JP2017095438A - Water-in-oil emulsion type cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil type emulsion cosmetic which forms a soft cosmetic film after application, causes no filmy feeling while having excellent followability to the skin, causes no finger marks even when a cosmetic coating after application is pressed and prevents peeling off of a cosmetic film.SOLUTION: There is provided a water-in-oil type emulsion cosmetic which comprises: (A) 0.01 to 20 mass% of a fluorine-modified silicone resin which is solid at 25°C having a structure represented by the following general formula (1): RSiO(1) (Rrepresents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group or the general formula: -R-Rf (Rrepresents a divalent alkylene group having 2 to 6 carbon atoms, Rf represents a perfluoroalkyl group having 1 to 8 carbon atoms), which is selected arbitrarily from a functional group essentially including a hydrocarbon group and the general formula, -R-Rf and g represents an average number and satisfies the following expression, 1.0≤g≤1.8); (B) 0.01 to 50 mass% of a perfluoropolyether which is liquid at 25°C; and 0.1 to 10 mass% of octyl p-methoxycinnamate.SELECTED DRAWING: None

Description

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

Conventionally, cosmetics excellent in feeling of use such as makeup sustainability, spread, and stickiness suppression have been studied using various polymers and the like.
For example, Patent Document 1 describes a cosmetic containing a fluorine-modified silicone resin having a silanol group in the molecule and having a specific structure, is difficult to collapse, has high water resistance, and has a long-lasting cosmetic effect. It has been proposed to be superior.

Japanese Patent Laid-Open No. 9-12431

  The water-in-oil emulsified cosmetic containing a fluorine-modified silicone resin makes the cosmetic film after application stiff, the skin and the cosmetic film are difficult to follow, and the cosmetic film floats off the skin, causing makeup to collapse and make up There was a problem of peeling off.

  By combining perfluoroether with a specific fluorine-modified silicone resin and octyl paramethoxycinnamate, the present inventors can obtain a sufficient cosmetic coating film while maintaining a natural finish. Water-in-oil emulsification where the film is soft and has excellent followability to the skin, but there is no film feeling, no finger marks are formed even if the applied cosmetic film is pressed, and the decorative film does not peel off even when pressed with a towel We found that cosmetics can be obtained.

The present invention comprises the following components (A), (B) and (C):
(A) The following general formula (1)
R ¹¹ _g SiO _{(4-g) / 2} (1)
(In the formula, R ¹¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ¹² —Rf (R ¹² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon a number indicating the 1-8 perfluoroalkyl group), an arbitrarily chosen a hydroxyl group and the general formula -R ¹² -Rf from the functional groups as an essential, g is 1.0 ≦ g ≦ average number 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(B) 0.01 to 50% by mass of a perfluoropolyether that is liquid at 25 ° C.
(C) Octyl paramethoxycinnamate 0.1 to 10% by mass
The present invention relates to a water-in-oil emulsified cosmetic containing

The water-in-oil type emulsified cosmetic of the present invention can provide a sufficient cosmetic coating film while maintaining a natural finish, the coated cosmetic film is soft, and has excellent followability to the skin. No finger marks are formed even when the applied decorative coating is pressed, and the decorative film does not peel off even when pressed with a towel.
Moreover, these effects last for a long time.

The component (A) fluorine-modified silicone resin used in the present invention has a structure represented by the general formula (1).
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. For this reason, it is preferable to use it by dissolving in cyclic silicone, dimethylpolysiloxane or the like. The cyclic silicone is preferably used by dissolving in one or more selected from octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5).

  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 Japan Goto Co., Ltd. can be used.

  Component (A) can be used singly or in combination of two or more. The content is sufficient to obtain a cosmetic coating film, the coated cosmetic film is soft, and has excellent followability to the skin. From the viewpoint of suppressing the feeling, the total composition is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, 20% by mass or less, and preferably 12% by mass or less. 7 mass% or less is more preferable. Moreover, content of a component (A) is 0.01-20 mass% in the whole composition, 0.1-12 mass% is preferable, and 1-7 mass% is more preferable.

