickiness is suppressed, the feeling of smooth use is maintained, the skin after applying powder foundation repeatedly does not dry, From the viewpoint that fine powder does not accumulate, the pore volume is preferably 0.05 to 1.0 mL / g, more preferably 0.1 to 0.6 mL / g.

In the present invention, the average particle diameter, specific surface area, oil absorption, and pore volume of spherical silica are measured by the following methods.
(1) Average particle size:
A slurry liquid (solid content concentration: 0.1 to 5% by mass) in which spherical silica is dispersed in a 40% by mass glycerin-containing aqueous solution is prepared, and this is applied to an ultrasonic generator (made by Iuch, US-2 type). Disperse for 5 minutes. Next, a sample is taken from the dispersion whose concentration has been adjusted by adding the glycerin aqueous solution, and the sample is placed in a glass cell (size of 10 mm in length, 10 mm in width, and 45 cm in height). The average particle size is measured using a product manufactured by CAPA-700.

(2) Specific surface area:
About 30 mL of spherical silica is collected in a magnetic crucible (type B-2), dried at a temperature of 150 ° C. for 2 hours, then placed in a desiccator and cooled to room temperature. Next, 1 g of a sample is taken, and the specific surface area (m ² / g) is measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).

(3) Oil absorption:
1.5 g of spherical silica is collected on a medicine wrapping paper and transferred to a glass measuring plate. Next, 4 or 5 drops of oil (as defined in JIS K 5101) is added to the sample at a time from the burette, and the whole is kneaded with a spatula. This dripping and kneading are repeated, and the oil absorption amount is calculated by the following formula, with the end point being when the spiral is wound.
Oil absorption (mL / 100g) = (A / W) × 100
(A is the amount of oil dripped in boiled sesame (mL), W is the amount of sample collected (g))

(4) Pore volume:
Take 10 g of spherical silica in a crucible, dry at 105 ° C. for 1 hour, put in a desiccator and cool to room temperature. Next, a 1 g sample is taken into a well-washed cell, nitrogen is adsorbed using a nitrogen adsorption device (manufactured by Catalyst Kasei Kogyo Co., Ltd.), and the pore volume is calculated from the following equation.
Pore volume (mL / g) = (0.001567 × (V−Vc) / w)
(V is the adsorption amount (mL) in the standard state at a pressure of 735 mmHg, Vc is the capacity (mL) of the cell blank at a pressure of 735 mmHg, W is the weight (g) of the sample, and the ratio of the density of nitrogen gas and liquid nitrogen Is 0.001567)

  As the spherical silica of component (D), commercially available products such as SATINER M5, SILICA MICRO BEAD L-1500 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) can be used.

  Component (D) can use 1 type (s) or 2 or more types, Even if 6 hours pass after application | coating, makeup collapse and stickiness are suppressed and the feeling of smooth use is maintained. In addition, when used as a makeup base, the skin after applying the powder foundation does not dry and the powder does not accumulate finely, so that it is 0.1% by mass or more and 0.5% by mass in the total composition. The above is preferable, 1 mass% or more is more preferable, 15 mass% or less is preferable, 12 mass% or less is preferable, and 8 mass% or less is more preferable. Moreover, content of a component (D) is 0.1-15 mass% in all the compositions, 0.5-12 mass% is preferable, and 1-8 mass% is more preferable.

  In the present invention, the mass ratio (A) / (D) of the components (A) and (D) is such that the cosmetic coating film immediately after application does not become uneven, and the time from application to skin becomes early, and the time after application Even after a while, makeup collapse and stickiness are suppressed, the feeling of smoothness is maintained, the skin after applying the powder foundation repeatedly does not dry, and the powder does not accumulate finely. 05 or more is preferable, 0.1 or more is more preferable, 0.3 or more is more preferable, 30 or less is preferable, 10 or less is more preferable, and 5 or less is more preferable. Moreover, 0.05-30 are preferable, as for mass ratio (A) / (D) of a component (A) and (D), 0.1-10 are more preferable, and 0.3-5 are more preferable.

  In addition, the mass ratio (C) / (D) of the components (C) and (D) is such that the cosmetic coating film immediately after application does not become uneven and the time from application to skin adapts quickly, and the time after application elapses. However, it is more than 0.03 because it prevents the makeup from being broken and sticky, keeps the feeling of smoothness, does not dry the skin after applying the powder foundation, and does not accumulate fine powder. Is preferable, 0.05 or more is more preferable, 0.2 or more is more preferable, 40 or less is preferable, 20 or less is more preferable, and 7 or less is more preferable. Moreover, 0.03-40 are preferable, as for the mass ratio (C) / (D) of a component (C) and (D), 0.05-20 are more preferable, and 0.2-7 are more preferable.

