JP2001131013A - Cosmetic containing fluorine-treated powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic having high water-resistance, forming durable make-up and giving good feeling. SOLUTION: The objective cosmetic contains 1-95 wt.% cosmetic powder treated with a fluorine copolymer containing (a) 5-95 wt.% repeating unit induced from a fluorine-containing (meth)acrylate and (b) 1-50 wt.% repeating unit induced from a silicon-containing polymerizable compound and/or (c) 0-50 wt.% repeating unit induced from a non-fluorine monomer other than the silicon- containing compound of the component (b) and 1-95 wt.% silicone and/or fluorine-modified silicone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for stably dispersing a fluorinated powder in silicone or fluorine-modified silicone, and a cosmetic using the same has good water resistance, has little makeup loss, and has good cosmetic properties. It has a nice feel. In addition, when the fluorinated powder stably dispersed in silicone or fluorine-modified silicone is emulsified with water using a lipophilic nonionic surfactant according to the present technology, a cosmetic that is very comfortable to use can be obtained.

[0002]

2. Description of the Related Art In recent years, in order to make powders used in summer cosmetics difficult to wet with sweat, sebum and water, the surface of the powders has to be perfluoroalkyl group-containing phosphoric acid ester ( For example, JP-A-3-24621
The technology for processing in 0) has become established. On the other hand, when the powder is fluorinated, it is difficult to disperse the silicone in silicones commonly used in many cosmetics, and there is a problem that it is difficult to mix it in the formulation. In order to solve this problem, a technique using fluorine-modified silicone instead of silicone has been developed (JP-A-5-124933), but the dispersibility has not been sufficiently satisfactory.

[0003]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above-mentioned problems, a powder for cosmetics surface-treated with a specific fluorine-based (meth) acrylate copolymer has been developed. It has been found that it is stably dispersed in silicone or fluorine-modified silicone. In addition, when the fluorinated powder stably dispersed in silicone or fluorine-modified silicone was emulsified with water using a lipophilic nonionic surfactant according to the present technology, a cosmetic that was very comfortable to use was obtained.

The fluorinated (meth) acrylate used for the fluorinated copolymer has, for example, the following general formula (I-1).

[0005]

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Wherein Rf is a polyfluoroalkyl group or a perfluoropolyether group having 6 to 16 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms,

[0007]

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(Where R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 4 carbon atoms), or

[0009]

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Wherein X is a hydrogen atom or a methyl group. Further, the fluorine-based (meth) acrylate may be a fluorine-based (meth) acrylate macromonomer having the following general formula (I-2).

[0011]

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Wherein Rf is a polyfluoroalkyl group having 6 to 16 carbon atoms or a perfluoropolyether group;
A ¹ is an alkylene group having 1 to 4 carbon atoms,

[0013]

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(Where R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 4 carbon atoms), or

[0015]

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X ¹¹ is a hydrogen atom or a methyl group, Y ¹¹ is a hydrogen atom or a methyl group, and m is 5
~ 100. The polyfluoroalkyl group (Rf group) may be a perfluoroalkyl group. The perfluoropolyether group is specifically as follows. F (CF (CF ₃ ) C
F ₂ O) _n CF ₂ CF ₂ —, wherein n is an integer of 3 to 30. _{] CF 3 O (CF (CF} 3) CF 2 O) n (CF 2 O) m CF 2 -,
[Wherein, n is an integer of 2 to 30 and m is an integer of 3 to 70. _{] CF 3 O (CF 2 CF} 2 O) n (CF 2 O) m CF 2 -, in the Expression,
n is an integer of 2 to 40 and m is an integer of 4 to 70. _{] F (CF 2 CF 2 CF} 2 O) n CF 2 CF 2 - [ wherein, n =. 3 to
It is an integer of 30. ] Number average molecular weight of perfluoropolyether group ( ¹⁹ F-N
(Measured by MR) is preferably in the range of 500 to 5,000.

Examples of the fluorinated (meth) acrylate are as follows. CF ₃ (CF ₂ ) ₇ (CH ₂ ) OCOCH = CH ₂ , CF ₃ (CF
₂ ) ₆ (CH ₂ ) OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (C
F ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH
₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O
COCH = CH ₂ , HCF ₂ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH
ＣＨCH ₂ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH ＝ CH ₂ ,
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = C
_{H 2, CF 3 (CF 2} ) 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOC
(CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OC
OCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF
(CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ ,

[0018]

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F (CF (CF ₃ ) CF ₂ O) ₁₀ CF ₂ CF ₂ -C
OOCH ₂ CH ₂ CH = CH ₂ ,

[0020]

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[0021]

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[0022]

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These fluorine (meth) acrylates may be used as a mixture of two or more kinds.

