JP6029378B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

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

  Conventionally, the carbosiloxane dendrimer structure is used as a cosmetic that has little uncomfortable feeling such as a film feeling, has an excellent effect of making the uneven parts of the skin such as pores inconspicuous, and is less likely to cause noticeable wrinkles and irregularities such as pores over time. A water-in-oil emulsified cosmetic containing a vinyl polymer in a chain, a specific nonvolatile oil agent, and a hydrophobized powder has been proposed (Patent Document 1).

JP 2010-18612 A

  However, the water-in-oil emulsified cosmetic containing a vinyl polymer having a carbosiloxane dendrimer structure in the side chain has a feeling of hardness and stiffness when the skin after application of the cosmetic is pressed with a finger, and the makeup is thick. I found the problem of being visible.

  The present inventors use a combination of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a powder surface-treated with tridecafluorooctyltriethoxysilane, and a specific fluorine-modified silicone in a specific ratio. Thus, it has been found that a water-in-oil emulsified cosmetic that solves the above problems can be obtained.

The present invention includes the following components (A), (B) and (C):
(A) Vinyl polymer having a carbosiloxane dendrimer structure in the side chain
0.1 to 30% by mass,
(B) Powder surface-treated with tridecafluorooctyltriethoxysilane,
(C) The following general formulas (3) and (4)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ²¹ , R ²² and R ²³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. A hydrocarbon group, m is a number from 2 to 6, n is a number from 1 to 6, p is a number from 3 to 50, and s is a number from 1 to 5)
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
And a water-in-oil emulsified cosmetic in which the mass ratio of the component (A) and the component (B) is (A) / (B) = 0.003-10.

In the water-in-oil emulsified cosmetic of the present invention, when the skin after application of the cosmetic is pressed with a finger, the skin is soft and does not feel stiff, and the makeup does not look thick with a moist feeling. Further, dullness over time can be suppressed.
The softness of the skin means a feeling that the skin feels like it can be pressed without difficulty when the skin after applying the cosmetic is pressed with a finger. Also, the feeling of stiffness refers to a feeling that the surface of the skin after application of the cosmetic is firm and caught.

  In the vinyl polymer having a carbosiloxane dendrimer structure as a component (A) in the side chain used in the present invention, the carbosiloxane dendrimer structure is preferably a group represented by the following formula (1).

In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group. X ¹ is a silylalkyl group represented by the following formula when i = 1.

In the formula, R ¹ is the same as described above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, X ^{i + 1} is a hydrogen atom, It is a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is an integer of 0 to 3.

  In formula (1), Z is a divalent organic group, alkylene group, arylene group, aralkylene group, ester-containing divalent organic group, ether-containing divalent organic group, ketone-containing divalent organic group, amide group-containing 2 A valent organic group is exemplified. Among these, an organic group represented by the following formula is preferable.

In the formula, R ⁹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group and a propylene group are preferable. R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable. R ¹¹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable. d is an integer of 0 to 4, and e is 0 or 1.

In the formula (1), R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, and isobutyl. Group, cyclopentyl group, and cyclohexyl group are exemplified, and as aryl group, phenyl group and naphthyl group are exemplified. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
X ¹ is a silylalkyl group represented by the following formula when i = 1.

In the formula, R ¹ is the same as described above. R ² is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as an ethylene group, a propylene group, a butylene group, or a hexylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, 1 And a branched alkylene group such as 1,4-dimethylbutylene group. Among these, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferable. R ³ is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. X ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. a ⁱ is an integer of 0-3. i is an integer of 1 to 10, which indicates the number of layers of the silylalkyl group, that is, the number of repetitions of the silylalkyl group.

  As the vinyl polymer of component (A), 0 to 99.9 parts by mass of vinyl monomers other than (A1) and (A2), and (A2) general formula (2):

(In the formula, Y is an organic group capable of radical polymerization, and R ¹ and X ¹ are the same as described above.)
A vinyl polymer containing a carbosiloxane dendrimer structure obtained by (co) polymerizing 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by

In the above formula, Y is an organic group capable of radical polymerization, and R ¹ is an alkyl or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.

