JP2015044759A - Oil-in-water type emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsion cosmetic which maintains water resistance and sebum resistance, suppresses a feeling of dryness in finished skin, suppresses feeling of being caught and feeling of stiffness at the time of initial application of a powder cosmetic, and provides smoothness and a moist feeling to the finished skin.SOLUTION: An oil-in-water type emulsion cosmetic comprises: (A) 0.01 to 5 mass% of a derivative of water-soluble polysaccharide; (B) 0.01 to 40 mass% of fluorine-modified silicone having a polysiloxane unit represented by general formulas (1) and (2), in which Rf represents a perfluoroalkyl group having a C6 straight or branched chain, R, Rand Rrepresent an alkyl group having a C1-6 straight or branched chain, m represents 2 to 6, n represents 1 to 6, p represents 3 to 50, and s represents 1 to 5; (C) powder treated by tridecafluorooctyl triethoxysilane; and (D) particulate zinc oxide which is subjected to surface treatment with silicone or alkylsilane and has specific surface area of 10 to 100 m/g. The mass ratio (B)/(A) of the component (B) to the component (A) is 3 to 200.

Description

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

Fluorine-modified silicone is used to improve the cosmetic durability and the feeling of use. For example, Patent Document 1 describes that a cosmetic material containing a specific fluorine-modified silicone derivative has a good cosmetic durability and excellent usability, and Patent Document 2 describes fluorine-modified silicone and fine-particle zinc oxide. It is described that the cosmetics to be contained are excellent in water resistance, sebum resistance and oil resistance, and have long lasting makeup.
Patent Document 3 describes that an oil-in-water emulsified cosmetic containing a fluorinated oil agent, a fluorinated powder, and a water-soluble polysaccharide has a refreshing and good feel and is excellent in water resistance and oil resistance. ing.

Japanese Patent Laid-Open No. 6-184212 JP-A-7-277914 JP 2001-48726 A

  In the oil-in-water emulsified cosmetic using a fluorine-modified silicone having a perfluoroalkyl group (C8), after applying to the skin, the finished skin has a feeling of bulkiness. As a result, the inventors found a problem that a feeling of sticking or stiffness was produced at the start of coating when a powder cosmetic such as the above was layered with a sponge.

  The present inventors maintain water resistance and sebum resistance by using a combination of a specific fluorine-modified silicone, a water-soluble polysaccharide derivative, a powder surface-treated with tridecafluorooctyltriethoxysilane, and fine zinc oxide. In addition, oil-in-water emulsified cosmetics that suppress the feeling of bulkiness of the finished skin, suppress the feeling of getting stuck in the initial stage of powder cosmetics such as powder foundation and white powder, and the firmness of the skin, and moisturize the finished skin It was found that can be obtained.

The present invention includes the following components (A), (B), (C) and (D):
(A) Water-soluble polysaccharide derivative 0.01-5% by mass,
(B) The following general formulas (1) and (2)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ¹ , R ² and R ³ are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 40% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(C) a powder treated with tridecafluorooctyltriethoxysilane,
(D) Fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g surface-treated with silicone or alkylsilane is contained, and the mass ratio (B) / (A) of components (A) and (B) is 3 to 200. It relates to an oil-in-water emulsified cosmetic.

  The oil-in-water emulsified cosmetic of the present invention suppresses the feeling of bulkiness of the finished skin while maintaining water resistance and sebum resistance, and the initial feeling of application of powder cosmetics such as powder foundation and white powder, It suppresses the feeling of stickiness and gives the finished skin a smooth and moist feeling.

The water-soluble polysaccharide derivative of the component (A) used in the present invention is preferably a water-soluble alkyl-substituted polysaccharide derivative, which is water-soluble at room temperature, for example, part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or its derivative. Are the following groups (a) and (b);
(A) a substituent having a hydrophobic part selected from a linear or branched alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group, an alkylaryl group, and a mixture thereof;
(B) a substituent having an ionic or nonionic hydrophilic part that may be substituted by a hydroxyl group,
And the ratio of the number of substituents (a) and substituents (b) is 1: 1000 to 100: 1.

  Here, as the substituent (a), for example, a linear or branched alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group, an alkylaryl group, an alkyl ether group, an alkenyl ether group, an arylalkyl ether group, Alternatively, an alkyl aryl ether group, an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms, an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms, and the like can be given. Among these, an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms are preferable. Specifically, 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy-1- (hydroxymethyl) Examples thereof include an ethyl group, which may be substituted with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to a polysaccharide molecule. The alkyl group or alkenyl group having 10 to 40 carbon atoms substituted on these glyceryl ether groups is preferably a linear or branched alkyl or alkenyl group having 12 to 36 carbon atoms and more preferably 16 to 24 carbon atoms. From the viewpoint of stability, an alkyl group is preferable, and a linear alkyl group is more preferable. In addition, when the substituent (a) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  Examples of the substituent (b) include a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group, and a sulfoalkyl group. Among these, a C1-C5 sulfoalkyl group which the hydroxyl group may substitute, or its salt is preferable. Specific examples include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, 2-sulfo-1- (hydroxymethyl) ethyl group, etc., all or part of which is Na. A salt with an alkali metal such as K, alkaline earth metals such as Ca and Mg, an organic cation group such as amines, or an ammonium ion. In addition, when the substituent (b) has a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a) or (b).