In the present invention, the non-fluorinated monomers copolymerized with the fluorine-based copolymer are roughly classified into a silicon-containing polymerizable compound, a polyalkylene glycol (meth) acrylate, an alkyl (meth) acrylate, and an alkyl (meth) acrylate. There are four types of macromonomers.

The silicon-containing polymerizable compound is at least one selected from the group consisting of a silicone macromonomer, a mercapto-modified silicone, an azo group-containing silicone, and a polymerizable silane.

The mercapto-modified silicone is a silicone having at least one SH group. The mercapto-modified silicone has, for example, the following general formula (II-1) or (II-2).

[0027]

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Or

[0029]

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[In the formula, R ³ is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms and having a linear or branched carbon chain optionally interrupted by one or two ether bonds. Where l is 10 to 20, m is 10 to 200, and n is 1 to 10. Specific examples of the mercapto-modified silicone are as follows.

[0031]

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[0032]

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The silicone macromonomer has, for example, the following general formula (III-1).

[0034]

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[Wherein Me is a methyl group;
⁴ is a methyl group or a hydrogen atom, and R ⁵ is a group of 1 to 10 carbon atoms having a linear or branched carbon chain optionally interrupted by one or two ether bonds.
A monovalent saturated hydrocarbon group, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and m is 3 to 300. ] R ^5, _{specifically, -CH 2 -, - (CH} 2) 3 -, - (C
_{H 2) 6 -, - (} CH 2) 10 -, - CH 2 -CH (CH 3) -CH
_{2 -, - CH 2 -CH 2} OCH 2 CH 2 CH 2 -, - CH 2 C
_{H 2 OCH 2 CH (CH 3} ) CH 2 -, - CH 2 CH 2 OCH 2
_{CH 2 OCH 2 CH 2 CH 2} - , etc. are exemplified.

The silicone macromonomer is suitably used as a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain, and specific examples include the following.

[0037]

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[0038]

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[In the above formula, Me is a methyl group. The azo group-containing silicone may be a silicone having an azo group and a urethane bond. The azo group-containing silicone has, for example, the following general formula (IV-1).

[0040]

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Wherein x is from 10 to 200, and n is 1
-20. Specific examples of the azo group-containing silicone are as follows.

[0042]

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The polymerizable silane is a compound having an ethylenically unsaturated double bond and a siloxane bond. The polymerizable silane is, for example, represented by the following general formula (V-1) or (V
-2).

[0044]

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Or CH ₂ ＣＨCHSi (OR ⁹ ) ₃ (V-2) wherein R ⁷ is a methyl group or a hydrogen atom;
⁸ is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms having a linear or branched carbon chain which is optionally interrupted by one or two ether bonds, and R ⁹ is It is an alkyl group having 1 to 4 carbon atoms. Specific examples of the polymerizable silane are as follows.

[0046]

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CH ₂ ＣＨCHSi (OCH ₃ ) ₃ These silicon-containing polymerizable compounds may be used as a mixture of two or more kinds.

The fluorine-containing copolymer of the present invention comprises at least one selected from the group consisting of polyalkylene glycol (meth) acrylates, alkyl (meth) acrylates and alkyl (meth) acrylate macromonomers.
It may have a repeating unit derived from a non-fluorinated monomer other than the silicon-containing polymerizable compound.

The polyalkylene glycol (meth) acrylate has, for example, the following structural formula (VI-1). CH ₂ ＣＲCR ¹⁰ COO— (R ¹¹ —O) _n —R ¹² (VI-1) wherein R ¹⁰ and R ¹² are hydrogen or a methyl group, R ¹¹ is an alkylene group having 2 to 6 carbon atoms, n Represents an integer of 1 to 50. Specifically, 2-hydroxyethyl (meth) acrylate, CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) _n H, wherein n is 2, 5 or 8. And the like.

The alkyl (meth) acrylate has, for example, the following structural formula (VII-1).

[0051]

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[In the formula, X is a hydrogen atom or a methyl group, and n is 1 to 22 (for example, 1 to 10). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n
-Butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, dorazyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and the like.