  In this vinyl polymer, the vinyl monomer as the component (A1) is not particularly limited as long as it has a radical polymerizable vinyl group. Examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Lower alkyl (meth) acrylates such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; 2-ethylhexyl (meth) acrylate, ( Higher alkyl (meth) acrylates such as octyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, laurin Fatty acid vinyl esters such as vinyl acid vinyl and vinyl stearate; Aromatic monomers such as len, vinyltoluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, isobutoxy Amide group-containing vinyl monomers such as methoxy (meth) acrylamide, N, N-dimethyl (meth) acrylamide, vinylpyrrolidone, N-vinylacetamide; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyl-containing vinyl monomers such as glyceryl (meth) acrylate and hydroxyethylacrylamide; (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other carboxylic acid-containing vinyl monomers and their salts ; Tetrahydroflu Ether linkages such as ril (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether Containing vinyl-type monomer; Reactive group-containing monomer such as (meth) acrylic acid glycidyl, (meth) allyl glycidyl ether, methacryloyloxyethyl isocyanate, (meth) acryloxypropyltrimethoxysilane; (meth) acrylic at one end Macromonomers such as polydimethylsiloxane containing a group, polydimethylsiloxane containing a styryl group at one end; butadiene; vinyl chloride; salt (Meth) acrylonitrile; dibutyl fumarate; maleic anhydride; radical polymerizable unsaturated monomers having sulfonic acid groups such as styrenesulfonic acid, acrylamide-2-methylpropanesulfonic acid, and alkali metals thereof Salts, ammonium salts, organic amine salts; quaternary ammonium salts derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; tertiary amino groups such as diethylaminoethyl methacrylate Examples thereof include methacrylic acid esters of alcohol, vinyl pyridine and quaternary ammonium salts thereof.

  Polyfunctional vinyl monomers can also be used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meta ) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, styryl-blocked polydimethylsiloxane, etc. Saturated group containing silicone - emission compounds and the like.

  The component (A2) carbosiloxane dendrimer is not particularly limited as long as it has an organic group capable of radical polymerization represented by the general formula (2). In general formula (2), Y is an organic group capable of radical polymerization, and any organic group capable of radical reaction may be used. Specifically, a (meth) acryloxy group-containing organic group represented by the following general formula , (Meth) acrylamide group-containing organic groups, styryl group-containing organic groups, alkenyl groups having 2 to 10 carbon atoms, and the like.

Wherein R ⁴ and R ⁶ are a hydrogen atom or a methyl group, R ⁵ and R ⁸ are alkylene groups having 1 to 10 carbon atoms, and R ⁷ is an alkyl group having 1 to 10 carbon atoms. B is an integer from 0 to 4 and c is 0 or 1.)

  Examples of such radically polymerizable organic groups include 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 2-methacryloyloxyethyl group, 3-methacryloyloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, Vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl Group, methallyl group, and 5-hexenyl group.

  In the general formula (2), when i = 1, that is, the number of silylalkyl groups is 1, the carbosiloxane dendrimer of the component (A2) has the general formula:

(Wherein, Y, R ^1, R ² and R ³ are as defined above, but .a ¹ R ¹² is the same as the hydrogen atom or the R ¹ is the same as the a ^i, in one molecule The average total number of a ¹ is 0 to 7.)
Examples of such carboxydendrimers (A2) containing radically polymerizable organic groups include carbosiloxane dendrimers represented by the following average composition formula.

  Such carbosiloxane dendrimers can be produced, for example, according to the production methods described in JP-A Nos. 11-1530 and 2000-63225.

  In the vinyl polymer containing a dendrimer structure used in the present invention, the mass ratio of the component (A1) to the component (A2) is (A1) :( A2) = 0: 100 to 99.9: 0.1. Is preferably 5:95 to 90:10, more preferably 10:90 to 80:20.