  The degree of substitution of the substituent (a) is preferably 0.001-1 per constituent monosaccharide residue, more preferably 0.002-0.5, and further preferably 0.003-0.1. Preferably, the degree of substitution of the substituent (b) is preferably 0.01 to 2.5, more preferably 0.02 to 2, more preferably 0.1 to 1.5 per constituent monosaccharide residue. Is more preferable. The ratio of the number of substituents (a) and substituents (b) is preferably 1: 1000 to 100: 1, more preferably 1: 500 to 10: 1, and 1: 300 to 10: 1. More preferably. In the water-soluble alkyl-substituted polysaccharide derivative, the substituents (a) and (b) are not necessarily present in the same repeating unit of the polysaccharide or its derivative, and when viewed as a whole molecule. The substituents (a) and (b) may be introduced. The degree of substitution is preferably within the above range on average.

  In addition, the polysaccharide that is the basic skeleton of the water-soluble alkyl-substituted polysaccharide derivative of component (A) or a derivative thereof includes cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch , Ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methylcellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, etc. Among them, cellulose, hydroxyethyl cellulose, Chill cellulose, ethyl cellulose, hydroxypropyl cellulose are preferred. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group and the like of these polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. The substitution degree per constituent monosaccharide residue is preferably 0.1 to 10, more preferably 0.5 to 5. The weight average molecular weight of these polysaccharides or derivatives thereof is preferably 10,000 to 10,000,000, more preferably 100,000 to 5,000,000, and still more preferably 300,000 to 2,000,000.

  As the polysaccharide derivative of component (A), a part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof are (a) a linear or branched alkyl group, alkenyl group, aryl having 8 to 40 carbon atoms. A substituent having a hydrophobic portion selected from an alkyl group and an alkylaryl group; and (b) a sulfo group optionally substituted by a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group, or a hydroxyl group. It is preferably substituted with a substituent selected from alkyl groups, and the ratio of the number of substituents (a) to (b) is 1: 1000 to 100: 1.

In addition, as the component (A), some or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof are represented by the following groups (a ′) and (b ′):
(A ′) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms,
(B ′) A water-soluble alkyl-substituted polysaccharide derivative substituted with a C 1-5 sulfoalkyl group or a salt thereof, which may be substituted with a hydroxyl group, is more preferred.
Here, when the substituents (a ′) and (b ′) have a hydroxyl group, the hydroxyl group may be further substituted with another substituent (a ′) or (b ′).

  Such water-soluble alkyl-substituted polysaccharide derivatives are partially hydrophobized (introduction of the substituent (a ′)) or sulfonated (substituents having a sulfonic acid group (b After introduction of ′), all or some of the remaining hydroxyl groups can be sulfonated or hydrophobized, or simultaneously hydrophobized and sulfonated.

  In the following, description will be made by dividing into hydrophobic reaction and sulfonation reaction. As described above, either the hydrophobization reaction or the sulfonation reaction may be performed first or at the same time, but it is more preferable that the hydrophobization is followed by sulfonation.

<Hydrophobic reaction>
The hydrophobization reaction of the polysaccharide or sulfonated polysaccharide is carried out by dissolving or dispersing the polysaccharide or sulfonated polysaccharide in an appropriate solvent, and from C ₁₀ -C ₄₀ alkyl glycidyl ether and / or C ₁₀ -C ₄₀ alkenyl glycidyl ether. This is done by reacting with a chosen hydrophobizing agent.

The alkyl group and alkenyl group of the C ₁₀ -C ₄₀ alkyl glycidyl ether and C ₁₀ -C ₄₀ alkenyl glycidyl ether used for the hydrophobization reaction may be either linear or branched, and the branch position in the case of branching, in the alkenyl group The number and position of unsaturated bonds are not limited. Specific examples of the alkyl group include a linear alkyl group such as n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n -Heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, n-hentriacontyl group, n-dotriacontyl group, n-tritriacontyl group, n-tetratriacontyl group, n-pentatria Contyl group, n-hexatriacontyl group, n-heptatriacontyl group, n-octatriacontyl group, n-no Triacontyl group and n-tetracontyl group are branched alkyl groups such as methylundecyl group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group, 2-octyldodecyl, 2 -Heptyl undecyl group, 2-decyl tetradecyl group, 2-dodecyl hexadecyl group, 2-tetradecyl octadecyl group, 2-tetradecyl behenyl group and the like. Specific examples of the alkenyl group include a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an icosenyl group, a heicocosenyl group, a dococenyl group, a tricosenyl group, A tetracocenyl group, a pentacocenyl group, a hexacocenyl group, a heptacocenyl group, an octacocenyl group, a nonacocenyl group, a triacontenyl group, an oleyl group, a linoleyl group, a linolenyl group, and the like can be given.

Among these, an alkyl group and an alkenyl group having 12 to 36 carbon atoms, and further 16 to 24 carbon atoms are preferable, and from the viewpoint of stability, an alkyl group and further a linear alkyl group are preferable. These alkyl glycidyl ethers and alkenyl glycidyl ethers can be used alone or in combination of two or more.
The amount of alkyl glycidyl ether and / or alkenyl glycidyl ether can be appropriately adjusted according to the desired amount of hydrophobic substituent introduced into the polysaccharide or derivative thereof, but usually the constituent monosaccharide of the polysaccharide or derivative thereof. A range of 0.001 to 10 equivalents, more preferably 0.003 to 1 equivalents per residue is preferred.