The alkyl (meth) acrylate macromonomer has, for example, the following structural formula (VIII-2).

[0054]

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[In the formula, each of X ²¹ and Y ²¹ is a hydrogen atom or a methyl group, n is 1 to 22, and m is 5 to 100. ] In particular,

[0056]

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[0057]

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And the like.

These non-fluorinated monomers may be used as a mixture of two or more kinds.

A suitable monomer may be used in combination with the non-fluorinated monomer in order to improve the feeling of use or to impart functions other than water resistance and water / oil repellency. Specific examples include glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, vinyl chloride, vinylidene chloride, and (meth) acrylic acid.

The fluorocopolymer used in the present invention imparts water resistance, water repellency and oil repellency to the powder for cosmetics and a favorable feeling upon use.

In a copolymer comprising a fluorine-based copolymer and a non-fluorine-based monomer, the content of the fluorine-based copolymer is as follows:
It is at least 5% by weight, more preferably from 10 to 95% by weight, particularly preferably from 20 to 90% by weight. In the copolymer, the greater the proportion of non-fluorinated monomers, the better the feeling of use when blended into cosmetics, i.e., "slip feeling", "smooth feeling", etc., and also, water, against non-fluorinated solvents Although the solubility is improved, if the proportion of the non-fluorinated monomer exceeds 95% by weight, sufficient water resistance and water / oil repellency cannot be imparted to the film.

The fluorocopolymer used in the present invention can be produced by bulk polymerization, solution polymerization, or emulsion polymerization. In the bulk polymerization, a method in which a mixture of a fluorine-based copolymer and a non-fluorine monomer is replaced with nitrogen, a polymerization initiator is charged, and the mixture is stirred for several hours in a range of 40 to 80 ° C. to perform polymerization. In the case of solution polymerization, a mixture of a fluorinated copolymer and a non-fluorinated monomer is dissolved in a suitable organic solvent in which these monomers are soluble and polymerized in the same manner. The organic solvent used here is a hydrocarbon-based, ester-based, ketone-based, alcohol-based, silicone-based, or fluorine-based solvent.

In the case of emulsion polymerization, these monomers are emulsified in water using a suitable emulsifier and then polymerized in the same manner.
In a certain combination of a fluorine-based copolymer and a non-fluorine-based monomer, the copolymerizability is deteriorated due to poor compatibility between the fluorine-based copolymer and the non-fluorine-based monomer in water.
In this case, a method of improving the compatibility of both monomers by adding a suitable auxiliary solvent such as glycols and alcohols is employed. The emulsifier used in the emulsion polymerization may have any of a hydrocarbon group, a silicone group, and a fluorine group as a hydrophobic group, and may have any of nonionic, anionic, cationic and amphoteric hydrophilic groups.

Examples of the polymerization initiator include various azo compounds and peroxides. At the time of polymerization, a chain transfer agent or a pH adjuster may be added as necessary. The molecular weight of the fluorocopolymer obtained after the polymerization is from 10,000 to 1,000,000.
0, preferably 20,000 to 300,000
It is.

The fluorinated copolymer prepared by solution polymerization or emulsion polymerization is processed into powder after isolating and purifying only the polymer. The treatment concentration of the fluorocopolymer is in the range of 0.5 to 20% by weight, preferably 1 to 5% by weight, based on the powder. If it is less than this range, the effect of the fluorine-based copolymer is not obtained, and if it is too large, the feeling of use of the powder is impaired.

In the present invention, the powder treated with the fluorocopolymer is not particularly limited as long as it is a powder commonly used in cosmetics. For example, talc, kaolin, sericite,
Mica, titanium mica, titanium oxide, iron oxide, magnesium oxide, zinc monoxide, zinc dioxide, heavy or light calcium carbonate, dicalcium phosphate, aluminum hydroxide, barium sulfate, silica, alumina, silica gel, carbon black, oxidation Inorganic powders such as antimony, magnesium aluminate silicate, magnesium aluminate metasilicate, and synthetic mica. Protein powder, fish scale foil, metal soap,
Organic powders such as tar dyes and lakes are exemplified.

When a powder previously treated with a low-molecular fluorine compound (for example, a phosphoric acid ester containing a perfluoroalkyl group) is surface-treated with this fluorine-based copolymer, the following disadvantages of the low-molecular fluorine compound-treated powder are obtained. Can be improved. -Poor affinity with non-fluorine materials. -Poor usability such as stretch and adhesion.・ It soars up as dust when manufacturing cosmetics. -Poor dispersibility in water and non-fluorinated solvents.