  Furthermore, the mass ratio ((A) + (B)) / (D) of the components (A) and (B) and the component (D) does not cause unevenness in the cosmetic coating film immediately after application, and it is applied to the skin. Even before the application time is long, the makeup break-up and stickiness are suppressed, the feeling of smoothness is maintained, the skin after applying the powder foundation repeatedly does not dry, and the powder is finely wrinkled. Is preferably 0.03 or more, more preferably 0.2 or more, further preferably 0.5 or more, preferably 50 or less, more preferably 20 or less, and even more preferably 8 or less. Moreover, 0.03-50 are preferable and, as for the mass ratio ((A) + (B)) / (D) of a component (A) and (B) and a component (D), 0.2-20 are more preferable. 0.5 to 8 is more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain (E) a fluorine-modified silicone, can suppress unevenness, and can improve the long lasting makeup.
As fluorine-modified silicone, 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 ¹¹ , R ¹² and R ¹³ 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)
A fluorine-modified silicone having a polysiloxane unit represented by

In the formula, examples of the hydrocarbon group represented by R ¹¹ , R ¹² and R ¹³ include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; 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.

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

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

  Component (E) can be used singly or in combination of two or more, and the content is 0.1% by mass or more in the total composition from the viewpoint of suppressing unevenness, having good makeup, and having excellent makeup. 1 mass% or more is more preferable, 2 mass% or more is more preferable, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable. Moreover, 0.1-20 mass% is preferable in the whole composition, as for content of a component (E), 1-15 mass% is more preferable, and 2-10 mass% is further more preferable.

  The content of water used in the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 70% by mass or less, and preferably 60% by mass in the total composition from the viewpoint of usability and storage stability. The following is more preferable. Moreover, 10-70 mass% is preferable in the whole composition, and, as for content of water, 20-60 mass% is more preferable.

In addition, the oil used in the present invention is other than the component (E) and is preferably liquid at 20 ° C. When a solid or paste oil is used, it is once dissolved in another oil or solvent. It is preferable to use after using.
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.
In addition, the content of the oil used in the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more in the total composition, from the viewpoint of usability and storage stability. 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is further more preferable. Moreover, 1-50 mass% is preferable in the whole composition, as for content of an oil agent, 5-40 mass% is more preferable, and 10-30 mass% is further 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. The nonionic surfactant preferably has an HLB value of 1 or more and 7 or less, and an HLB value of 2 or more from the viewpoint of stably emulsifying the aqueous phase in the oil phase containing the components (A) and (B) and other oil agents. 6 or less are 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 content of the surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 6% by mass or less, and more preferably 3% by mass or less in the total composition. Moreover, 0.1-6 mass% is preferable in the whole composition, and, as for content of surfactant, 0.2-3 mass% is more preferable.

  The water-in-oil emulsified cosmetic of the present invention includes components used in normal cosmetics in addition to the above components, such as water-soluble and oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives , Antioxidants, pigments, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling 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 is preferred.

In addition, the water-in-oil emulsified cosmetic of the present invention comprises makeup foundations, liquid foundations, oily foundations, powder foundations, lipsticks, blushers, eye shadows, and other make-up cosmetics; It can be a protective cosmetic. Of these, a makeup base and a liquid foundation are preferable.
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B), (C) and (D):
(A) Trimethylsiloxysilicic acid 0.01 to 20% by mass,
(B) The following general formula (1)
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8, which is arbitrarily selected from a functional group having a hydroxyl group and a general formula —R ² —Rf as essential, and a is an average number of 1.0 ≦ a ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g,
(D) Spherical silica having an average particle diameter of ^{2 to} 10 μm, a specific surface area of 50 to 400 m ² / g, and an oil absorption of 200 mL / 100 g or less 0.1 to 15% by mass
Water-in-oil emulsified cosmetic containing

<2> The trimethylsiloxysilicate of component (A) is preferably represented by [(CH ₃ ) ₃ SiO _1/2 ] _X [SiO ₂ ] _Y (X is 1-3, Y is 0.00. The water-in-oil emulsified cosmetic according to <1>, which is 5 to 8).
<3> The trimethylsiloxysilicic acid of component (A) preferably has a weight average molecular weight of 1000 to 10,000, more preferably 2000 to 9000, and further preferably 3000 to 6000. <1> or <2> Water-in-oil emulsified cosmetic.
The content of <4> component (A) is preferably 0.5% by mass or more, more preferably 2% by mass or more, more preferably 10% by mass or less, and more preferably 6% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of the above <1> to <3>.