The component (B) perfluoropolyether used in the present invention is liquid at 25 ° C. The liquid state at 25 ° C. means fluidity, and includes paste.
As perfluoropolyether, the following general formula (2)

Wherein R ²¹ , R ²³ , R ²⁴ and R ²⁵ are the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and R ²² represents a fluorine atom or a perfluoroalkyl group. , D, e and f represent a number of 0 or more with a molecular weight of 500 to 5000. However, d = e = f = 0, where each perfluoroalkyleneoxy group shown in parentheses Need not be arranged in this order, and may be random polymerization or block polymerization)
A perfluoropolyether represented by the formula is preferred.
As such a perfluoropolyether, for example, the general formula (3)

(In the formula, k and h represent numbers with a molecular weight of 500 to 5000, and k / h is 0.2 to 2)
FOMBLIN HC-04 (mass average molecular weight 1500), FOMBLIN HC-25 (mass average molecular weight 3200) represented by the formula (4), and the general formula (4)

(Where j represents a number from 4 to 500)
Commercially available products such as demnum S-20 (mass average molecular weight 2,700) and demnum S-65 (mass average molecular weight 4500) (manufactured by Daikin Industries, Ltd.) represented by

The perfluoropolyether of component (B) preferably has a mass average molecular weight of 500 or more, more preferably 1000 or more, more preferably 5000 or less, and preferably 4500 or less from the viewpoint of water / oil repellency and makeup durability. More preferred. Here, the mass average molecular weight is a value measured by a kinematic viscosity measurement method.
The perfluoropolyether of component (B) preferably has a viscosity at 25 ° C. of 5 to 5000 cSt.

  Component (B) can be used singly or in combination of two or more. From the point of being excellent in makeup paste and makeup retention and suppressing peeling of the cosmetic film, the content is 0.01% in the total composition. % By mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, 50% by mass or less, preferably 30% by mass or less, and more preferably 8% by mass or less. Moreover, content of a component (B) is 0.01-50 mass% in the whole composition, 0.1-30 mass% is preferable, and 0.5-8 mass% is more preferable.

  In the present invention, the mass ratio (A) / (B) of the component (A) with respect to the component (B) can provide a sufficient cosmetic film while maintaining a natural finish, and the decorative film after application is soft, 0.05 or more is preferable, because it has excellent skin followability but does not have a feeling of film, does not leave a finger mark when pressed after application, and does not peel off even if pressed with a towel. 0.2 or more is more preferable, 0.3 or more is more preferable, 8 or less is preferable, 4 or less is more preferable, and 2 or less is more preferable. Moreover, 0.05-8 are preferable, as for the mass ratio (A) / (B) of the component (A) with respect to a component (B), 0.2-4 are more preferable, and 0.3-2 are more preferable.

  The content of octyl paramethoxycinnamate of component (C) is 0.1% by mass or more in the total composition from the point that the cosmetic film after application is soft and has excellent followability to the skin while protecting against ultraviolet rays. 0.5 mass% is preferable, 1 mass% or more is more preferable, 10 mass% or less is preferable, 8 mass% or less is preferable, and 6 mass% or less is more preferable. Moreover, content of a component (C) is 0.1-10 mass% in all the compositions, 0.5-8 mass% is preferable, and 1-6 mass% is more preferable.

  In the present invention, the mass ratio (A) / (C) of the component (A) with respect to the component (C) is such that a sufficient cosmetic coating film is obtained while maintaining a natural finish, and the cosmetic film after application is soft, It is preferably 0.1 or more, because it has excellent skin followability, does not have a feeling of film, does not leave a finger mark even if it is pressed after application, and does not peel off even if pressed with a towel. 0.2 or more is more preferable, 0.4 or more is more preferable, 10 or less is preferable, 4 or less is more preferable, and 2 or less is more preferable. Moreover, 0.1-10 are preferable, as for the mass ratio (A) / (C) of the component (A) with respect to a component (C), 0.2-4 are more preferable, and 0.4-2 are more preferable.