  The number average molecular weight of the vinyl polymer having a carbosiloxane dendrimer structure as the component (A) used in the present invention is preferably 3,000 to 2,000,000 from the ease of blending as a cosmetic raw material. More preferably, it is 5,000 to 800,000. The property may be any of liquid, gum, paste, solid, etc. at room temperature, but is preferably solid from the viewpoint of the durability of the resulting cosmetic film. Further, from the viewpoint of compoundability, a solution or dispersion diluted with a solvent is preferable. As the solvent, decamethylcyclopentasiloxane and isododecane are preferable.

  The vinyl polymer having a carbosiloxane dendrimer structure in the side chain is particularly preferably a silicone dendrimer / acrylic copolymer, FA4001CM (decamethylcyclopentasiloxane solution), FA4002ID (isododecane solution) (above, Toray Dow Corning Co., Ltd.) (Commercially available) can be used.

  Component (A) can be used singly or in combination of two or more. From the viewpoint of suppressing dullness over time, the content is 0.1% by mass or more in the total composition, preferably 0.2%. It is at least mass%, more preferably at least 0.3 mass%. And from the point which the feeling of use is good and is excellent in the dispersibility of the powder at the time of manufacture, it is 30 mass% or less, Preferably it is 8 mass% or less, More preferably, it is 5 mass% or less. Moreover, 0.1-30 mass% of components (A) are contained in the whole composition, Preferably it is 0.2-8 mass%, More preferably, 0.3-5 mass% is contained.

The powder of component (B) used in the present invention has been surface-treated with tridecafluorooctyltriethoxysilane represented by the following formula.
F ₃ C— (CF ₂ ) ₅ — (CH ₂ ) ₂ —Si— (OCH ₂ CH ₃ ) ₃
Among the fluorine compounds that surface-treat the powder, the powder surface-treated with tridecafluorooctyltriethoxysilane is used in combination with component (A) to improve skin dullness and brighten the skin, making pores conspicuous Suppresses skin tone and smoothes skin texture. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

  The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, Bengala, clay, bentonite, titanium coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, oxidation Inorganic powders such as chromium, chromium hydroxide, calamine and carbon black, and composites thereof; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine Resin, Epoxy Organic powders such as resins, polycarbonate resins, divinylbenzene / styrene copolymers, silk powder, cellulose, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and complexes thereof; A composite powder of inorganic powder and organic powder can be used.

As a method of surface-treating the powder with tridecafluorooctyltriethoxysilane, for example, tridecafluorooctyltriethoxysilane is dropped or added in a mixer and mixed with the powder, followed by heat treatment, and if necessary And a method in which an organic solvent liquid in which tridecafluorooctyltriethoxysilane is dissolved or dispersed and a powder are mixed, the organic solvent is removed, and the mixture is crushed after drying.
Among them, tridecafluorooctyltriethoxysilane is dissolved or dispersed in an organic solvent, and while mixing the powder and the mixer in the mixer, the mixer is heated under reduced pressure to remove the organic solvent. A production method for crushing is preferred. Examples of the organic solvent used here include polar organic solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone, dichloromethane, chloroform, and normal hexane, toluene, xylene, and the like. Hydrocarbon organic solvents are suitable.

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

Component (B) preferably has an average particle size of 0.01 to 20 μm, more preferably 0.01 to 10 μm, from the standpoint of powderiness and finish at the time of application.
In the present invention, the particle diameter of the component (B) is measured with an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

  Component (B) can be used singly or in combination of two or more, and when touching the skin after applying the cosmetic with a finger, the skin is soft, and the content is as follows. 0.1 mass% or more is preferable in the whole composition, More preferably, it is 1 mass% or more, More preferably, it is 5 mass% or more. And, when the skin after applying the cosmetic is touched with a finger, the skin is soft, suppresses the feeling of stiffness, and the makeup does not become thick, preferably 40% by mass or less, more preferably 30% by mass or less. Yes, and more preferably 25% by mass or less. Moreover, it is preferable that a component (B) contains 0.1-40 mass% in the whole composition, More preferably, it is 1-30 mass%, More preferably, it contains 5-25 mass%.