Further, when a powder previously treated with silicone (for example, methyl hydrogen polysiloxane) is surface-treated with this fluorine-based copolymer, a more favorable feeling of use is obtained.

The fluorine-based copolymer is attached to the surface of the powder by a wet method or a dry method, but the wet method is more preferable for more uniform surface treatment. Specifically, the powder is mixed with a solution obtained by diluting the fluorine-based copolymer with an organic solvent, and the mixture is stirred at room temperature or under heating until the powder is uniformly wetted with the organic solvent solution. For the stirring at this time, a Henschel mixer, a vibration ball mill, a rotary ball mill,
A stirring device such as a super mixer or a planetary mixer is used. When stirring on a lab scale, a household juicer mixer may be used. The concentration of the copolymer in the organic solvent solution is not particularly limited, but is adjusted so that the viscosity does not become too high during stirring during powder mixing. After stirring, the organic solvent is distilled off by heating in a vacuum or by heating, and the treated powder is uniformly dispersed by the above-described stirring device.
When stirring on a laboratory scale, a household juicer mixer or a speed cutter may be used.

When a water-soluble (or water-dispersible) low molecular fluorine compound is to be treated in advance by an aqueous wet method before the treatment with the fluorine-based copolymer, the treatment should be carried out with a mixed system of water and an organic solvent. It is preferable in terms of simplification of the process to use a flushing method characterized by the following.

In the present invention, if necessary at the time of surface treatment,
An appropriate drug for improving the usability may be used in combination.
Drugs for improving the feeling of use of powder include lecithin, N-mono long chain acyl basic amino acids, silicone,
Examples include chitosan, collagen, and wax.

These fluorine copolymers can be used alone or in combination of two or more, and preferably 1 to 95% by weight, more preferably 5 to 70% by weight in the total composition.
Be blended.

The silicone used in the present invention may be the one usually used in cosmetics, and in particular, volatile low-molecular silicone is preferred from the viewpoint of feeling of use. For example, dimethylpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane (= cyclic silicone trimer),
Octamethylcyclotetrasiloxane (= cyclic silicone tetramer), decamethylcyclopentasiloxane (= cyclic silicone pentamer), dodecamethylcyclohexasiloxane (= cyclic silicone hexamer) and the like can be mentioned.

The fluorine-modified silicone used in the present invention is
For example, those represented by the following general formula are used.

[0076]

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(Wherein Rf is CH ₃ or C _n F _{2n + 1} CH
₂ CH ₂ , at least one of which is C _n F _{2n + 1} CH ₂ CH ₂
It is. Here, n is 1 to 9, m ≧ 1, l ≧ 1) n, l
Is a numerical value determined according to the use in cosmetics, but usually 2 to 100 is preferable.

Specifically, for example, F-type manufactured by Asahi Glass Co., Ltd.
SL-300, X-22-81 manufactured by Shin-Etsu Chemical Co., Ltd.
9, X-22-820, X-22-821, X-22
Commercial products such as 822 and FL-100 and FS1265 manufactured by Toray Dow Corning Silicone Co., Ltd. can be used.

These silicones or fluorine-modified silicones can be used singly or in combination of two or more, and preferably 1 to 95% by weight, more preferably 5 to 70% by weight in the total composition.

When the fluorinated powder stably dispersed in silicone or fluorine-modified silicone is emulsified with water using a lipophilic nonionic surfactant according to the above-mentioned technique, a cosmetic that is very comfortable to use can be obtained. . The emulsion in this case is preferably a W / O type from the viewpoint of water resistance.

The lipophilic nonionic surfactant used in the present invention has an HLB value of 1-10, and includes, for example, polyether-modified silicone, sorbitan fatty acid ester, fatty acid monoglyceride, and alkyl glyceryl ether. Polyether-modified methylpolysiloxane is preferred from the viewpoint of usability.

The polyether-modified silicone is a silicone in which polyethers such as polyoxyethylene, polyoxypropylene, and poly (oxyethylene-oxypropylene) are copolymerized in a block or graft form. And HLB values that vary depending on the copolymerization ratio with respect to silicone.