The water-in-oil emulsified cosmetic of the present invention can further contain (D) iron oxide and / or titanium oxide.
Examples of iron oxide include bengara, yellow iron oxide, and black iron oxide.
Further, the shape and particle diameter of titanium oxide are not limited, but the average particle diameter is preferably 0.01 to 2 μm, more preferably 0.05 to 1 μm, and more preferably 0.1 to 0. More preferably, it is 5 μm.
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 component (D) iron oxide and titanium oxide may be untreated or surface-treated. As the surface treatment, one or two or more of these may be subjected to a hydrophobic treatment. The hydrophobizing treatment is not limited as long as it is a treatment applied to normal cosmetic powders, such as fluorine compounds, silicone compounds, metal soaps, amino acid compounds, lecithin, alkylsilanes, oil agents, organic titanates, etc. The surface treatment agent may be used for dry treatment, wet treatment, or the like.
Specific examples of the surface treating agent include perfluoroalkylalkoxysilanes such as tridecafluorooctyltriethoxysilane, fluorine-based compounds such as perfluoropolyether, perfluoroalkyl phosphate, and fluorine-modified silicone; dimethylpolysiloxane, methyl Silicone compounds such as hydrogen polysiloxane, cyclic silicone, one- or both-end trialkoxy group-modified organopolysiloxane, cross-linked silicone, silicone resin, fluorine-modified silicone resin, acrylic-modified silicone; aluminum stearate, aluminum myristate, Metal soaps such as zinc stearate and magnesium stearate; proline, hydroxyproline, alanine, glycine, sarcosine, glutamic acid, aspartic acid, lysine and Amino acid compounds such as these derivatives; lecithin, hydrogenated lecithin; alkylsilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane; polyisobutylene, wax, Oil agents such as fats and oils; organic titanates such as isopropyl titanium triisostearate.
Of these, tridecafluorooctyltriethoxysilane, dimethylpolysiloxane, methylhydrogenpolysiloxane, and octyltriethoxysilane are preferable, and tridecafluorooctyltriethoxysilane is more preferable.
The iron oxide and titanium oxide of component (D) do not include those encapsulated in polymer powders, those coated with inorganic powders, and those composite-treated with various powders.

  Component (D) can be used singly or in combination of two or more, and a sufficient cosmetic film can be obtained while maintaining a natural finish, and the content after coating is soft, since the decorative film after application is soft. In the composition, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, 0.1% by mass or more is more preferable, 8% by mass or less is preferable, and 3% by mass or less is more preferable. A mass% or less is more preferable. Moreover, 0.01-8 mass% is preferable in the whole composition, as for content of a component (D), 0.05-3 mass% is more preferable, and 0.1-2.5 mass% is further more preferable.

  In the present invention, the mass ratio (A) / (D) of the component (A) with respect to the component (D) can provide a sufficient cosmetic film while maintaining a natural finish, and the decorative film after application is soft, 0.3 or more is preferable because it has excellent followability to the skin, but there is no film feeling, finger marks do not stick even if the applied cosmetic film is pressed, and the decorative film does not peel off even if pressed with a towel. 0.5 or more is more preferable, 1.1 or more is further preferable, 20 or less is preferable, 10 or less is more preferable, and 5.5 or less is more preferable. Moreover, 0.3-20 are preferable, as for the mass ratio (A) / (D) of the component (A) with respect to a component (D), 0.5-10 are more preferable, and 1.1-5.5 are more preferable. .