  In the present invention, the mass ratio (A) / (B) of the component (A) and the component (B) is soft and moist when the skin after the cosmetic is applied is touched with a finger. From the point of view that there is no feeling of stiffness and the makeup does not become thick and suppresses dullness over time, it is preferably 0.003 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. 10 or less is preferable, more preferably 2 or less, and still more preferably 0.8 or less. Moreover, the mass ratio of a component (A) and a component (B) is (A) / (B) = 0.003-10, Preferably it is 0.005-2, More preferably, it is 0.01-0.8. It is.

The fluorine-modified silicone of component (C) used in the present invention has a polysiloxane unit represented by the general formulas (3) and (4).
In the formula, examples of the hydrocarbon group represented by R ²¹ , R ²² and R ²³ include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, 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.

  The ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (3) with respect to the total p + s of the polysiloxane units represented by the general formulas (3) and (4) When the skin is touched with a finger after applying the coating, the skin is soft and moist, with no feeling of stickiness, and the makeup does not become thick. In view of suppressing dullness over time, 0.66 ≦ p / (p + s) ≦ 0.9 is preferable, and 0.75 ≦ p / (p + s) ≦ 0.83 is more preferable.

The fluorine-modified silicone as component (C) can be produced, for example, according to the method described in JP-A-6-184212.
As a component (C), what is represented by following General formula (5) is preferable.

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

  The component (C) has a content of 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 2% by mass or more in the total composition from the viewpoint of moist feeling of use. And it is 50 mass% or less from the point of a moist feeling, without oily feeling, Preferably it is 30 mass% or less, More preferably, it is 15 mass% or less. Moreover, a component (C) is contained 0.01-50 mass% in the whole composition, Preferably it is 0.1-30 mass%, More preferably, 2-15 mass% is contained.

  In the present invention, the mass ratio (A) / (C) of the component (A) and the component (C) is soft and moist when the skin after touching the cosmetic is touched with a finger. From the point of view that there is no stickiness, the makeup does not become thick, and the dullness over time is suppressed, it is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.1 or more. , 50 or less, more preferably 10 or less, and still more preferably 2 or less. Moreover, as for the mass ratio of a component (A) and a component (C), (A) / (C) = 0.01-50 is preferable, More preferably, it is 0.02-10, More preferably, it is 0.1-2. is there.

  In the present invention, the mass ratio (B) / (C) of the component (B) and the component (C) is used when the skin after touching the cosmetic is touched with a finger, the skin is soft and moist. In terms of feeling, there is no stickiness, and the makeup does not become thick, and from the viewpoint of suppressing dullness over time, 0.1 or more is preferable, more preferably 0.3 or more, and still more preferably 0.5 or more And is preferably 100 or less, more preferably 30 or less, and still more preferably 1020 or less. Moreover, as for the mass ratio of a component (B) and a component (C), (B) / (C) = 0.1-100 is preferable, More preferably, it is 0.3-30, More preferably, it is 0.5-1020. is there.

The water-in-oil emulsified cosmetic of the present invention can further contain (D) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, has excellent makeup, suppresses conspicuous pores, It is excellent in improving dullness and brightening the skin, and can provide a good feeling of use. The particulate zinc oxide of component (D) is more preferably one having a specific surface area of 15 to 95 m ² / g.
In addition, the component (D) used by this invention excludes a component (B), and does not contain a component (B).

  The fine particle zinc oxide of component (D) can be used as it is, but if necessary, it is subjected to water and / or oil repellent treatment with silicone, metal soap, lecithin, N-acylamino acid, fluorine compound or the like. Can also be used. From the standpoint of preventing makeup collapse and improving the dispersibility of the fine zinc oxide in the cosmetic, a silicone-treated one is preferred, and a silicone treatment using methylhydrogenpolysiloxane is more preferred. These processes can be performed by a normal method.

  Component (D) can be used singly or in combination of two or more, and the content is preferably 0.01% by mass or more, more preferably from the viewpoint of suppressing dullness over time. Is 0.1% by mass or more, more preferably 1% by mass or more. And from the point of the makeup holding, 20 mass% or less is preferable, More preferably, it is 10 mass% or less, More preferably, it is 8 mass% or less. Moreover, it is preferable that a component (D) is contained 0.01-20 mass% in the whole composition, More preferably, it is 0.1-10 mass%, More preferably, it is contained 1-8 mass%. .