  The hydrophobization reaction is preferably performed in the presence of an alkali, if necessary. Examples of such an alkali include, but are not limited to, alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, and the like. Of these, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of alkali used is preferably 0.01 to 10 mole times the alkyl glycidyl ether or alkenyl glycidyl ether used, more preferably 0.1 to 5 mole times giving good results.

  Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of increasing the reactivity with the hydrophobizing agent by swelling the polysaccharide or sulfonated polysaccharide, a mixed solvent in which 1 to 50% by weight, more preferably 2 to 30% by weight of water is added to the lower alcohol. May be used to carry out the reaction.

  The reaction temperature is preferably in the range of 0 to 200 ° C, more preferably 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. Moreover, the next reaction can also be performed without neutralizing on the way.

  When the thus obtained hydrophobized polysaccharide is subsequently used in the sulfonation reaction, it can be used as it is without being neutralized, and it can be separated by filtration or the like if necessary. It can also be used after washing with alcohol, hydrous acetone solvent or the like to remove unreacted hydrophobizing agents or salts by-produced by neutralization. In addition, when the sulfonation reaction has already been performed before the hydrophobization reaction, after separation by filtration or the like, washing, neutralization or the like is performed as necessary, followed by drying to obtain the polysaccharide derivative of component (A). Can be obtained.

<Sulfonation reaction>
The sulfonation reaction of polysaccharides or hydrophobized polysaccharides is carried out by dissolving or dispersing polysaccharides or hydrophobized polysaccharides in a suitable solvent, and vinyl sulfonic acid or a halo C ₁ -C ₅ alkane optionally substituted with a hydroxyl group. It is carried out by reacting with a sulfonating agent selected from sulfonic acids and their salts.

Among the sulfonating agents used in the sulfonation reaction, examples of the halo C ₁ -C ₅ alkanesulfonic acid that may be substituted with a hydroxyl group include 3-halo-2-hydroxypropanesulfonic acid, 2-halo-2- (Hydroxymethyl) ethanesulfonic acid, 3-halopropanesulfonic acid, 2-haloethanesulfonic acid and the like can be mentioned, and examples of the substituted halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of these salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and ammonium salts. These sulfonating agents can be used alone or in combination of two or more.
The amount of the sulfonating agent can be adjusted as appropriate depending on the amount of sulfonic acid groups introduced into the polysaccharide, but usually 0.1 to 10 equivalents are preferred per constituent monosaccharide residue of the polysaccharide or hydrophobized polysaccharide, The range of 0.2-5 equivalent is more preferable.

This reaction is preferably carried out in the presence of an alkali, if necessary. Such an alkali is not limited, but is the same as that used in the hydrophobization reaction, that is, hydroxylation of an alkali metal or alkaline earth metal. Such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.
As for the usage-amount of an alkali, 1.0-3.0 mol times amount is preferable with respect to the sulfonating agent to be used, and 1.05-1.5 mol times amount gives the favorable result, and is more preferable.

  Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. Further, for the purpose of increasing the reactivity between the polysaccharide or the hydrophobic polysaccharide and the sulfonating agent, 0.1 to 100% by mass is preferable with respect to the lower alcohol, and a mixed solvent in which 1 to 50% by mass of water is added. May be used to carry out the reaction.

  The reaction temperature is preferably 0 to 150 ° C, more preferably 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. The next reaction can also be carried out without neutralization.

  When the sulfonated polysaccharide thus obtained is subsequently used in a hydrophobization reaction, it can be used as it is without being neutralized, and it can be separated by filtration or the like as necessary, or with hot water or hydrous isopropyl. It can also be used by removing unreacted alkylating agent or by-produced salts by neutralization, etc. by washing with alcohol, hydrous acetone solvent or the like. In addition, when the hydrophobization reaction has already been performed before the sulfonation reaction, after separation by filtration, washing, neutralization, etc. are performed as necessary, followed by drying to obtain the polysaccharide derivative of component (A). Can be obtained.

  As described above, the substituents (a) and (b) in the polysaccharide derivative obtained as described above include not only the hydroxyl group of the polysaccharide or its derivative used as a raw material, but also other substituents (a) and In some cases, the hydroxyl group of the substituent (b) may be substituted, and such substitution may occur in a superimposed manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxyl group of the polysaccharide or derivative thereof is substituted with the substituents (a) and (b), when the sulfonation is carried out after the hydrophobization, the substituent (a) is further substituted. The group (a) or (b) may be substituted, and the substituent (b) may be further substituted with the substituent (b). When the group is hydrophobized after sulfonation, the substituent (a ) May be further substituted with a substituent (a), and the substituent (b) may be further substituted with a substituent (b) or (a). May include those in which the substituent (a) is further substituted with the substituent (a) or (b), and the substituent (b) is further substituted with the substituent (a) or (b). Furthermore, there may be included those in which substitution with other substituents occurs in a superimposed manner. In the present invention, any of such polysaccharide derivatives can be used.

  Examples of the water-soluble alkyl-substituted polysaccharide derivative of component (A) include modified cellulose ethers described in Examples 1 to 3 of JP-A No. 3-12401, and non-patents described in US Pat. No. 4,228,277. Ion long-chain alkylated cellulose ether; commercially available products such as alkyl-modified hydroxyethyl cellulose such as NATROSOL PLUS 330 and NATROSOL PLUS D-67 (manufactured by Aqualon Company), and hydrophobic modification Sulfonated polysaccharide derivatives and the like can be preferably used.