The water-in-oil emulsified cosmetic of the present invention can further contain (E) a polymer powder encapsulating a colored inorganic pigment, and is uniform with respect to skin groove portions and skin hill portions such as pores after application. It has excellent adhesion and can suppress the conspicuous pores. The colored inorganic pigment contained in component (E) does not contain component (D).
The polymer powder of component (E) contains a polymer as a base material and encloses a colored inorganic pigment therein. Examples include those in which colored inorganic pigments are dispersed in polymer particles, and those in which colored inorganic pigments are present on the surface of polymer particles, and those in which colored inorganic pigments are uniformly dispersed in polymer particles. Is preferred.
Examples of the colored inorganic pigment include a white inorganic pigment, a red inorganic pigment, a yellow inorganic pigment, a black inorganic pigment, a ceramic pigment, and the like, and one or more of these can be included. Among these, (a) a polymer powder containing a white inorganic pigment, (a) a white inorganic pigment, (b) a red inorganic pigment, and (c) a polymer powder containing a yellow inorganic pigment are preferred, and (a) a white inorganic pigment. It is more preferable to use together a polymer powder encapsulating (a) a white inorganic pigment, (b) a red inorganic pigment and (c) a yellow inorganic pigment.
In addition to the above (a), (b) and (c), the colored inorganic pigment can contain a black inorganic pigment (black iron oxide or the like), a ceramic pigment (ceramic pigment) or the like.

  (A) Examples of white inorganic pigments include metal oxides such as aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide (rutile type, anatase type, etc.); zinc oxide / titanium dioxide composite oxide Composite metal oxides such as aluminum oxide / magnesium oxide composite oxide, calcium oxide / zirconium oxide composite oxide; sulfates such as barium sulfate; carbonates such as calcium carbonate, and the like. It can use individually or in mixture of 2 or more types. Of these, metal oxides such as titanium dioxide, aluminum oxide, zinc oxide, and zirconium oxide, and zinc oxide / titanium dioxide composite oxide are preferable, and titanium dioxide is more preferable from the viewpoint of stability in cosmetics.

(B) Examples of red inorganic pigments include Bengala, iron oxide / titanium oxide sintered product, cadmium red, and molybdenum red. Bengala is preferable.
Examples of (c) yellow inorganic pigments include yellow iron oxide, cerium oxide, bismuth vanadium yellow, yellow lead, and cadmium yellow, and yellow iron oxide is preferable.

  The average particle diameters of (a) white inorganic pigment, (b) red inorganic pigment, and (c) yellow inorganic pigment are each preferably 0.01 to 2 μm from the viewpoint of being uniformly dispersed in the polymer powder. 0.05 to 1 μm is more preferable, and 0.1 to 0.5 μm is even more preferable.

  In the case of a polymer powder containing (a) white inorganic powder, (b) red inorganic pigment and (c) yellow inorganic pigment, the mass ratio in the polymer powder of (a), (b) and (c) is From the viewpoint of cutting the short wavelength side of light so that pores and color unevenness are not noticeable, (a) :( b) :( c) = 70 to 99: 0.1 to 10: 0.1 20, more preferably 70 to 98: 0.5 to 10: 1.5 to 20, more preferably 80 to 97: 1 to 5: 2 to 15, and 90 to 97: 1 to 3: 2 to 7 Even more preferred.

  The inorganic pigment is preferably subjected to surface treatment such as silicone treatment for imparting water repellency and fluorine treatment for imparting water and oil repellency from the viewpoint of excellent dispersibility in the polymer powder.

  The content of the inorganic pigment in the polymer powder is preferably 5 to 40% by mass in total, more preferably 10 to 20% by mass, from the balance of light transmittance and light scattering of the powder. preferable.

On the other hand, the polymer used as the polymer powder as a base material is not limited as long as it is usually used in cosmetics. For example, a (meth) acrylic resin such as polymethyl methacrylate, nylon, Examples thereof include polyester, polyethylene, polystyrene, polyurethane, silicone resin, and cellulose. Especially, (meth) acrylic-type resin and a cellulose are preferable and (meth) acrylic-type resin is more preferable.
In addition, the polymer is transparent or translucent, and its production is easy, and those having excellent particle strength and solvent resistance are preferred, a crosslinked polymer is preferred, and lauryl (meth) acrylate-ethylene glycol di (meth) acrylate is preferred. More preferred are copolymers.