These lipophilic nonionic surfactants include 1
Species or a combination of two or more kinds can be used, and 0.1 to 5% by weight, preferably 0.3 to 2% by weight is blended in the whole composition. If the amount is less than 0.1% by weight, the emulsifiability deteriorates, and if it exceeds 5% by weight, the feeling of use and the durability of the makeup deteriorate, which is not preferable.

In the present invention, water is blended as the inner phase of the W / O emulsion or the outer phase of the O / W emulsion, and is blended in an amount of 1 to 70% by weight.

In the cosmetic of the present invention, in addition to these essential components, raw materials generally used in cosmetics may be blended. For example, solid / semi-solid oil components such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids and higher alcohols. Liquid oils such as squalane, liquid paraffin, ester oil, diglyceride, triglyceride, and silicone oil. Fluorinated oils such as perfluoropolyether, perfluorodecalin and perfluorooctane. Water-soluble and oil-soluble polymers, surfactants, coloring agents such as organic dyes, ethanol, preservatives, antioxidants, pigments, thickeners,
pH adjusters, fragrances, ultraviolet absorbers, humectants, blood circulation enhancers, cooling agents, antiperspirants, bactericides, skin activators, and the like are used.

The cosmetics of the present invention can be produced according to a usual method, and make-up cosmetics such as foundation, tongue, eye color, cheek color, etc., body cosmetics such as body powder, baby powder, sunscreen cream, sunscreen It can be applied to sunscreen cosmetics such as screen lotions.

If the cosmetic powder used in the present invention is dispersed in silicone or / and fluorine-modified silicone in advance, it is easy to handle during the production of the cosmetic. In order to improve the stability of this dispersion, it is effective to incorporate a polyether-modified silicone having an HLB value of 2-7.

For preparing the dispersion, it is preferable to use a dedicated device for dispersing powder, such as a jet mill, a paint shaker, a sand mill, and a ball mill.

[0089]

EXAMPLES Examples of the present invention will be specifically described, but the description does not limit the present invention.

Production Example 1 In a four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer, CH2 = CHCOO (CH2) 2 (C
F2CF2) nCF2CF3 (hereinafter abbreviated as FA, n =
3,4,5 compound in a weight ratio of 5: 3: 1) 2
0 g, side-chain mercapto-modified silicone (hereinafter referred to as Si-S
Abbreviated as H, Shin-Etsu Chemical KF-2001) 10 g,
10 g of butyl acrylate (hereinafter abbreviated as BA) and 158 g of toluene are added, heated to 80 ° C., and stirred for 30 minutes under a nitrogen stream. To this, 2 g of t-butyl peroxypivalate (trade name: Perbutyl PV, manufactured by NOF Corporation) was added and polymerized for 6 hours. By analyzing the residual FA in the reaction solution by gas chromatography, the polymerization rate of FA was 9
It was confirmed that it was 5%. A part of the obtained reaction solution was precipitated with methanol and dried under vacuum to obtain FA / Si-SH / B
A (= 5 / 2.5 / 2.5 wt.) Copolymer was isolated. When the molecular weight of the obtained FA / Si-SH / BA copolymer was measured by GPC, the weight average molecular weight was 35,000.
(In terms of polystyrene). Production Example 2 10 g of Si-SH, which is a monomer of Production Example 1, was replaced with silicone methacrylate [hereinafter abbreviated as Si-MA, trade name Cylaprene FM-0721 (molecular weight 6900),
Polymerization and isolation were carried out in exactly the same manner except for replacing with 10 g, and FA / Si-MA / BA (= 5 /
2.5 / 2.5 wt. ) A copolymer was obtained. GP to molecular weight
The weight average molecular weight measured by C was 78,000 (in terms of polystyrene). Production Example 3 A total of 40 g of the monomer of Production Example 1 was subjected to 24 g of FA and CH2.
Polymerization was carried out by exactly the same method except that toluene, which is a polymerization solvent, was replaced with 16 g of = CHCOOCH2CH2OH (hereinafter abbreviated as HEMA).
And precipitated with n-hexane instead of methanol,
Then, it is vacuum-dried to obtain FA / HEMA (= 6 / 4w).
t. ) A copolymer was obtained. When the molecular weight is measured by GPC,
The weight average molecular weight was 28,000 (in terms of polystyrene).

Production Examples 4 and 5 The fluorocopolymers of Production Examples 1 and 2 were treated with perfluoroalkyl group-containing phosphate ester-treated titanium oxide fine particles (7% treatment) by the following method. 4 g of the fluorocopolymer was dissolved in 120 g of xylene by heating at 80 ° C. and cooled to room temperature. This polymer solution and 40 g of perfluoroalkyl group-containing phosphate ester-treated fine particle titanium oxide were placed in a juicer mixer and stirred for 30 seconds. The powder dispersion was poured into an aluminum vat and dried in a steam dryer (50 ° C.) for 24 hours.

Production Example 6 The fluorocopolymers of Production Examples 1 and 3 were treated with perfluoroalkyl group-containing phosphate ester-treated titanium oxide fine particles (7% treatment) by the following method. 3.6 g of the fluorinated copolymer of Production Example 1, 0.4 g of the fluorinated copolymer of Production Example 3
Was dissolved in a mixed solvent of 60 g of xylene / 60 g of isopropyl alcohol by heating at 80 ° C., and cooled to room temperature. The subsequent operation is the same as in Production Examples 4 and 5. Examples 1 to 3, Comparative Example 1 Production Examples 4 to 6, and a sunscreen lotion was prepared using a powder not surface-treated with a fluorocopolymer,
Water resistance (FDA method), SPF (JCIA method, coating amount 2m
g / cm2). The feeling of use was evaluated according to the following criteria. ：: Very good ○: Good △: Normal ×: Poor XX: Very poor Evaluation was performed by five panelists specialized in sensory evaluation, and the average was taken as the result.

[0093]

[Table 1]

Example 4, Comparative Example 2 A mixture of 30 g of the finely divided titanium oxide prepared in Production Example 4, 30 g of polyether-modified silicone KF-60176, and 64 g of decamethylcyclopentasiloxane was preliminarily dispersed by a homomixer, and then jet-milled. A dispersion prepared by performing 5 passes is referred to as Example 4. on the other hand,
Comparative Example 2 did not contain 6 g of polyether-modified silicone KF-60176, and instead used 70 g of decamethylcyclopentasiloxane.

In Example 4, no liquid-separating layer was formed after one month, whereas in Comparative Example 2, a liquid-separating layer of 5% of the total volume was formed after one month.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 220/18 C08F 220/18 4J100 220/28 220/28 220/38 220/38 230/08 230/08 290/06 290/06 299/02 299/02 299/08 299/08 C08G 77/442 C08G 77/442 77/52 77/52 C08K 9/06 C08K 9/06 C08L 83/04 C08L 83/04 83 / 08 83/08 // C07F 9/09 C07F 9/09 JKZF term (reference) 4C083 AB242 AC102 AC122 AC482 AC812 AD021 AD151 AD152 AD161 AD162 BB04 BB25 CC01 CC02 CC04 CC19 EE07 FF01 4H050 AB12 4J002 AD00X CP03W CP031 CP08W CP08 DA08 DE076 DE106 DE116 DE126 DE136 DE146 DE236 DG046 DH046 DJ006 DJ016 DJ036 DJ046 DJ056 EG006 FB08X FB086 FB26X FB266 FD096 GB00 HA07 4J027 AC02 AC03 AC04 AC06 AC09 AF05 AJ02 AJ08 AJ09 BA04 BA06 BA07 BA04 BA09 BA10 CB09 A26N CA261 GA02 GB07 HA03 LB14 4J100 AL03R AL04R AL05R AL08P AL08Q AL08R AL09R AP16Q BA02P BA03P BA03R BA05R BA08R BA15P BA15R BA51P BA51R BA59P BA77Q BB12P BB13P BB17P BB18P BC43P CA04 FA04

Claims (11)

[Claims] 1. A repeating unit derived from (a) a fluorine-containing (meth) acrylate in an amount of from 5 to 95% by weight and (b) a repeating unit derived from a silicon-containing polymerizable compound in an amount of from 1 to 5%.
0% by weight and / or a fluorine-containing copolymer containing 0 to 50% by weight of a repeating unit derived from a non-fluorinated monomer other than the silicon-containing polymerizable compound as the component (c) or (b). 1 to 95% by weight of powder for cosmetics,
Silicone and / or fluorine-modified silicone 1-9
Cosmetics characterized by containing 5% by weight. 2. The method according to claim 1, wherein the fluorinated (meth) acrylate has the general formula (I-1): [Wherein, Rf is a polyfluoroalkyl group or a perfluoropolyether group having 6 to 16 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms, (Where R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 4 carbon atoms), or And X is a hydrogen atom or a methyl group. Or a compound represented by the general formula (I-2): [In the formula, Rf is a polyfluoroalkyl group or a perfluoropolyether group having 6 to 16 carbon atoms, A ¹ is an alkylene group having 1 to 4 carbon atoms, (Where R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 4 carbon atoms), or X ¹¹ is a hydrogen atom or a methyl group, and Y ¹¹
Is a hydrogen atom or a methyl group, and m is 5 to 100. The cosmetic according to claim 1, which is a fluorine-containing (meth) acrylate represented by the following formula: 3. The compound containing a silicon-containing polymerizable compound represented by the general formula (II-
1) or (II-2): Or [Wherein, R ³ is optionally one or two ether bonds;
A divalent saturated hydrocarbon group having 1 to 10 carbon atoms having a linear or branched carbon chain interrupted by
Is 10 to 20, m is 10 to 200, and n is 0.1 to 10. And a mercapto-modified silicone represented by the general formula (III-1): [Wherein Me is a methyl group, R ⁴ is a methyl group or a hydrogen atom, and R ⁵ is a linear or branched linear group which is optionally interrupted by one or two ether bonds. A divalent saturated hydrocarbon group having 1 to 10 carbon atoms having a carbon chain of R ⁶ is an alkyl group having 1 to 4 carbon atoms,
m is 3 to 300. A silicone macromonomer represented by the general formula (IV-1): Wherein x is from 10 to 200 and n is from 1 to 20. And an azo group-containing silicone represented by the general formula (V-1) or (V-2): Or CH ₂ ＣＨCHSi (OR ⁹ ) ₃ (V-2) wherein R ⁷ is a methyl group or a hydrogen atom;
⁸ is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms having a linear or branched carbon chain which is optionally interrupted by one or two ether bonds, and R ⁹ is It is an alkyl group having 1 to 4 carbon atoms. The cosmetic according to claim 1, which is at least one member selected from the group consisting of polymerizable silanes represented by the formula: 4. A non-fluorinated monomer represented by the general formula (VI-
1): CH ₂ ＣＲCR ¹⁰ COO— (R ¹¹ —O) _n —R ¹² (VI-1) wherein R ¹⁰ and R ¹² are hydrogen or a methyl group, and R ¹¹ is alkylene having 2 to 6 carbon atoms. The group, n represents an integer of 1 to 50. A polyalkylene glycol (meth) acrylate represented by the general formula (VII-1): Wherein X ² is a hydrogen atom or a methyl group, and n is 1
~ 22. An alkyl (meth) acrylate represented by the general formula (VIII-1): [In the formula, each of X ²¹ and Y ²¹ is a hydrogen atom or a methyl group, n is 1 to 22, and m is 5 to 100. The cosmetic according to claim 1, which is at least one member selected from the group consisting of alkyl (meth) acrylate macromonomers represented by the formula: 5. The cosmetic according to claim 1, wherein the cosmetic powder to be treated with the fluorocopolymer is a powder previously treated with silicone. 6. The cosmetic according to claim 1, wherein the cosmetic powder treated with the fluorocopolymer is a powder previously treated with a low molecular fluorine compound. 7. The low molecular fluorine compound represented by the general formula (IX-
1): [Rf-AO] _n PO (OM) _3-n (IX-1) [wherein, Rf is a polyfluoroalkyl group or a perfluoropolyether group having 6 to 16 carbon atoms, and A is a carbon number. 1
An alkylene group of 4 to (Where R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 4 carbon atoms), or And M represents a hydrogen atom, a metal atom, ammonium or substituted ammonium, and n represents a number of 1 to 3. The cosmetic powder according to claim 6, which is a fluorophosphate ester represented by the formula: 8. A cosmetic comprising water and a lipophilic nonionic surfactant having an HLB value of 1-10 in addition to the cosmetic according to claim 1. 9. A cosmetic according to claim 9, wherein the lipophilic nonionic surfactant is a polyether-modified silicone having an HLB value of 2-7. 10. A cosmetic powder treated with the fluorocopolymer of (a) to (c) according to claim 1 having an HLB value of 2-7.
A dispersion dispersed in a silicone and / or a fluorine-modified silicone in the presence of the polyether-modified silicone. 11. A cosmetic composition containing the dispersion according to claim 10.