  Component (A) can be used alone or in combination of two or more. From the point of forming a stable oil-in-water emulsion, the content is 0.01% by mass or more in the total composition, and 0 0.05 mass% or more is preferable, and 0.1 mass% or more is more preferable. And from the point which forms the emulsion which is excellent in the fresh feeling of use and the powder foundation foundation, and is excellent in stability, it is 5 mass% or less, 2 mass% or less is preferable, and 1 mass% or less is more. preferable. Moreover, content of a component (A) is 0.01-5 mass% in the whole composition, 0.05-2 mass% is preferable, and 0.1-1 mass% is more preferable.

The fluorine-modified silicone of component (B) used in the present invention has a polysiloxane unit represented by the general formulas (1) and (2).
In the formula, examples of the alkyl group represented by R ¹ , R ² and R ³ include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; isopropyl group, sec- Examples thereof include branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; cyclic alkyl groups such as cyclopentyl and cyclohexyl.

Moreover, m shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. n shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.

  Further, the ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (2) with respect to the total p + s of the polysiloxane units represented by the general formulas (2) and (3) is used. 0.66 ≦ p / (p + s) ≦ 0.9, and 0.75 ≦ from the viewpoint that it is excellent in feeling and makeup, is less likely to cause uneven appearance, and is less likely to cause uneven application after the cosmetic is applied. p / (p + s) ≦ 0.83 is preferable.

The fluorine-modified silicone as component (B) can be produced, for example, according to the method described in JP-A-6-184212.
As the component (B), those represented by the following general formula (3) are preferable.

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

  Component (B) can be used singly or in combination of two or more. From the standpoint of excellent water resistance, sebum resistance, and long-lasting makeup, the content is 0.01% by mass or more in the total composition, and 0 1 mass% or more is preferable, 1 mass% or more is more preferable, and 4 mass% or more is more preferable. And from the point of feeling of use, sebum resistance, makeup lasting, and no feeling of catch when applying powder foundation, it is 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass. The following is more preferable. Moreover, content of a component (B) is 0.01-40 mass%, 0.1-30 mass% is preferable, 1-20 mass% is more preferable, 4-15 mass% is further more preferable.

  In the present invention, the mass ratio (B) / (A) of the components (A) and (B) maintains emulsion formation, water resistance and sebum resistance with good stability, and suppresses the feeling of bulkiness of the finished skin. On the other hand, it is 3 or more, and 5 or more from the point that it suppresses the initial squeezing and powdery feeling of powder cosmetics such as powder foundation and white powder, and the finished skin can be smooth and moist. Preferably, 10 or more is more preferable, 200 or less, 150 or less is preferable, and 100 or less is more preferable. Moreover, mass ratio (B) / (A) of component (A) and (B) is 3-200, 5-150 is preferable and 10-100 are more preferable.

The powder of component (C) 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, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, it is possible to suppress uneven skin and obtain a natural finish. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

  The powder to be treated is not limited as long as it is an extender or a color pigment used in ordinary cosmetics. For example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, bengara , 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, chromium oxide , Chromium hydroxide, calamine and carbon black, inorganic powders such as these composites; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine resin , Epoxy tree , Polycarbonate resin, divinylbenzene / styrene copolymer, silk powder, cellulose, long-chain alkyl phosphate metal salt, N-mono long-chain alkyl acyl basic amino acid, organic powders such as these complexes; A composite powder of a powder and an 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, and chloroform, and normal hexane, toluene, and xylene. Hydrocarbon organic solvents are suitable.

  The treatment amount of tridecafluorooctyltriethoxysilane varies depending on the powder, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 50% by mass with respect to the mass of the powder of the component (C). % Or less is preferable, and 20% by mass or less is more preferable. 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 (C) 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 size of the component (C) 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 (C) can be used singly or in combination of two or more, and it has excellent water resistance, sebum resistance, and long-lasting makeup. From the viewpoint of finish and stability, the content is 0.01 mass in the total composition. % Or more, preferably 1% by weight or more, more preferably 3% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less, and 12% by weight or less. Even more preferred. Moreover, 0.01-30 mass% is preferable in the whole composition, as for content of a component (C), 1-25 mass% is more preferable, 3-20 mass% is further more preferable, and 3-12 mass% is more. Further preferred.

  In the present invention, the mass ratio (C) / (A) of the components (A) and (C) maintains the water resistance and sebum resistance and suppresses the feeling of bulkiness of the finished skin, while maintaining the powdery foundation, white powder, etc. 3 or more is preferable, 8 or more is more preferable, and 10 or more is more preferable from the viewpoint that the feeling of catching and the feeling of firmness of the skin in the initial application of the powder cosmetic is suppressed, and the finished skin can be smooth and moist. 100 or less, more preferably 80 or less, and even more preferably 70 or less. Moreover, 3-100 are preferable, as for the mass ratio (C) / (A) of a component (A) and (C), 8-80 are more preferable, and 10-70 are still more preferable.