  The method of encapsulating the inorganic pigment in the polymer can be appropriately selected depending on the type of polymer used. For example, when the type of polymer is nylon resin, paraffin or the like and cyclic lactam are mixed, heated and dissolved, and a desired amount of inorganic pigment powder is added to the resulting mixture. While stirring this, a polymerization accelerator such as phosphorus trichloride is added to perform alkali polymerization to obtain particles. Further, the particles are separated by filtration, and the obtained particles are washed with an organic solvent such as isopropyl alcohol, benzene, or water, and then dried.

  Also, for example, when the polymer type is a silicone resin, an aqueous solution of ammonia, amine, etc. and an inorganic pigment powder are mixed, and the resulting mixture is mixed with hydrolyzable silane, alkoxysilane, acetoxysilane, etc. Hydrolyze silane and the like. Next, a condensation reaction between a hydrolyzate such as alkoxysilane and a hydrolyzate such as alkoxysilane or an unhydrolyzed alkoxysilane is performed to obtain particles. Further, there may be mentioned a method of filtering the particles, washing the obtained particles with water and drying.

  Furthermore, for example, when the polymer type is a (meth) acrylic resin, (meth) acrylic acid ester as a monomer and lauroyl peroxide as a polymerization initiator are mixed and dissolved, and the desired amount is added to the resulting mixture. The inorganic pigment (including components (a), (b) and (c)) is added and dispersed. The obtained dispersion is added to and dispersed in an aqueous polyvinyl alcohol solution and heated with stirring to perform polymerization (suspension polymerization) to obtain particles. Examples include a method of filtering the particles, washing the obtained particles with water and drying.

  Further, the dispersion state of the inorganic pigment in the polymer particles is preferably a high dispersion state, and as a method for controlling the dispersion state, a machine such as a homogenizer, a high-pressure homogenizer, an ultrasonic disperser, an attritor mill, or a ball mill is used. Dispersion method used: low molecular surfactant (for example, anionic surfactant (sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate, etc.), cationic surfactant, nonionic surfactant, etc.), polymer dispersant [for example , Starch, polyvinyl alcohol, carboxymethylcellulose, methylpolysiloxane, etc.] and the like.

The average particle size of the polymer powder of component (E) is excellent in uniform adhesion to the skin groove and hill part such as pores after application, suppresses the conspicuous pores, and suppresses the thick finish Therefore, the thickness is preferably 1 μm or more, and more preferably 3 μm or more. In addition, the upper limit of the average particle diameter of the polymer particles is preferably 30 μm or less, and more preferably 15 μm or less, from the viewpoint of suppressing powderiness during use.
In the present invention, the average particle size of component (E) refers to a volume-based average particle size measured using ethanol as a solvent and a laser diffraction particle size distribution analyzer. The particle diameter of the pigment in the polymer powder may be measured by observation with an electron microscope.

  The shape of the component (E) polymer powder may be spherical, spindle-shaped, rod-shaped, plate-shaped, or indefinite, and is preferably spherical or spindle-shaped from the viewpoint of excellent light scattering effect and usability. The “spherical shape” does not need to be a true sphere, for example, a true sphere; a substantially spherical shape; a spheroid that exhibits a property of suppressing regular reflection and / or irregular reflection; Something.

The polymer powder preferably has a total transmittance of 40% or more and less than 80%, preferably 50% or more and less than 80%, from the viewpoint of making the skin color unevenness, skin irregularities and pores inconspicuous. More preferably, the haze value is preferably 45 or more and less than 100, and more preferably 60 or more and less than 100.
The total transmittance and haze value are measured by applying 0.4 g of powder and 1.6 g of amino-modified silicone (SF8417, manufactured by Dow Corning Toray) well onto a glass plate to obtain a sample. -Meter HM-150 (manufactured by Murakami Color Research Laboratory). For the measurement, light having a peak at a wavelength of 550 nm and 8 ° field light are used.