<5> The fluorine-modified silicone resin of component (B) preferably has a silanol group in the molecule, and the ratio of the OH group in the silanol group is 0.1 to 5% by mass relative to the resin mass. The water-in-oil emulsified cosmetic according to any one of <1> to <4>, wherein 0.5 to 5% by mass is more preferable.
<6> The water-in-oil type according to any one of <1> to <5>, wherein the fluorine-modified silicone resin of component (B) is preferably trifluoropropyldimethyl / trimethylsiloxysilicate. Emulsified cosmetic.
The content of <7> component (B) is preferably 0.2% by mass or more in the total composition, more preferably 1% by mass or more, and preferably 10% by mass or less, and more preferably 4% by mass or less. The water-in-oil type emulsified cosmetic according to any one of the above items <1> to <6>.
<8> The mass ratio (A) / (B) of the components (A) and (B) is preferably 0.05 or more, more preferably 0.2 or more, still more preferably 0.6 or more, 30 or less is preferable, 10 or less is more preferable, and 4 or less is more preferable. The water-in-oil emulsified cosmetic according to any one of <1> to <7>.

<9> The finely divided zinc oxide component (C) is preferably a water-in-oil emulsified cosmetic according to any one of <1> to <8>, wherein the specific surface area is 15 to 95 m ² / g. .
<10> The fine particle zinc oxide of component (C) is preferably water-repellent and / or oil-repellent treated, more preferably silicone-treated, and silicone treatment using methylhydrogenpolysiloxane The water-in-oil emulsified cosmetic according to any one of the above items <1> to <9>, which is more preferable.
The content of <11> component (C) 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 20% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <10>, wherein the following is preferable, 12% by mass or less is more preferable, and 8% by mass or less is further preferable.

The spherical silica of <12> component (D) is preferably an average particle diameter of 3 to 9 μm, and more preferably 4 to 8 μm. Water-in-oil emulsification according to any one of the above <1> to <11> Cosmetics.
<13> spherical silica component (D) is preferably a specific surface area ^{75~260m 2 / g, 100~200m 2 /} g and more preferably the <1> to any one of the described <12> Water-in-oil emulsified cosmetic.
<14> The spherical silica of component (D) is preferably in the oil according to any one of the above items <1> to <13>, wherein the oil absorption is 10 to 150 mL / 100 g, and 40 to 100 mL / 100 g is more preferable. Water-type emulsified cosmetic.
<15> The spherical silica of the component (D) is preferably a porous volume of 0.05 to 1.0 mL / g, more preferably 0.1 to 0.6 mL / g. <14> The water-in-oil emulsified cosmetic according to any one of <14>.
The content of <16> component (D) is preferably 0.5% by mass or more in the total composition, more preferably 1% by mass or more, preferably 12% by mass or less, and more preferably 8% by mass or less. The water-in-oil emulsified cosmetic according to any one of the above <1> to <15>.

<17> The mass ratio (A) / (D) of the components (A) and (D) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.3 or more, 30 or less is preferable, 10 or less is more preferable, and 5 or less is more preferable. The water-in-oil emulsified cosmetic according to any one of the above items <1> to <16>.
<18> The mass ratio (C) / (D) of the components (C) and (D) is preferably 0.03 or more, more preferably 0.05 or more, and further preferably 0.2 or more, 40 or less is preferable, 20 or less is more preferable, and 7 or less is more preferable. The water-in-oil emulsified cosmetic according to any one of the above items <1> to <17>.
<19> The mass ratio ((A) + (B)) / (D) of the components (A) and (B) and the component (D) is preferably 0.03 or more and 0.2 or more. More preferably, 0.5 or more is more preferable, 50 or less is preferable, 20 or less is more preferable, and 8 or less is further more preferable, The water-in-oil type emulsion cosmetic in any one of said <1>-<18>.
<20> Furthermore, it contains (E) fluorine-modified silicone, preferably 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 ¹¹ , R ¹² and R ¹³ 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)
A fluorine-modified silicone having a polysiloxane unit represented by the following general formula (4)

(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 <19>, more preferably represented by formula (1).

The content of <21> component (E) is preferably 0.1% by mass or more in the entire composition, more preferably 1% by mass or more, further preferably 2% by mass or more, and 20% by mass or less. The water-in-oil emulsified cosmetic according to the above <20>, preferably 15% by mass or less, more preferably 10% by mass or less.
<22> The water content is preferably 10% by mass or more in the total composition, more preferably 20% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass or less <1>. The water-in-oil emulsified cosmetic according to any one of to <21>.