The fine particle zinc oxide of the component (D) used in the present invention has a specific surface area of 10 to 100 m ² / g, preferably 15 to 95 m ² / g. By using the fine particle zinc oxide having such a specific surface area, the cosmetic durability is excellent and a good feeling of use can be obtained.
The finely divided zinc oxide component (D) has been surface-treated with silicone or alkylsilane. By using such a surface-treated product, sebum resistance and the feeling of bulkiness of the finished skin are suppressed, and the initial feeling of application of powder cosmetics such as powder foundation and white powder, and the feeling of firmness of the skin are suppressed. In addition, smoothness and moist feeling can be obtained on the finished skin.

  Examples of the silicone for treating the fine zinc oxide include silicone oils containing Si—H groups such as methylhydrogenpolysiloxane, silicone oils containing Si—OH groups, cyclic dimethylpolysiloxane, dimethylsilicones and the like. Of these, dimethylpolysiloxane or methylhydrogenpolysiloxane is preferred from the viewpoints of feeling in use, blendability, and long-lasting makeup.

As a method of treating fine particle zinc oxide with silicone, a usual method can be used.
The treatment amount of silicone is preferably 0.1 to 30% by mass, and more preferably 0.1 to 10% by mass with respect to the fine particle zinc oxide.

On the other hand, alkylsilane for treating fine zinc oxide is a compound represented by the following formula.
R ⁴ R ⁵ _n -SiX _(3-n)
(In the formula, R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms, preferably 4 to 12 carbon atoms, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, and X represents a carbon number. 1 to 3 alkoxy groups or halogen atoms (such as chlorine atoms), and n represents an integer of 0 to 2)

  Examples of such alkylsilanes include isobutyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dimethylbutylchlorosilane, and the like. Of these, those having an octyl group are preferred, and octyltriethoxysilane is more preferred because it is easy to produce and the treated powder exhibits sufficient water repellency.

As a method for treating fine particle zinc oxide with alkylsilane, a reaction by a gas phase or a surface treatment method by an organic slurry which are usually performed can be used.
As an example, first, a fine particle zinc oxide is charged into a mixer and stirred, and a silane solution in which an alkoxyalkylsilane compound is dissolved in an organic solvent alone or a mixture of an organic solvent and water is added in advance. Mix and knead. Next, the obtained fine particle zinc oxide mixed solution is dried at 80 to 90 ° C., and further heat-treated at 110 to 160 ° C., whereby an alkylsilane-treated powder treated with an alkoxyalkylsilane compound is obtained.
The treatment amount of the alkylsilane is preferably 0.1 to 30% by mass, more preferably 0.1 to 10% by mass with respect to the fine particle zinc oxide.

  Component (D) can be used alone or in combination of two or more. From the standpoint of makeup, the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the total composition. 1 mass% or more is still more preferable, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 8 mass% or less is still more preferable. Moreover, 0.01-20 mass% is preferable in the whole composition, as for content of a component (D), 0.1-10 mass% is more preferable, and 1-8 mass% is still more preferable.

  In the present invention, the mass ratio (B) / (D) of the components (B) and (D) suppresses the feeling of bulkiness of the finished skin while maintaining water resistance and sebum resistance, such as powder foundation and white powder. 0.5 or more is preferable, 1 or more is more preferable, and 1.2 or more is preferable from the point that smoothness and moist feeling can be obtained in the finished skin by suppressing the feeling of catching and the feeling of skin firmness in the initial application of the powder cosmetic. The above is more preferable, 10 or less is preferable, 8 or less is more preferable, and 7 or less is more preferable. Moreover, 0.5-10 are preferable, as for the mass ratio (B) / (D) of a component (B) and (D), 1-8 are more preferable, and 1.2-7 are still more preferable.

  In the present invention, the mass ratio (C) / (D) of the components (C) and (D) suppresses the feeling of bulkiness of the finished skin while maintaining water resistance, sebum resistance, and sebum resistance. , 0.5 or more is preferable, because it suppresses the initial squeezing feeling and firmness of the skin when powder cosmetics such as powder foundation and white powder are applied, and the finished skin is smooth and moist. Is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is still more preferable. Moreover, 0.5-10 are preferable, as for the mass ratio (C) / (D) of a component (C) and (D), 1-5 are more preferable, and 1-3 are still more preferable.

Furthermore, in the present invention, the total content of components (C) and (D) suppresses the feeling of bulkiness of the finished skin while maintaining water resistance, sebum resistance, sebum resistance, powder foundation, white powder, etc. It is preferably 70% by mass or more of the total powder from the viewpoint of suppressing the feeling of catching and the feeling of firmness of the skin in the initial application of the powder cosmetic, and obtaining a smooth and moist feeling on the finished skin, 90 The mass% or more is more preferable.
Further, the total content of the components (C) and (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, in the total composition, from the viewpoint of having a makeup. % By mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is more preferable.

  The content of water used in the present invention is preferably 10% by mass or more, more preferably 40% by mass or more, and preferably 90% by mass or less, and 80% by mass in the total composition from the viewpoint of usability and storage stability. % Or less is more preferable. Moreover, it is preferable to contain 10-90 mass% of water in the whole composition, and 40-80 mass% is more preferable.

In addition, the oil used in the present invention may be liquid at 20 ° C. excluding component (B). When using a solid or paste oil, dissolve it in another oil or solvent once. Is preferably used.
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, 5 mass% or more is preferable in the whole composition, as for content of the oil agent used for this invention, 7 mass% or more is more preferable, 50 mass% or less is preferable, and 30 mass% or less is more preferable. Moreover, it is preferable to contain 5-50 mass% of oil agents in the whole composition, and 7-30 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 8 or less, more preferably 6 or less, and still more preferably 4 or less.
The content of the nonionic surfactant is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, more preferably 3% by mass or less, and more preferably 1% by mass or less in the total composition. Moreover, it is preferable to contain 0.001 to 3 mass% of surfactant in the whole composition, and 0.01 to 1 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 oil-in-water 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; Water-soluble and oil-soluble polymers; powders other than the above components; ethanol, polyhydric alcohols, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, ultraviolet absorbers, humectants, blood circulation promoters , A cooling sensation agent, an antiperspirant, a disinfectant, a skin activator, and the like.

The oil-in-water 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 and cream are preferred.
Further, the oil-in-water emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc .; sunscreen emulsion, suntan It can be applied as UV protection cosmetics such as a stop cream. Among these, a makeup base, a liquid foundation, and a concealer are more preferable, and a makeup base is more preferable.
The oil-in-water emulsified cosmetic composition of the present invention can be used in the case of using a single product alone or in the layering of powder cosmetic products such as powder foundation and white powder.

The oil-in-water emulsified cosmetic of the present invention preferably has a viscosity at 25 ° C. of 0.5 to 200 Pa · s, more preferably 1 to 100 Pa · s from the viewpoint of blending stability, usability, and feeling of use. 2 to 50 Pa · s is more preferable. 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), (C) and (D):
(A) Water-soluble polysaccharide derivative 0.01-5% by mass,
(B) The following general formulas (1) and (2)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ¹ , R ² and R ³ are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 40% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(C) a powder treated with tridecafluorooctyltriethoxysilane,
(D) Fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g surface-treated with silicone or alkylsilane is contained, and the mass ratio (B) / (A) of components (A) and (B) is 3 to 200. Is an oil-in-water emulsified cosmetic.

<2> Component (A) is preferably the following groups (a) and (b) in which some or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof are:
(A) a substituent having a hydrophobic part selected from a linear or branched alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group, an alkylaryl group, and a mixture thereof;
(B) a substituent having an ionic or nonionic hydrophilic part that may be substituted by a hydroxyl group,
A water-soluble polysaccharide derivative in which the ratio of the number of substituents (a) and (b) is 1: 1000 to 100: 1,
A part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof are (a) a hydrophobic group selected from linear or branched alkyl groups, alkenyl groups, arylalkyl groups and alkylaryl groups having 8 to 40 carbon atoms. And (b) a substituent selected from a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group, and a sulfoalkyl group that may be substituted with a hydroxyl group. The oil-in-water emulsion cosmetic according to <1>, wherein a water-soluble polysaccharide derivative in which the ratio of the number of substituents (a) to substituents (b) is 1: 1000 to 100: 1 is more preferable.

<3> Component (A) is preferably such that some or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof are the following groups (a ′) and (b ′):
(A ′) an alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms and / or an alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms,
(B ′) The oil-in-water emulsion cosmetic according to the above <1>, which is a water-soluble alkyl-substituted polysaccharide derivative substituted with a C1-C5 sulfoalkyl group or a salt thereof that may be substituted with a hydroxyl group.

The content of the <4> component (A) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 2% by mass or less, and preferably 1% by mass or less in the total composition. The oil-in-water emulsified cosmetic according to any one of <1> to <3>, more preferably.
<5> Component (B) is preferably the following general formula (3)

(Wherein p and s have the same meaning as described above, and q represents a number of 5)
The oil-in-water emulsified cosmetic according to any one of <1> to <4>, which is represented by:

The content of <6> component (B) is preferably 0.1% by mass or more in the total composition, more preferably 1% by mass or more, further preferably 4% by mass or more, and 30% by mass or less. The oil-in-water emulsified cosmetic according to any one of <1> to <5>, preferably 20% by mass or less, more preferably 15% by mass or less.
<7> The mass ratio (B) / (A) of the components (A) and (B) is preferably 5 or more, more preferably 10 or more, preferably 150 or less, and more preferably 100 or less. The oil-in-water emulsified cosmetic according to any one of 1> to <6>.

The content of <8> component (C) is preferably 0.01% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and more preferably 30% by mass or less in the total composition. The oil-in-water emulsion cosmetic according to any one of <1> to <7>, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 12% by mass or less.
<9> The mass ratio (C) / (A) of the components (A) and (C) is preferably 3 or more, more preferably 8 or more, further preferably 10 or more, preferably 100 or less, 80 The oil-in-water emulsified cosmetic according to any one of <1> to <8>, wherein the following is more preferable, and 70 or less is more preferable.

<10> The oil-in-water emulsion cosmetic according to any one of <1> to <9>, wherein the specific surface area of the particulate zinc oxide of component (D) is preferably 15 to 95 m ² / g.
<11> The oil-in-water emulsion cosmetic according to any one of <1> to <10>, wherein the component (D) is preferably surface-treated with dimethylpolysiloxane or methylhydrogenpolysiloxane.
<12> Component (D) is preferably surface-treated with isobutyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, or dimethylbutylchlorosilane, and the surface is treated with octyltriethoxysilane The oil-in-water emulsified cosmetic according to any one of the above items <1> to <10>, which is more preferably processed.