The polymer powder can be used as it is, but it can also be used after its surface has been subjected to a hydrophobizing treatment with a commonly used hydrophobizing agent.
The hydrophobizing agent is not particularly limited as long as it is usually used. For example, silicone oil such as hydrogen organopolysiloxane, fatty acid metal salt, alkyl phosphoric acid, alkali metal salt of alkyl phosphoric acid or amine salt, Examples thereof include N-monoaliphatic acyl basic amino acids having 8 to 22 carbon atoms, phosphate esters having a perfluoroalkyl group, and the like, each of which can be used alone or in admixture of two or more. Of the hydrophobizing agents, silicone oil and phosphoric acid ester having a perfluoroalkyl group are preferred.

  Ingredient (E) can be used alone or in combination of two or more, and it has excellent uniform adhesion to the crevice and skin part such as pores after application, suppresses conspicuous pores, and has a thick finish. From the viewpoint of suppressing the length, the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, preferably 10% by mass or less, and 8% by mass in the total composition. % Or less is more preferable, and 6% by mass or less is more preferable. Moreover, 0.5-10 mass% is preferable in the whole composition, as for content of a component (E), 1-8 mass% is more preferable, and 2-6 mass% is further more preferable.

  In the present invention, the content of water is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, more preferably 70% by mass or less, and more preferably 60% by mass or less in the total composition. Preferably, 50 mass% or less is more preferable. Moreover, in this invention, 10-70 mass% is preferable in the whole composition, as for content of water, 20-60 mass% is more preferable, and 25-50 mass% is further more preferable.

  The water-in-oil emulsified cosmetic of the present invention is a component that is usually used in cosmetics in addition to the above components, such as other oily components, powders other than the above, surfactants, pigments, water-soluble polymers, Antioxidants, fragrances, pigments, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, fungicides, skin activators, moisturizers, refreshing agents, etc. can be contained. .

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and can be made into a liquid, emulsion, paste, cream, gel, etc., emulsion, 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 composition of the present invention preferably has a viscosity immediately after production at 25 ° C. of 500 to 15000 mPa · s, and is preferably 1000 to 12000 mPa · s. s is more preferable, and 3000 to 7000 mPa · s is more preferable.
In the present invention, the viscosity is measured at 25 ° C. using a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVB-10 viscometer, rotational speed 6 r / min, rotor No. 3, 1 min).

Production Example 1 (Production of poly (N-propionylethyleneimine) dimethylsiloxane copolymer)
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.
Further, 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, manufactured by Shin-Etsu Silicone Co., Ltd., mass average molecular weight 100000, amine equivalent 20000) and 203 g of ethyl acetate 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 mass average molecular weight of the final product was 115,000.

Production Example 2 (Production of 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 in the ratio shown in Table 1, and water repellent treatment using methylhydrogenpolysiloxane (2% with respect to inorganic powder) )did. Next, the obtained solution and the water-repellent-treated inorganic pigment were mixed and dispersed so as to have the inclusion rate shown in Table 1 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 shown in Table 1.
About the obtained polymer powder, the transmittance | permeability and the haze value were measured. The results are also shown in Table 1.

(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, and the haze value (H) described in the present invention (Example). Is a value (H15) converted to a value when each sample is 15 μm in order to eliminate measurement errors due to the thickness of each sample. 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.

Examples 1-10 and Comparative Examples 1-2
Immediately after manufacturing a water-in-oil emulsified cosmetic composition (foundation) shown in Table 2 and applying it to the skin, it is difficult to remove the foundation, and it is applied to the skin. Softness of skin immediately after application, no feeling of film immediately after application to skin, application to skin and ease of follow-up of skin and cosmetic film after 5 hours, and application after 5 hours The difficulty of peeling the cosmetic film from the skin was evaluated. The results are also shown in Table 2.

(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 (foundation).

(Evaluation method)
(1) Immediately after application to skin, difficulty in removing foundation:
Each of the five specialist panelists applied each foundation to the skin, and the sensory evaluation of the difficulty of removing the foundation when the skin after application was pressed with a finger was performed according to the following criteria. The results are shown as the total score of 5 people.
5: Even if the skin after application | coating is pushed with a finger, a foundation does not adhere to a finger at all.
4: Even if the skin after application | coating is pushed with a finger, a foundation does not adhere to a finger.
3; Even if the skin after application is pressed with a finger, the foundation does not adhere to the finger.
2; Even if the skin after application is pressed with a finger, the foundation is slightly attached to the finger.
1; Even if the skin after application is pressed with a finger, the foundation is attached to the finger.

(2) It is applied to the skin and it is difficult for the makeup to collapse after 5 hours:
Each foundation was applied to the skin by five specialist panelists, and after application, the difficulty of collapsing the makeup after 5 hours was subjected to sensory evaluation based on the following criteria. The results are shown as the total score of 5 people.
5: No makeup collapse.
4; No makeup collapse.
3; There is not much makeup collapse.
2; There is a little makeup collapse.
1: There is a collapse of makeup.

(3) Skin softness immediately after application to the skin:
Each foundation was applied to the skin by five professional panelists, and the softness of the skin after the application was sensory evaluated according to the following criteria. The results are shown as the total score of 5 people.
5: The skin after application is quite soft.
4; The skin after application is soft.
3; The skin after application is slightly soft.
2: The skin after application is not so soft.
1: The skin after application is not soft.

(4) No film feeling immediately after application to skin:
Each foundation was applied to the skin by five professional panelists, and the lack of film feeling after application was sensory-evaluated according to the following criteria. The results are shown as the total score of 5 people.
5: No film feeling after application.
4: There is no film feeling after application.
3; There is not much film feeling after application.
2: There is a little film feeling after application.
1: There is a feeling of film after application.

(5) Ease of following skin and decorative film after 5 hours of application to skin:
Each foundation was applied to the skin by 5 specialist panelists, and the ease of following the cosmetic film and the skin after 5 hours was subjected to sensory evaluation based on the following criteria. The results are shown as the total score of 5 people.
5; Even if the face is moved, the applied cosmetic film follows the skin firmly.
4; Even if the face is moved, the applied cosmetic film almost follows the skin.
3; When the face is moved, the decorative film after application becomes slightly streaky and does not follow the skin.
2: When the face is moved, the decorative film after application is partially broken and does not follow the skin.
1: When the face is moved, the cosmetic film after application is clearly broken and does not follow the skin

(6) When applied to the skin, the makeup film is difficult to peel off from the skin after 5 hours:
Each foundation was applied to the skin by five specialist panelists, and sensory evaluation was performed according to the following criteria for the difficulty of peeling off the cosmetic film from the skin after application for 5 hours. The results are shown as the total score of 5 people.
5; The cosmetic film does not peel off from the skin at all.
4; The cosmetic film does not peel from the skin.
3; The cosmetic film does not peel off much from the skin.
2; The cosmetic film peels off slightly from the skin.
1: The decorative film peels from the skin after application.

Examples 11-14
In the same manner as in Examples 1 to 10, water-in-oil emulsified cosmetics (foundations) having the compositions shown in Table 3 were produced.
In any of the obtained cosmetics (foundations), it is difficult to remove the foundation immediately after application to the skin, the makeup does not collapse even after 5 hours, and the skin immediately after application to the skin is soft and has no film feeling. After 5 hours, the skin and the decorative film were easy to follow, and the decorative film was difficult to peel off from the skin.

Claims (3)

The following components (A), (B) and (C):
(A) The following general formula (1)
R ¹¹ _g SiO _{(4-g) / 2} (1)
(In the formula, R ¹¹ represents a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ¹² —Rf (R ¹² represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents carbon a number indicating the 1-8 perfluoroalkyl group), an arbitrarily chosen a hydroxyl group and the general formula -R ¹² -Rf from the functional groups as an essential, g is 1.0 ≦ g ≦ average number 1. 8)
0.01 to 20% by mass of a fluorine-modified silicone resin having a structure represented by
(B) 0.01 to 50% by mass of a perfluoropolyether that is liquid at 25 ° C.
(C) Octyl paramethoxycinnamate 0.1 to 10% by mass
Water-in-oil emulsified cosmetic containing   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 0.05 to 8.   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 0.1 to 10.