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

In addition, the oil used in the present invention may be liquid at 20 ° C. When a solid or paste oil is used, it is preferably used after being dissolved in another oil or solvent.
Examples of the oil used in the present invention include silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils (including fats and oils), ether oils, mineral oils, etc. Ester oil is more preferable, and silicone oil is more preferable. Of these, dimethylpolysiloxane and cyclopolysiloxane are more preferable.
These oil agents can be used alone or in combination of two or more.
Moreover, 10 mass% or more is preferable in the whole composition, as for content of the oil agent used for this invention, 20 mass% or more is more preferable, 50 mass% or less is preferable, and 40 mass% or less is more preferable. Moreover, it is preferable to contain 10-50 mass% of oil agents in the whole composition, and 20-40 mass% is more preferable.

Examples of the surfactant used in the present invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, nonionic surfactants are preferable, and polyether-modified silicones are more preferable. From the viewpoint of stably emulsifying the components (A), (B), and (C), the HLB value is preferably 1 or more and 7 or less, and the HLB value is more preferably 2 or more and 6 or less.
The content of the surfactant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 8% by mass or less, and more preferably 6% by mass or less in the total composition. Moreover, it is preferable to contain 0.1-8 mass% of surfactant in the whole composition, and 0.2-6 mass% is more preferable.

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lypophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant. For nonionic surfactants, Griffin ( Griffin).
The HLB of the mixed surfactant composed of two or more kinds of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is obtained by averaging the HLB values of the nonionic surfactants based on the blending ratio.

Mixed HLB = Σ (HLBx × Wx) / ΣWx
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

  The water-in-oil emulsified cosmetic of the present invention is a component used in ordinary cosmetics in addition to the above components, for example, solid oils such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax; And oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, blood circulation promoters, cooling sensations Agents, antiperspirants, bactericides, skin activators, moisturizers 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.
Further, the water-in-oil emulsified cosmetic of the present invention comprises a foundation, a makeup base; makeup cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc .; sunscreen emulsion, sunscreen It can be applied as UV protection cosmetics such as cream. Of these, a foundation and a makeup base are preferable.

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

<1> The following components (A), (B) and (C):
(A) Vinyl polymer having a carbosiloxane dendrimer structure in the side chain
0.1 to 30% by mass,
(B) Powder surface-treated with tridecafluorooctyltriethoxysilane,
(C) The following general formulas (3) and (4)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ²¹ , R ²² and R ²³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. A hydrocarbon group, m is a number from 2 to 6, n is a number from 1 to 6, p is a number from 3 to 50, and s is a number from 1 to 5)
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
A water-in-oil emulsified cosmetic comprising: (A) / (B) = 0.003 to 10 in mass ratio of component (A) and component (B).

<2> The content of the component (A) is 0.1 to 30% by mass, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and 8% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to the above <1>, preferably 5% by mass or less.
<3> The content of the component (B) is 0.1 to 40% by mass, preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 30% by mass or less in the total composition, 25 The water-in-oil emulsified cosmetic according to <1> or <2>, wherein the water content is more preferably at most% by mass.
<4> The content of the component (C) is 0.01 to 50% by mass, preferably 0.1% by mass or more, more preferably 2% by mass or more, and preferably 30% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <3>, more preferably 15% by mass or less.

<5> In the component (A), the carbosiloxane dendrimer structure has the following formula (1):

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. X ¹ is a silylalkyl group represented by the following formula when i = 1.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to any one of <1> to <4>, which is a group represented by the formula:

<6> The water-in-oil emulsion cosmetic according to any one of <1> to <5>, wherein the average particle size of the component (B) is 0.01 to 20 μm, and preferably 0.01 to 10 μm.
<7> The mass ratio of the component (A) and the component (B) is (A) / (B) = 0.003 to 10, preferably 0.005 or more, more preferably 0.01 or more, and 2 The water-in-oil type emulsified cosmetic according to any one of the above items <1> to <6>, preferably not more than 0.8.
<8> The mass ratio of the component (A) and the component (C) is (A) / (C) = 0.01 to 50, preferably 0.02 or more, more preferably 0.1 or more, and 10 The water-in-oil emulsified cosmetic according to any one of <1> to <7>, wherein the following is preferable and 2 or less is more preferable.
<9> The mass ratio of the component (B) and the component (C) is (B) / (C) = 0.1 to 100, preferably 0.3 or more, more preferably 0.5 or more, 30 The water-in-oil emulsified cosmetic according to any one of <1> to <8>, wherein the following is preferable and 20 or less is more preferable.

<10> In the component (C), the ratio of p and s is 0.66 ≦ p / (p + s) ≦ 0.9, and preferably 0.75 ≦ p / (p + s) ≦ 0.83 The water-in-oil emulsified cosmetic according to any one of 1> to <9>.
<11> Further, (D) in the oil according to any one of the above <1> to <10>, which contains fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g, preferably a specific surface area of 15 to 95 m ² / g. Water-type emulsified cosmetic.

<12> The content of the component (D) is 0.01 to 20% by mass, preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to <11>, more preferably 8% by mass or less.
<13> Furthermore, the content of water is 10 to 60% by mass, preferably 15% by mass or more and preferably 50% by mass or less in the entire composition, and any one of the above <1> to <12> Water-in-oil emulsified cosmetic.

Synthesis Example 1 (Synthesis of Compound A1)

Synthesis of _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).

  To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (Compound A1) (yield 89%).

Synthesis Example 2 (Synthesis of Compound A2)

In the same manner as in Synthesis Example 1, C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ was synthesized.
21.29 g (51 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added to a 300 mL four-necked flask equipped with a thermometer, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.26 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 78.71 g (195 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 78.9 g of the target compound (Compound A2) (yield 85%).

Synthesis Example 3 (Synthesis of Compound A3)

In the same manner as in Synthesis Example 1, C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ was synthesized.
To a 300 mL four-necked flask equipped with a thermometer, 17.61 g (33 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2 mass% chloroplatinic acid hexahydrate / isopropyl alcohol 0.27 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 82.39 g (206 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 0.13 NaOH solution 10.03g was added and it stirred for 2 hours. After dehydration at 60 ° C./5 KPa, after completion of the dehydration, 1.00 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature and stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 25 g of water to obtain 75.8 g of the target compound (Compound A3) (yield 82%).

Synthesis Example 4 (Synthesis of Compound A4)

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

Synthesis Example 5 (Synthesis of Compound A5)

In a 100 mL two-necked flask equipped with a condenser and a magnetic stirrer, 19.0 g (44.1 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ M) (manufactured by Toshiba Silicone) under a nitrogen atmosphere, C ₈ F ₁₇ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 53.3 g (105.8 mmol) was charged. Next, after raising the temperature in the flask to 80 ° C., 174.5 μL of a 2% isopropyl alcohol solution of chloroplatinic acid was added and stirred at 60 ° C. for 5 hours. The reaction mixture was cooled to room temperature, 50 mL of hexane and 2.2 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off and the solvent was distilled off. The unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective compound (Compound A5) as a colorless and transparent oil (yield 78%).

Examples 1 to 10 and Comparative Examples 1 to 5
W / O type liquid foundation having the composition shown in Table 1 was manufactured, and the softness of the skin immediately after application of the cosmetic, the lack of thickness of the makeup, the lack of firmness and moistness, and the dullness over time Evaluated. The results are also shown in Table 1.

(Manufacturing method)
The powder phase was mixed and ground, added to the separately mixed oil phase component, and dispersed with a disper. Thereafter, an aqueous phase component was added, dispersed with a disper, and then stirred with a homomixer to obtain a W / O type liquid foundation.

(Evaluation method)
(1) Softness of skin immediately after applying cosmetics:
Each W / O type liquid foundation was used by 10 professional evaluators. The softness of the skin when the skin immediately after applying the cosmetic was pressed with a finger was subjected to a sensory evaluation and judged according to the following criteria. The results are shown as a total score of 10 people.
5; The skin is very soft.
4; The skin is soft.
3; I can't say either.
2; The skin is not so soft.
1: The skin is not soft.

(2) Poorness of makeup immediately after applying cosmetics:
Each W / O type liquid foundation was used by 10 professional evaluators. The thickness of the makeup immediately after the cosmetic application was sensory evaluated and judged according to the following criteria. The results are shown as a total score of 10 people.
5; The makeup does not look thick.
4; The makeup does not look too thick.
3; I can't say either.
2: The makeup looks somewhat thick.
1: The makeup looks thick.

(3) No worries immediately after applying cosmetics:
Each W / O type liquid foundation was used by 10 professional evaluators. Sensory evaluation was performed for the lack of skin irritation immediately after application of the cosmetic, and the determination was made according to the following criteria. The results are shown as a total score of 10 people.
5: There is no feeling of stiffness.
4; There is not much sense of inconvenience.
3; I can't say either.
2; There is a slight feeling of stickiness.
1;

(4) Moist feeling immediately after applying cosmetics:
Each W / O type liquid foundation was used by 10 professional evaluators. The moist feeling of the skin immediately after the cosmetic application was sensory evaluated and judged according to the following criteria. The results are shown as a total score of 10 people.
5: Moist.
4; Somewhat moist.
3; I can't say either.
2; not very moist.
1; not moist.

(5) Dullness over time:
Ten professional evaluators used each W / O type liquid foundation, sensory-evaluated the dullness in the finish of the skin after 8 hours of cosmetic application, and determined according to the following criteria. The results are shown as a total score of 10 people.
5; It is difficult to dull in the finish over time.
4: Slightly less dull in the finish over time.
3; I can't say either.
2; Slightly dull in the finish over time.
1: It is easy to dull in the finish over time.

Example 11 (makeup base)
(component)
(1) Acrylic / silicone dendrimer (FA4002ID: 40% isododecane solution, manufactured by Toray Dow Corning)
12.5 (mass%)
(2) Fluorine-modified silicone (Synthesis Example 1) 4.5
(3) Dimethylpolysiloxane / polyoxyalkylene copolymer (SH3775M, manufactured by Toray Dow Corning) 3.0
(4) Decamethylcyclopentasiloxane (silicone TSF405,
Momentive Performance Materials Japan GK)
17.0
(5) Dimethylpolysiloxane (KF-96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.)
18.5
(6) 2-Ethylhexyl paramethoxycinnamate 2.0
(7) Ethanol 9.8
(8) Magnesium sulfate 0.3
(9) Purified water Remaining amount (10) Tridecafluorooctyltriethoxysilane 5% by mass treated titanium oxide
0.5
(11) Silicone-treated fine particle zinc oxide 1.0
Total 100

(Manufacturing method)
In the same manner as in Examples 1 to 10 , a makeup base (water-in-oil emulsified cosmetic) was produced.
The resulting makeup base is soft when the skin is pressed with a finger immediately after application, has a moist feeling of use, does not feel stiff, the makeup does not look thick, and is difficult to dull over time .

Claims (4)

The following components (A), (B) and (C):
(A) Vinyl polymer having a carbosiloxane dendrimer structure in the side chain
0.1 to 30% by mass,
(B) Powder surface-treated with tridecafluorooctyltriethoxysilane,
(C) The following general formulas (3) and (4)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ²¹ , R ²² and R ²³ are the same or different and each represents a linear 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 )
0.01 to 50% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
The mass proportion of component (A) and component (B) is (A) / (B) = 0.003-10, and the mass proportion of component (A) and component (C) is (A ) / (C) = 0.01-10 .   The water-in-oil emulsified cosmetic according to claim 1, wherein the content of the component (B) is 0.1 to 40% by mass. In component (A), the carbosiloxane dendrimer structure has the following formula (1)

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. X ¹ is a silylalkyl group represented by the following formula when i = 1.

(In the formula, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a ⁱ is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein The water-in-oil emulsified cosmetic according to any one of claims 1 to 3 , further comprising (D) fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g.