The content of <13> component (D) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and 20% by mass in the total composition. The oil-in-water emulsified cosmetic according to any one of the above items <1> to <12>, preferably 10% by mass or less, more preferably 8% by mass or less.
<14> The mass ratio (B) / (D) of the components (B) and (D) is preferably 0.5 or more, more preferably 1 or more, further preferably 1.2 or more, and 10 or less. The oil-in-water emulsified cosmetic according to any one of the above items <1> to <13>, preferably 8 or less, more preferably 7 or less.
<15> The mass ratio (C) / (D) of the components (C) and (D) is preferably 0.5 or more, more preferably 1 or more, preferably 10 or less, more preferably 5 or less. 3. The oil-in-water emulsified cosmetic according to any one of <1> to <14>, wherein 3 or less is more preferable.

<16> Any one of <1> to <15>, wherein the total content of components (C) and (D) is preferably 70% by mass or more and more preferably 90% by mass or more in the total powder. 1. The oil-in-water emulsified cosmetic according to 1.
<17> The total content of components (C) and (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and 40% by mass in the total composition. % Or less, 30 mass% or less is more preferable, and 20 mass% or less is more preferable, The oil-in-water type emulsion cosmetic in any one of said <1>-<16>.

<18> The content of water is preferably 10% by mass or more, more preferably 40% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less in the total composition. The oil-in-water emulsified cosmetic according to any one of ~ <17>.
<19> The oil-in-water emulsified cosmetic according to any one of <1> to <18>, preferably a makeup base, a liquid foundation, or a concealer, and more preferably a makeup base.

Synthesis Example 1 (Synthesis of Compound A1)
(1) A 1000 mL glass separable reaction vessel equipped with a stirrer, a thermometer, and a cooling tube is charged with hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP4400, Union Carbide). 50 g, 88 g isopropyl alcohol 400 g, and 48% sodium hydroxide aqueous solution 3.5 g were added to prepare a slurry, which was stirred at room temperature for 30 minutes in a nitrogen atmosphere. To this, 5.4 g of stearyl glycidyl ether was added and reacted at 80 ° C. for 8 hours for hydrophobization. After completion of the hydrophobic reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of 80% acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 49.4 g of a hydrophobized hydroxyethylcellulose derivative.

(2) In a 500 mL glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 10.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 80.0 g of isopropyl alcohol and 48% sodium hydroxide A slurry solution was prepared by charging 0.33 g of an aqueous solution, and stirred at room temperature for 30 minutes under a nitrogen stream. To the reaction solution, a mixed solution consisting of 6.4 g of sodium 3-chloro-2-hydroxypropanesulfonate, 2.7 g of 48% sodium hydroxide aqueous solution and 20.0 g of water was added, and sulfonation was performed at 50 ° C. for 9 hours. . After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was filtered off. The product was washed 3 times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and then dried at 70 ° C. for 1 day under reduced pressure, and replaced with stearyl glyceryl ether groups and sulfo-2-hydroxypropyl groups. Thus, 7.2 g of the water-soluble alkyl-substituted polysaccharide derivative (1) was obtained.

  The degree of substitution of the stearyl glyceryl ether group of the obtained water-soluble alkyl-substituted polysaccharide derivative (1) is 0.030, the degree of substitution of the sulfo-2-hydroxypropyl group is 0.15, and the hydrophobic part substituent (a) and The ratio of the number of hydrophilic part substituents (b) was 30: 150.

Synthesis Example 2 (Synthesis of Compound A2)
In Production Example 1, after hydrophobizing in the same manner except that the amount of stearyl glycidyl ether was 10.8 g, the amount of sodium 3-chloro-2-hydroxypropanesulfonate was 9.6 g, 48% sodium hydroxide aqueous solution Sulfonation was carried out in the same manner except that the amount of 2.7 g was changed to 4.0 g to obtain a water-soluble alkyl-substituted polysaccharide derivative (2).

  The obtained water-soluble alkyl-substituted polysaccharide derivative (2) has a stearyl glyceryl ether group substitution degree of 0.058 and a sulfo-2-hydroxypropyl group substitution degree of 0.20, and the hydrophobic part substituent (a) and The ratio of the number of hydrophilic substituents (b) was 58: 200.

Synthesis Example 3 (Synthesis of Compound B1)

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 B1) (yield 89%).

Synthesis Example 4 (Synthesis of Compound B2)

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 B2) (yield 85%).

Synthesis Example 5 (Synthesis of Compound B3)

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 B3) as a colorless and transparent oil (yield 87%).

Synthesis Example 6 (Synthesis of Compound B4)

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. Unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective compound (Compound B4) as a colorless and transparent oil (yield 78%).

Examples 1-13 and Comparative Examples 1-6
Producing oil-in-water emulsified cosmetics (makeup base) having the composition shown in Table 1, freshness, feeling of roughness of the finished skin, durability of sebum, persistence of powder foundation application, smoothness after application of powder foundation, Evaluation was made on the lack of firmness of the skin after applying the powder foundation, the moist feeling of the skin after applying the powder foundation, water resistance and sebum resistance. The results are also shown in Table 1.

(Production method)
After roughly mixing the powder components, the powder components were mixed and pulverized using an Admizer pulverizer (Fuji Paudal). The oil phase component was mixed, and the pulverized powder component was added and dispersed with a disper. Furthermore, the water phase component was mixed and added to the oil phase and powder mixture to emulsify. Thereafter, the viscosity was adjusted with a homomixer to obtain an oil-in-water emulsified cosmetic (makeup base).

