JP2016222599A - Water-in-oil type emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a difficult-to-remove water-in-oil type emulsion cosmetic, excellent in covering power, hardly removed even when rubbed, and forming an even coating even when a powder foundation is applied thereon.SOLUTION: The water-in-oil type emulsion cosmetic comprises: (A) a crosslinking polyether-modified silicone represented by formula (1); (B) a spherical silicone elastic powder; (C) a specific synthetic mica; and a volatile oil.(R is methyl or phenyl; R' is H, alkyl or acyl; and R" is an alkyl, acyl or siloxane.)SELECTED DRAWING: None

Description

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

  In order to improve the feeling of use and finish of cosmetics, cross-linked polyether-modified silicone is used. In Patent Document 1, a water-in-oil emulsified cosmetic containing a cross-linked polyether-modified silicone, a dextrin fatty acid ester and / or an inulin fatty acid ester, an acrylamide-based thickener, and a powder has a light and fresh feel. And excellent in powder dispersibility and stability over time. Patent Document 2 discloses that a water-in-oil emulsified cosmetic containing a cross-linked polyether-modified silicone, a fluorine-modified silicone and a fluorine compound-treated powder adheres evenly to the skin crevice and skin mound, It is described that it can be applied to the entire skin, prevents the skin from appearing rough, produces a finish with an inconspicuous feeling of powder, and makes the skin appear brighter.

JP 2010-116354 A JP 2014-101311 A

  The present inventors apply a water-in-oil emulsified cosmetic to the skin, and when the finished cosmetic skin is rubbed with a hand, cloth or tissue paper, the applied cosmetic coating is peeled off and the finish is significantly reduced. I found it.

  The present inventors have used a cosmetic coating film made of a specific cross-linked polyether-modified silicone in combination with a spherical silicone elastic powder and a plate-like synthetic mica, whereby the cosmetic coating film after volatile oil has been volatilized. It has been found that the spherical powder inside reduces excessive load on the decorative coating film, suppresses the ease of falling off the cosmetic, and does not easily fall even when rubbed with hands or cloth.

The present invention includes the following components (A), (B), (C) and (D):
(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)
0.1 to 15% by mass of a crosslinked polyether-modified silicone represented by
(B) Spherical silicone elastic powder having an average particle size of 10 to 50 μm, 0.1 to 10% by mass,
(C) 0.1-10% by mass of synthetic mica selected from synthetic phlogopite and iron-containing synthetic phlogopite
(D) It is related with the water-in-oil type emulsion cosmetics which contain volatile oil and whose mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.2-10.

  Since the water-in-oil emulsified cosmetic of the present invention forms a firm and uniform film on the skin crevice and hill, it has excellent coverage of stains and freckles, and the unevenness of pores is not noticeable, such as hands and cloth, Even if it is rubbed with tissue paper or the like, it is difficult to fall off, and even when a powder foundation is overlaid, it forms a uniform film and is difficult to fall off. Moreover, these effects last for a long time.

The crosslinked polyether-modified silicone of component (A) used in the present invention is represented by the general formula (1).
In the formula, R ″ is preferably an alkyl group having 1 to 15 carbon atoms. Further, g is a number of 0 to 15, h is a number of 1 to 40, i is a number of 10 to 200, and j is 1 to 50. The number k is preferably a number from 1 to 50.

The crosslinked polyether-modified silicone of component (A) can be produced, for example, by the method described in JP-A-4-72932.
The crosslinked polyether-modified silicone of component (A) is preferably diluted or dispersed in volatile hydrocarbon oil or silicone oil. As the volatile hydrocarbon oil, isododecane and polyisobutene are more 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). Commercially available products such as KSG-340 ((PEG-10 / lauryl dimethicone) cross polymer and (PEG-15 / lauryl dimethicone) cross polymer) (above, Shin-Etsu Chemical Co., Ltd.) can be used.

  The component (A) can be used alone or in combination of two or more, and the content thereof is excellent in the adhesion to the skin of the water-in-oil emulsified cosmetic and is uniform even when the powder foundation is overlaid. From the point of forming a thick film, it is 0.1% by mass or more in the total composition, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and 15% by mass. %, Preferably 10% by mass or less, more preferably 5% by mass, and even more preferably 3.5% by mass or less. Moreover, content of a component (A) is 0.1-15 mass% in all the compositions, 0.5-10 mass% is preferable, 1-5 mass% is more preferable, 1.5-3. 5 mass% is more preferable.

The spherical silicone elastic powder of component (B) used in the present invention is a composite polymer powder obtained by coating a silicone rubber spherical fine particle with a polyorganosilsesquioxane resin.
The spherical silicone elastic powder preferably has a rubber elasticity of 5 to 80, and more preferably 20 to 50. Rubber elasticity is measured by durometer A according to JIS K 7215.

  Such a spherical silicone elastic powder is prepared by, for example, adding a catalyst to an oil-based oil-in-water emulsion containing (a) a vinyl group-containing organopolysiloxane and (b) an organohydrogenpolysiloxane to cause a curing reaction. After the spherical silicone rubber cured product fine particle dispersion, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to the aqueous dispersion, and the organotrialkoxysilane is hydrolyzed, subjected to a condensation curing reaction, and then dried. Can be obtained. Details of the method for producing the composite powder are described in JP-A-7-196815.

The spherical silicone elastic powder of the component (B) has an average particle diameter of 10 to 50 μm, is excellent in slipperiness on the skin, has excellent adhesion to the skin, and forms a uniform film. 40 μm is preferred. The shape may be a spherical powder including a spherical shape, including a true sphere, a substantially spherical shape, and a spheroid, and having irregularities on the surface.
The particle diameter of the powder is measured by a particle size distribution measuring machine using a laser diffraction / scattering method. Specifically, 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.

  Such a spherical silicone elastic powder can be produced and used by the above-described production method, and a commercially available product can also be used. As a commercial item, Shin-Etsu Chemical Co., Ltd. make, KSP-101 (average particle diameter 12 micrometers, rubber elasticity 30), KSP-102 (average particle diameter 30 micrometers, rubber elasticity 30) etc. can be used, for example.

  The component (B) can be used alone or in combination of two or more, and the content thereof is excellent in the adhesion to the skin of the water-in-oil emulsified cosmetic, and is uniform even when the powder foundation is overlaid. From the point of forming a thin film, it is 0.1% by mass or more in the total composition, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, It is 10 mass% or less, 7 mass% or less is preferable, 5 mass% is more preferable, and 3 mass% or less is further more preferable. Moreover, content of a component (B) is 0.1-10 mass% in the whole composition, 0.2-7 mass% is preferable, 0.3-5 mass% is more preferable, 0.5- 3% by mass is more preferable.

  In the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is excellent in adhesion to the skin, and it is easy to form a firm and uniform film on the skin crevice and cuticle. In view of excellent covering power of stains and freckles and long-lasting effect, 0.2 or more is preferable, 0.4 or more is more preferable, 0.6 or more is more preferable, 20 or less is preferable, and 12 or less is More preferred is 6 or less. Moreover, 0.2-20 are preferable, as for the mass ratio (A) / (B) of the component (A) with respect to a component (B), 0.4-12 are more preferable, and 0.6-6 are more preferable.

The component (C) synthetic mica is selected from synthetic phlogopite and iron-containing synthetic phlogopite.
Examples of the synthetic phlogopite include those obtained by mixing and melting anhydrous silicic acid, aluminum oxide, magnesium oxide, and potassium silicofluoride, crystallizing crystals, pulverizing, and heat treatment.
Examples of the iron-containing synthetic phlogopite include those obtained by mixing and melting silicic anhydride, aluminum oxide, magnesium oxide, potassium silicofluoride, and iron oxide, crystallizing crystals, pulverizing, and heat treatment. The iron-containing synthetic phlogopite preferably has an iron content of 0.5 to 10% by mass in terms of iron oxide from the viewpoint of giving a highly transparent finish.

The shape of these synthetic mica is preferably flaky, and the average particle size is excellent in adhesion to the skin, and it is easy to form a firm and uniform film on the skin crevice and hill. 5-100 micrometers is preferable and 5-40 micrometers is more preferable from the point which is excellent in covering power and an effect lasts for a long time. The aspect ratio is preferably 15 to 100, and more preferably 20 to 80.
In the present invention, the average particle diameter 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, ethanol is used as a dispersion medium and measured with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.), and the 50% median diameter is the average particle diameter. And The thickness is determined by measuring the difference from the reference plane with an atomic force microscope, and calculating the arithmetic mean to obtain the average thickness.
The aspect ratio is calculated by the ratio between the average particle diameter and the average thickness, and is defined by aspect ratio = (average particle diameter / average thickness).

  Such synthetic mica can be produced and used by the above-described production method, and a commercially available product can also be used. Examples of commercially available products include PDM-1000 (average particle size 12 μm, aspect ratio 20), PDM-10L (average particle size 12 μm, aspect ratio 60), PDM-20L (average particle size 20 μm, aspect ratio) manufactured by Topy Industries, Ltd. Ratio 70), PDM-40L (average particle diameter 40 μm, aspect ratio 80), PDM-NFES (average particle diameter 5 μm, aspect ratio 40) and the like can be used.

  Component (C) can be used alone or in combination of two or more thereof, and its content is excellent in adhesion to the skin, and it is easy to form a firm and uniform film on the skin crevice and hill. -From the point that the freckle has excellent covering power and the effect lasts for a long time, it is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, in the total composition. More preferably, it is 10 mass% or less, 8 mass% or less is more preferable, 6 mass% is more preferable, and 4 mass% or less is further more preferable. Moreover, content of a component (C) is 0.1-10 mass% in the whole composition, 0.2-8 mass% is preferable, 0.5-6 mass% is more preferable, 1-4 mass % Is more preferable.

  In the present invention, the mass ratio (A) / (C) of the component (A) to the component (C) is excellent in adhesion to the skin, and it is easy to form a firm and uniform film on the skin crevice and cuticle. , Excellent covering power for freckles and freckles, unevenness of pores is not conspicuous, difficult to rub off with hands, cloth, tissue paper etc., and even when powder foundation is overlaid, a uniform film is formed, From the point that it is difficult to drop and the effect lasts for a long time, it is 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, 10 or less, 6 or less, and 3 or less. Moreover, mass ratio (A) / (C) of the component (A) with respect to a component (C) is 0.2-10, 0.3-6 are preferable and 0.4-3 are more preferable.

In the volatile oil of the component (D), volatile has a flash point of 35 to 87 ° C.
Any volatile oil may be used as long as it is used in ordinary cosmetics. For example, linear dimethylpolysiloxane such as dimethylpolysiloxane (1.5cs) and dimethylpolysiloxane (2cs); tris (trimethylsilyl). ) Branched siloxanes such as methylsilane and tetrakis (trimethylsilyl) silane; volatile silicone oils such as cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; isododecane, isotridecane, isohexadecane, etc. And volatile hydrocarbon oils; fluorine oils such as ethyl perfluorobutyl ether.
Among these, volatile silicone oils and volatile hydrocarbon oils are preferable from the viewpoint of excellent usability after the component (D) volatilizes after application to the skin and suppress discoloration, and dimethylpolysiloxane (1. 5cs), dimethylpolysiloxane (2cs), decamethylcyclopentasiloxane, and isododecane are more preferable.

  Component (D) can be used singly or in combination of two or more, and the content thereof is 10 in the total composition from the viewpoint of excellent use feeling after component (D) volatilizes and suppressing discoloration. % By mass or more is preferred, 15% by mass or more is more preferred, 22% by mass or more is more preferred, 60% by mass or less is preferred, 50% by mass is more preferred, and 40% by mass or less is further preferred. Moreover, 10-60 mass% is preferable in the whole composition, as for content of a component (D), 15-50 mass% is more preferable, and 22-40 mass% is further more preferable.

  The water-in-oil emulsified cosmetic of the present invention can further contain (E) spherical polyurethane particles. Polyurethane particles are preferably cross-linked urethane-based cross-linked polymers from the viewpoint of being hard to come off even if they are rubbed with hands, cloth, tissue paper, etc., especially hexamethylene diisocyanate / trimethylol hexyl lactone cross-linked. Polyurethane particles made of polymer / silicic anhydride are more preferred.

The average particle diameter of the spherical polyurethane particles of the component (E) is preferably 2 to 40 μm from the viewpoint that even when powder foundation is overlaid, it is difficult to fall off even by rubbing with hands, cloth, tissue paper or the like. -30 μm is more preferable, and 5-20 μm is more preferable. The shape of the polyurethane particles is spherical, and 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.
The particle diameter of the powder is measured by a particle size distribution measuring machine using a laser diffraction / scattering method. Specifically, 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.

  As such spherical polyurethane particles, plastic powder D-400 (average particle size 15 μm) manufactured by Tohoku Pigment Co., Ltd., plastic powder D-800 (average particle size 7 μm), and Daimic Beads UCN manufactured by Dainichi Seika Kogyo Co., Ltd. Commercial products such as -8070 CM clear (average particle diameter 7 μm), UCN-8150 CM clear (average particle diameter 15 μm), and the like can be used. Among them, plastic powder D-400 (average particle size 15 μm) manufactured by Tohoku Pigment, which is a polyurethane particle made of hexamethylene diisocyanate / trimethylol hexyl lactone cross-linked polymer / silicic anhydride, plastic powder D manufactured by Tohoku Pigment -800 (average particle diameter of 7 μm) is preferable.

  Ingredient (E) can be used alone or in combination of two or more thereof, and the content of the component (E) is not limited even when it is rubbed with hands, cloth, tissue paper, etc. 0.1 mass% or more is preferable in a composition, 0.5 mass% or more is more preferable, 1 mass% or more is further more preferable, 10 mass% or less is preferable, 6 mass% is more preferable, 4 mass% or less is further preferable. Moreover, 0.1-10 mass% is preferable in the whole composition, as for content of a component (E), 0.5-6 mass% is more preferable, and 1-4 mass% is further more preferable.

  In the present invention, the content of water is not particularly limited as long as it is an adjustable amount as a water-in-oil emulsified cosmetic, but it is preferably 5 to 60% by mass from the viewpoint of finish, 13-50 mass% is more preferable, and 23-40 mass% is further more preferable.

  Further, 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, oily components other than those described above, powders other than those described above, surfactants, perfumes, and moisturizers. , Cosmetic ingredients, medicinal ingredients, ultraviolet absorbers, thickeners, bactericides, pH adjusters, antioxidants, preservatives, inorganic salts, and the like.

Any of the powders used in the present invention can be used as it is, and further, one or two or more of these powders which have been subjected to a hydrophobic treatment can be used.
The hydrophobizing treatment is not limited as long as it is a treatment applied to normal cosmetic powders, and a surface treatment agent such as a fluorine compound, a silicone compound, a metal soap, an amino acid compound, or an oil agent is used, and a dry treatment is performed. What is necessary is just to perform a process, a wet process, etc. Specific examples of the surface treatment agent include fluorine compounds such as perfluoroalkyl phosphate esters and perfluoroalkylalkoxysilanes; methylhydrogenpolysiloxanes, cyclic silicones, one- or both-end trialkoxy group-modified organopolysiloxanes, etc. Examples include silicone compounds; metal soaps such as aluminum stearate and zinc stearate; amino acid compounds such as lauroyllysine.
Of these, fluorine compound treatment and silicone treatment are preferred, and fluorine compound treatment and silicone treatment may be used in combination.

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

The water-in-oil emulsified cosmetic of the present invention can be produced by a usual method, and is suitable as a skin cosmetic for emulsions, creams, foundations, makeup bases, concealers, lip balms, blushers, eye shadows, mascaras, etc. is there.
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B), (C) and (D):
(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)
0.1 to 15% by mass of a crosslinked polyether-modified silicone represented by
(B) Spherical silicone elastic powder having an average particle size of 10 to 50 μm, 0.1 to 10% by mass,
(C) 0.1-10% by mass of synthetic mica selected from synthetic phlogopite and iron-containing synthetic phlogopite
(D) A water-in-oil emulsified cosmetic containing a volatile oil and having a mass ratio (A) / (C) of the component (A) to the component (C) of 0.2 to 10.

<2> The crosslinked polyether-modified silicone of component (A) is preferably diluted or dispersed in volatile hydrocarbon oil or silicone oil, and more preferably diluted or dispersed in isododecane or polyisobutene. The water-in-oil type emulsified cosmetic described in <1> above.
The content of the <3> component (A) is preferably 0.5% by mass or more in the total composition, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and 10% by mass. The water-in-oil emulsified cosmetic according to <1> or <2> above, preferably 5% by mass or less, and more preferably 3.5% by mass or less.

<4> The spherical silicone elastic powder of the component (B) is preferably in the range of 5 to 80, more preferably 20 to 50, and any one of the above <1> to <3>. Water-in-oil emulsified cosmetic.
<5> The water-in-oil emulsified cosmetic according to any one of <1> to <4>, wherein the spherical silicone elastic powder of component (B) preferably has an average particle size of 10 to 40 μm.
The content of <6> component (B) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more in the total composition, 7 The water-in-oil emulsified cosmetic according to any one of <1> to <5>, preferably 5% by mass or less, more preferably 5% by mass, and still more preferably 3% by mass or less.
<7> The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.2 or more, more preferably 0.4 or more, and even more preferably 0.6 or more. 20 or less, more preferably 12 or less, and even more preferably 6 or less, The water-in-oil emulsified cosmetic according to any one of <1> to <6>.

The synthetic mica of <8> component (C) is preferably flaky and has an average particle diameter of preferably 5 to 100 μm, more preferably 5 to 40 μm, and an aspect ratio of preferably The water-in-oil emulsified cosmetic according to any one of <1> to <7>, which is 15 to 100, and more preferably 20 to 80.
The content of <9> component (C) is preferably 0.2% by mass or more in the total composition, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and 8% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <8>, preferably 6% by mass or less, and more preferably 4% by mass or less.
<10> The mass ratio (A) / (C) of the component (A) to the component (C) is preferably 0.3 or more, more preferably 0.4 or more, preferably 6 or less, and 3 or less. The water-in-oil type emulsified cosmetic according to any one of the above items <1> to <9>, wherein

<11> The volatile oil of component (D) is preferably a volatile silicone oil or a volatile hydrocarbon oil, and includes dimethylpolysiloxane (1.5 cs), dimethylpolysiloxane (2 cs), and decamethylcyclopenta The water-in-oil emulsified cosmetic according to any one of <1> to <10>, wherein siloxane and isododecane are more preferable.
The content of <12> component (D) is preferably 10% by mass or more in the total composition, more preferably 15% by mass or more, further preferably 22% by mass or more, and preferably 60% by mass or less, The water-in-oil emulsified cosmetic according to any one of <1> to <11>, wherein 50% by mass is more preferable, and 40% by mass or less is more preferable.
<13> The water-in-oil emulsified cosmetic according to any one of <1> to <12>, further comprising (E) spherical polyurethane particles.

<14> The spherical polyurethane particles of the component (E) are preferably a crosslinked urethane-based crosslinked polymer, more preferably polyurethane particles made of hexamethylene diisocyanate / trimethylol hexyl lactone crosslinked polymer / silicic anhydride. The water-in-oil emulsified cosmetic described.
<15> The oil according to <13> or <14>, wherein the spherical polyurethane particles of component (E) preferably have an average particle diameter of 2 to 40 μm, more preferably 4 to 30 μm, and even more preferably 5 to 20 μm. Water-in-water emulsified cosmetic.
The content of <16> component (E) 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 10% by mass. The water-in-oil emulsified cosmetic according to any one of the above <13> to <15>, preferably 6% by mass or less, and more preferably 4% by mass or less.
<17> The water content is preferably 5 to 60% by mass, more preferably 13 to 50% by mass, and even more preferably 23 to 40% by mass, and any one of the above <1> to <16> The water-in-oil emulsified cosmetic described.

Synthesis Example 1 (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 condenser 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 (yield 89%).

Synthesis Example 2 (Production of poly (N-propionylethyleneimine) -modified silicone)
Dissolve 19.0 g (0.12 mol) of diethyl sulfate and 81.0 g (0.82 mol) of 2-ethyl-2-oxazoline in 203.0 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. Reactive poly (N-propionylethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1100. A 33% ethyl acetate solution of 300 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 2000) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (390 g, yield 97%). The content of the organopolysiloxane segment in the final product was 75% by mass, and the weight average molecular weight was 40000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 20 mol% of amino groups remained.

Synthesis 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 content of the organopolysiloxane segment in the final product was 87% by mass, and the weight average molecular weight of the final product was 115,000.

Examples 1-12 and Comparative Examples 1-4
Manufactures water-in-oil emulsified cosmetics with the composition shown in Table 1, homogeneity of the cosmetic coating on the skin, coverage of spots and freckles, difficulty in conspicuous pores, and resistance to removal when rubbed with fingers And the uniformity of the cosmetic coating film on the skin after application of the powder foundation and the difficulty of being rubbed with a finger, and the resistance of being rubbed with the finger after 4 hours of application of the powder foundation. evaluated. The results are also shown in Table 1.

(Production method)
The oil phase (including the active agent) containing the components (A) and (D) is preliminarily dispersed using a disper (1500 r / min, 5 minutes). Next, the powder phase containing the components (B), (C) and (E) is dispersed in the oil phase (2000 r / min, 5 minutes), and it is confirmed that the powder phase is uniformly dispersed. Using an oil phase in which the powder phase has become uniform, the aqueous phase is gradually added with emulsification while stirring with a disper (3000 r / min, 5 minutes), emulsified and retained, and then the viscosity is adjusted with a homomixer (5800 r / Min, 5 minutes) and defoaming to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
(1) Homogeneity of the makeup coating on the skin:
When five specialist panelists applied each cosmetic to the face, the homogeneity of the cosmetic coating film on the skin was subjected to sensory evaluation according to the following criteria. The result was shown as an integrated value of 5 persons.
5: A decorative coating film having no powder agglomeration and uniform uniformity.
4: A cosmetic coating film with less powder aggregation and uniform uniformity.
3; A slightly non-uniform decorative coating film with powder agglomeration.
2: It is a non-uniform coating film with powder aggregation.
1; Clearly powder agglomeration, unevenness is conspicuous, and the coating film is uneven.

(2) Coverage of stains and freckles:
Five expert panelists performed sensory evaluations on the coverage of stains and freckles according to the following criteria when each cosmetic was applied to the face. The result was shown as an integrated value of 5 persons.
5: Spots and freckles are not noticeable.
4: Spots and freckles are hardly noticeable.
3; Spots and freckles are not very noticeable.
2: Spots and freckles are slightly noticeable.
1: Spots and freckles are conspicuous.

(3) Hard to notice pores:
Five expert panelists performed sensory evaluation on the following criteria for the difficulty of conspicuous pores when each cosmetic was applied to the face. The result was shown as an integrated value of 5 persons.
5: Pore is not conspicuous.
4; The pores are hardly noticeable.
3; pores are not very noticeable.
2; The pores are slightly noticeable.
1; pores are conspicuous.

(4) Difficult to fall off when rubbed with fingers:
For each cosmetic, a decorative coating film was prepared on a black artificial leather with a coater of 0.152 mm and dried for 12 hours. Then, when 5 expert panelists rubbed the said cosmetic coating film lightly using one right hand middle finger, it evaluated by the following references | standards whether a cosmetic coating film could not be rubbed. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

(5) Homogeneity of the cosmetic coating film on the skin after applying the powder foundation:
Five professional panelists applied each cosmetic material to the face, and then overlaid with a powder foundation, and then sensory-evaluated the homogeneity of the cosmetic coating film on the skin according to the following criteria. The result was shown as an integrated value of 5 persons.
5: A decorative coating film having no powder agglomeration and uniform uniformity.
4: A cosmetic coating film with less powder aggregation and uniform uniformity.
3; A slightly non-uniform decorative coating film with powder agglomeration.
2: It is a non-uniform coating film with powder aggregation.
1; Clearly powder agglomeration, unevenness is conspicuous, and the coating film is uneven.

(6) Difficult to fall off when rubbed with fingers after applying powder foundation:
When five specialist panelists apply each cosmetic on their face, and then apply a powder foundation, and then gently rub the cosmetic film with one middle finger on their right hand, the cosmetic film is rubbed off. The following criteria were used to assess whether there was any. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

(7) Difficult to fall off when rubbed with fingers 4 hours after application of powder foundation:
Five professional panelists applied each cosmetic to the face and then overlaid with powder foundation. After the lapse of 4 hours, whether or not the decorative coating film was rubbed when it was lightly rubbed with one middle finger on the right hand was evaluated according to the following criteria. The result was shown as an integrated value of 5 persons.
5: Even if rubbed, the decorative coating cannot be removed.
4; Even if rubbed, the decorative coating film is hardly removed.
3; When it is rubbed, a slight cosmetic film can be removed.
2; When rubbed, a decorative coating can be removed.
1; When rubbed, the decorative coating peels off.

Example 13 (Liquid Foundation)
In the same manner as in Examples 1 to 12, water-in-oil emulsified cosmetics (liquid foundation) having the following composition were produced.
The resulting liquid foundation forms a firm and uniform film on the skin crevice and hills, so it has excellent stain / freckle coverage, and conspicuous pores are not noticeable, rubbing with hands, cloth, tissue paper, etc. However, even when the powder foundation was layered, a uniform film was formed and it was difficult to fall off. Moreover, these effects last for a long time.

(component)
Cross-linked polyether-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KSG-320; 25% isododecane solution) 10.0 (mass%)
Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96A-2CS) 20.0
Cyclopentasiloxane (Momentive Performance Materials Japan GK, TSF405A)
7.0
Octyl paramethoxycinnamate 3.0
Fluorine-modified silicone (Synthesis example 1) 1.0
Polyoxyethylene / methylpolysiloxane copolymer (manufactured by Dow Corning Toray, SH-3775M) 3.0
Poly (N-propionylethyleneimine) modified silicone (Synthesis Example 2)
1.5
Poly (N-propionylethyleneimine) modified silicone (Synthesis Example 3)
5.0
Spherical silicone elastic powder (average particle size 30μm; manufactured by Shin-Etsu Chemical Co., KSP-102)
1.0
Spherical silicone elastic powder (average particle size 12μm; manufactured by Shin-Etsu Chemical Co., Ltd., KSP-101)
0.5
Synthetic phlogopite (average particle size 12 μm; manufactured by Topy Industries, PDM-1000) 0.7
Synthetic phlogopite (average particle size 20 μm; manufactured by Topy Industries, PDM-20L) 0.7
Iron-containing synthetic phlogopite (average particle size 5μm; PDM-NFES, manufactured by Topy Industries, Ltd.)
0.6
Spherical polyurethane particles (average particle size 15μm)
(Toyo Pigment, Plastic Powder D-400) 1.0
Spherical polyurethane particles (average particle size 7μm)
(Toyo Pigment, Plastic Powder D-800) 1.0
Polymethylsilsesquioxane (average particle size 5 μm) 2.0
Tridecafluorooctyltriethoxysilane 5% by mass treated titanium oxide
3.0
Tridecafluorooctyltriethoxysilane 5% by weight treated bengara
0.1
Black iron oxide treated with 3% by mass of tridecafluorooctyltriethoxysilane
0.01
Tridecafluorooctyltriethoxysilane 5% by mass treated yellow iron oxide
0.6
Silicone 6% by mass treated fine particle zinc oxide (Finex-50 made by Sakai Chemical Industry Co., Ltd. treated with 6% silicone, specific surface area 45m ² / g)
5.8
Ethanol 1.0
Purified water 31.49
Total 100

Claims (4)

The following components (A), (B), (C) and (D):
(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)
0.1 to 15% by mass of a crosslinked polyether-modified silicone represented by
(B) Spherical silicone elastic powder having an average particle size of 10 to 50 μm, 0.1 to 10% by mass,
(C) 0.1-10% by mass of synthetic mica selected from synthetic phlogopite and iron-containing synthetic phlogopite
(D) A water-in-oil emulsified cosmetic containing a volatile oil and having a mass ratio (A) / (C) of the component (A) to the component (C) of 0.2 to 10.   The water-in-oil emulsified cosmetic according to claim 1, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.2 to 20.   The water-in-oil emulsified cosmetic according to claim 1 or 2, further comprising (E) spherical polyurethane particles.   The average particle diameter of a component (E) is 2-40 micrometers, The water-in-oil type emulsified cosmetics of any one of Claims 1-3.