Production Example 1 (Production of inorganic pigment-containing polymer powder)
In a 1300 mL beaker, 56 g of lauryl methacrylate, 19 g of ethylene glycol dimethacrylate and 1.5 g of lauroyl peroxide were charged to obtain a solution. In addition, titanium oxide with an average particle size of 0.25 μm (CR-50, manufactured by Ishihara Sangyo Co., Ltd.), Bengala with an average particle size of 0.38 μm (Bengara Cloisonne, manufactured by Morishita Bengala), average particle size of 0.07 × 0.7 μm Yellow iron oxide (for needle shape) (Yellow LLXLO, manufactured by Titanium Industry Co., Ltd.) was mixed at a ratio of 95: 1: 4, and water repellent treatment (with respect to inorganic powder) using methylhydrogenpolysiloxane. 2%). Next, the obtained solution and the water-repellent treated inorganic pigment were mixed and dispersed so that the content of the inorganic pigment was 20% by mass to obtain a dispersion. To this dispersion was added 750 g of a 1% by weight polyvinyl alcohol (GOHSENOL GH-17, manufactured by Nippon Synthetic Chemical Industry) aqueous solution and dispersed using an ultrasonic disperser (the particle size can be controlled by time and strength). The obtained dispersion was charged into a 1000 mL separable flask, and then the gas phase in the separable flask was purged with nitrogen. Next, while stirring the dispersion at 150 r / min, polymerization was carried out at 75 ° C. for 8 hours under a nitrogen atmosphere. After the polymerization was completed, the obtained product was filtered to collect a solid, washed with water, and then dried under reduced pressure to obtain 120 g of an inorganic pigment-containing polymer powder having an average particle size of 10 μm.
About the obtained polymer powder, the transmittance | permeability and the haze value were measured with the following method.
As a result, the total transmittance was 60% and the haze value was 69.

(Measuring method)
The total transmittance and haze value of each powder were measured using Haze-meter HM-150 (Murakami Color Research Laboratory Co., Ltd.). For the measurement, light having a peak at a wavelength of 550 nm was used.
The sample was prepared as follows. 0.4 g of the powder is weighed and kneaded into 1.6 g of amino-modified silicone (SF8417, Toray Dow Corning) and applied to a glass plate. The kneading was performed at 100 revolutions using a Hoover Marler (kneader: YOSHIMITSU, Hoover Marler), after scraping once, and further kneading at 100 revolutions. The glass plate was coated using a 0.025 mm coater (manufactured by YOSHIMITSU, coater).

  The haze value (H) is calculated by multiplying the value obtained by dividing the diffuse transmittance (Td) by the total transmittance (Tt) by 100. In the present invention, the haze value (H) is the thickness of each sample. In order to eliminate the measurement error due to the above, it is a value (H15) converted to a value when each sample is 15 μm. The conversion formula is as follows. The thickness of the sample is measured using a film thickness meter (manufactured by YOSHIMITSU) after measuring the transmittance and haze value.

  In the formula, Tt is the total transmittance, Td is the diffuse transmittance, and L is the film thickness. For the film thickness, a value obtained by measuring the coating film after measurement with a film thickness meter is used.

Production Example 2 (Production 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 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%).

Production Example 3 (Production of poly (N-propionylethyleneimine) -modified silicone)
12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate were mixed, and the mixture was 2.0 g of molecular sieve (Zeoram A-4, manufactured by Tosoh Corporation) at 28 ° C. 15 Time dehydration was performed.
Also, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shin-Etsu Silicone Co., Ltd., weight average molecular weight 100000, amine equivalent 20000) and ethyl acetate 203 g were mixed, and the mixture was 15.2 g of molecular sieve. Dehydration was performed at 28 ° C. for 15 hours.
To the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline was added 0.77 g (0.005 mol) of diethyl sulfate, and the mixture was heated to reflux at 80 ° C. for 8 hours under a nitrogen atmosphere, and terminal reactive poly (N-propionyl). Ethyleneimine) was synthesized. The number average molecular weight measured by GPC was 2700.
To this terminal-reactive poly (N-propionylethyleneimine) solution, the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution was added all at once and heated to reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g). The mass ratio of the organopolysiloxane segment in the final product was 0.87, and the weight average molecular weight of the final product was 115,000.