(Evaluation method)
Five professional panelists apply each oil-in-water emulsified cosmetic (makeup base) to their skin by hand, evaluates the “freshness” immediately after application, and the “feel of the finished skin”, and 6 hours after application. The later “sebum resistance persistence” was evaluated according to the following criteria. A result is shown by the integrated value of 5 persons.

(1) Freshness:
5; I feel quite fresh after application.
4; Feels fresh after application.
3; Feels a little fresh after application.
2; Does not feel much freshness after application.
1; Does not feel fresh after application.

(2) Finished skin feel:
5; No feeling of bulkiness after application.
4; Almost no feeling of bulk after application.
3: A feeling of roughness after application is slightly felt.
2; feels a feeling of bulk after application.
1; A feeling of bulkiness after application is considerably felt.

(3) Sebum durability:
5: The sebum resistance persistence is quite good.
4; Good sebum durability.
3; Sebum resistance persistence is slightly good.
2: The sebum resistance persistence is not so good.
1: The sebum resistance persistence is not good.

(Evaluation method)
Immediately after 5 specialist panelists apply each oil-in-water emulsified cosmetic (makeup base) to their skin by hand, and then apply a powder foundation (Sophina Fine Fit Powder Foundation UV, manufactured by Kao Corporation) with a special sponge. Were evaluated in accordance with the following criteria: “A feeling of catching at the initial stage of application”, “Smoothness after application”, “A feeling of firmness of the skin after application”, and “Moisture feeling after application”. A result is shown by the integrated value of 5 persons.

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

(5) Smoothness after powder foundation application:
5: Sliding after application is quite good.
4; Good sliding after application.
3; Slip after application is slightly good.
2; Slip after application is slightly bad.
1; Slip after application is poor.

(6) No firmness of skin after applying powder foundation:
5; Does not feel a feeling of stiffness on the skin after application.
4; Almost no feeling of stiffness on the skin after application.
3; feels a little stiff on the skin after application.
2; feels firmness on the skin after application.
1; The skin after application | coating feels a feeling of firmness considerably.

(7) Moisturized skin after applying powder foundation:
5; The skin after application | coating feels a moist feeling considerably.
4; feels moist on the skin after application.
3; The skin after application is slightly moist.
2; Does not feel much moist on the skin after application.
1; Does not feel moist on the skin after application.

(8) Water resistance (water contact angle):
Prepare an artificial leather sheet (made of polyurethane, 10 cm square), apply 80 mg of each cosmetic material with fingers so that the surface is uniform on 5 cm square (25 cm ² ), and dry at 40 ° C. and 50% humidity for 1 hour. . Then, the sheet is divided into equal parts using a cutter so that it can be inserted into a contact angle measuring device, and one drop of ion exchange water is dropped from the tip of the microsyringe onto the sample surface in an environment of 20 ° C. and 50% humidity. The contact angle (degree) at that time was measured after 1 minute.

(9) Sebum resistance (Squaran contact angle):
In the same manner as in (8), one drop of squalane was dropped on the sample surface from the tip of the microsyringe, and the contact angle (degree) at that time was measured after 1 minute.

Claims (8)

The following components (A), (B), (C) and (D):
(A) Water-soluble polysaccharide derivative 0.01-5% by mass,
(B) The following general formulas (1) and (2)

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ¹ , R ² and R ³ are the same or different and each represents a linear or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, m represents a number of 2 to 6, n represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
0.01 to 40% by mass of a fluorine-modified silicone having a polysiloxane unit represented by
(C) a powder treated with tridecafluorooctyltriethoxysilane,
(D) Fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g surface-treated with silicone or alkylsilane is contained, and the mass ratio (B) / (A) of components (A) and (B) is 3 to 200. Is an oil-in-water emulsified cosmetic.   Component (A) is a part of or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or derivative thereof: (a) a linear or branched alkyl group, alkenyl group, arylalkyl group and alkyl group having 8 to 40 carbon atoms A substituent having a hydrophobic portion selected from an aryl group, and (b) a sulfoalkyl group optionally substituted by a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group and a hydroxyl group. The oil-in-water emulsion cosmetic according to claim 1, which is a water-soluble polysaccharide derivative that is substituted with a substituent that has a ratio of the number of substituents (a) to (b) of 1: 1000 to 100: 1. Fee.   The oil-in-water emulsified cosmetic according to claim 1 or 2, comprising 0.01 to 30% by mass of the component (C).   The oil-in-water emulsified cosmetic according to any one of claims 1 to 3, comprising 0.01 to 20% by mass of the component (D).   The oil-in-water emulsified cosmetic according to any one of claims 1 to 4, wherein the total content of components (C) and (D) is 70% by mass or more in the total powder.   The oil-in-water type milk cosmetic according to any one of claims 1 to 5, wherein the mass ratio (C) / (D) of the components (C) and (D) is 0.5 to 10.   The oil-in-water emulsified cosmetic according to any one of claims 1 to 6, wherein the mass ratio (C) / (A) of the components (A) and (C) is 3 to 100.   The oil-in-water emulsified cosmetic according to any one of claims 1 to 7, wherein the mass ratio (B) / (D) of the components (B) and (D) is 0.5 to 10.