Examples 1-11, Comparative Examples 1-4
When water-in-oil emulsified cosmetics having the composition shown in Table 1 were produced and each cosmetic was applied, “fastness from application of cosmetic to skin conforming”, “no unevenness immediately after application” The evaluation was “Suppression of makeup loss”, “Suppression of stickiness” and “Sustained smoothness” 6 hours after application. Next, after applying each cosmetic, a powder foundation was applied, and the “fine wrinkle state (powder accumulation)” and “no dryness” after application were evaluated. The results are also shown in Table 1.

(Production method)
About Examples 1-11 and Comparative Examples 1-4, the whole quantity is measured with a scale of 100 g. The oil phase (including the active agent) containing the components (A) and (B) is preliminarily dispersed using a disper (1500 r / min, 5 minutes). Next, the powder phase containing components (C) and (D) is dispersed in the oil phase (3000 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 a water phase while stirring with a disper (1500 r / min), then add an ethanol phase to emulsify and retain the emulsification. The viscosity was adjusted (5000 r / min) and defoamed to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
Five specialist panelists immediately applied each water-in-oil emulsified cosmetic to their skin with "fastness from application of cosmetics to skin,""no unevenness immediately after application", “Suppression of makeup loss”, “Suppression of stickiness” and “Sustained smoothness” after 6 hours from application were evaluated. Next, after applying each cosmetic, powder foundation (Sofina Alblan Trans Clear White Foundation UV Powder, manufactured by Kao Corporation) is applied, and after application, “fine wrinkles (powder)” and “no dryness” Was evaluated according to the following criteria. A result is shown by the integrated value of 5 persons.

(1) Speed of time from cosmetic application to skin adjustment:
5: The time to adjust to the skin is very fast.
4: Time to adjust to skin is fast.
3: Slightly faster time to adjust to the skin.
2: Time to adjust to the skin is not so fast.
1: Time to adjust to skin is not fast

(2) No unevenness immediately after applying cosmetics:
5: Unevenness is not seen in the skin after application.
4: There is almost no unevenness in the skin after application.
3; Some unevenness is seen in the skin after application.
2: Unevenness is seen in the skin after application.
1: Unevenness is noticeably observed on the skin after application.

(3) Suppression of makeup loss after 6 hours from application:
5: There is no makeup collapse.
4; There is not much makeup collapse.
3; Some makeup collapse is seen.
2; makeup collapse is observed.
1; Makeup breakage is noticeable.

(4) Stickiness control after 6 hours from application:
5; I do not feel sticky.
4; I do not feel much stickiness.
3; I feel a little sticky.
2; I feel stickiness.
1; Stickiness is noticeable.

(5) Persistence of smoothness after 6 hours from application:
5; I feel very smooth.
4; I feel a smooth feeling.
3; I feel a little smooth.
2: I do not feel much smoothness.
1; Does not feel smooth.

(6) Fine wrinkles after powder foundation application (powder pool):
5: The powder does not easily accumulate in fine lines and the fine lines are not noticeable.
4: The powder does not easily accumulate in fine lines, and the fine lines are not so noticeable.
3; Powder accumulates in fine lines, and fine lines are slightly noticeable.
2: Powder accumulates in fine lines and the fine lines are conspicuous.
1; Powder accumulates in fine lines and the fine lines are noticeable.

(7) No dry feeling after applying powder foundation:
5; Does not feel dry.
4; Does not feel much dryness.
3; I feel a little dry.
2: Feels dry.
1; A feeling of dryness is considerably felt.

Claims (5)

The following components (A), (B), (C) and (D):
(A) Trimethylsiloxysilicic acid 0.01 to 20% by mass,
(B) The following general formula (1)
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf (R ² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon A perfluoroalkyl group having a number of 1 to 8, which is arbitrarily selected from a functional group having a hydroxyl group and a general formula —R ² —Rf as essential, and a is an average number of 1.0 ≦ a ≦ 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(C) Fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, 0.1 to 20% by mass ,
(D) Spherical silica having an average particle diameter of ^{2 to} 10 μm, a specific surface area of 50 to 400 m ² / g, and an oil absorption of 10 to 200 mL / 100 g 0.1 to 15% by mass
Water-in-oil emulsified cosmetic containing   The water-in-oil emulsified cosmetic according to claim 1, comprising 0.1 to 20% by mass of component (C).   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (D) of the components (A) and (D) is 0.05 to 30.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the mass ratio (A) / (B) of the components (A) and (B) is 0.05 to 30. Further, (E) 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 ¹¹ , R ¹² and R ¹³ 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)
The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, comprising 0.1 to 20% by mass of a fluorine-modified silicone having a polysiloxane unit represented by: