JPH10167931A - Water-and oil-repellent powder for cosmetics and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain water- and oil-repellent powder for cosmetics in easy way and at low cost by treating polymer-containing solvent solution which is obtained by polymerizing a specific polymerizable monomer in a specific solvent, and diluting the polymer with a non-fluorine solvent. SOLUTION: This water- and oil-repellent powder for cosmetics is obtained by polymerizing a polymerizable monomer that contains 60wt.% or more of a fluorine-based monomer which is a polyfluoroalkyl group-containing (meth) acrylate of formula I [Rf is a 6-16C polyfluoroalkyl; A is a 1-4C alkylene, formula II (R<1> is a 1-4C alkyl; R<2> is a 1-4C alkylene, or formula III; X is H or methyl] in a solvent which contains a fluorinecontaining solvent (for example, dichloropentafluoropropane) preferably in a quantity of 30wt.% or more, diluting the obtained polymer solution with a non-fluorine solvent (for example, perchloroethylene), and treating power for cosmetic use (for example, talc) with the obtained polymer solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a water- and oil-repellent powder for producing cosmetics which are excellent in water- and oil-repellency, do not disintegrate the makeup, and have a good feeling in use, and the produced water- and oil-repellent powder. The present invention relates to an oily powder and a cosmetic containing a water and oil repellent powder.

[0002]

2. Description of the Related Art Cosmetics containing powders include foundations, white powders, cheek colors, eye colors, body powders and the like. Cosmetics usually contain powders called extenders, white pigments, and color pigments. The extender is composed of an inorganic powder such as talc, kaolin and mica, an organic powder such as a protein powder and a fish scale foil. In addition, white pigments are inorganic powders such as titanium oxide and zinc oxide,
The coloring pigment includes inorganic powders such as red iron oxide, black iron oxide and yellow iron oxide, and organic powders such as lake and tar dye. The above powders are usually amphiphilic and have a property of being compatible with water and oil. For this reason, cosmetics containing such powders are easily wetted by water and secretions such as sweat and sebum, and when wetted, the color tone of the cosmetics originally deteriorates or the color of the skin becomes transparent due to transparency. So-called “make-up collapse”, where the makeup film moves and aggregates due to sweating or facial movement
Phenomenon occurs.

Conventionally, as a technique for preventing makeup collapse due to water and sweat, it is common to impart water repellency by subjecting powder to surface treatment with silicone. However, since the silicone-treated powder has water repellency but no oil repellency, it was not possible to prevent makeup collapse due to sebum.

[0004] In recent years, it has been proposed to impart water and oil repellency by treating the surface of a powder with a fluorine compound in order to prevent makeup collapse due to sebum. For example, Japanese Patent Application Laid-Open
JP 250074 discloses the use of a perfluoroalkyl phosphate diethanolamine salt as a fluorine compound, which has already been put to practical use. However, this fluorine compound is very expensive, it is a price problem, it is difficult to change the properties of the compound because it is non-polymerizable, and the powder is exposed in water because it is hydrophilic. Processing has to be performed, and there is a manufacturing problem that the manufacturing process becomes complicated.

Japanese Patent Application Laid-Open No. 55-167209 discloses the use of a water- and oil-repellent made of a polymer containing a perfluoroalkyl group. There was a problem that it could not always be provided. Specifically, even when a commercially available perfluoroalkyl group-containing acrylate polymer emulsion described in the examples of this publication is diluted with water and treated with a powder, most of the emulsion does not adsorb to the powder surface. Water and oil repellency cannot be imparted.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water- and oil-repellent powder for cosmetics which is inexpensive, has a simple production process, and is excellent in water- and oil-repellency. Another object of the present invention is to provide cosmetics having a good feeling in use.

[0007]

SUMMARY OF THE INVENTION The present invention provides at least 6
Preparing a polymer solution by polymerizing a polymerizable monomer containing 0% by weight of a fluorine-based monomer in a polymerization solvent containing a fluorine-based solvent; Diluting with a system solvent to prepare a polymer diluent,
Provided is a method for producing a water / oil repellent powder for cosmetics, comprising a step of treating the powder with a polymer diluent. In the present invention, a step of preparing a polymer solution by polymerizing a polymerizable monomer containing at least 60% by weight of a fluorine-based monomer in a polymerization solvent containing a fluorine-based solvent, Dissolving the polymer isolated from the coalesced solution in a solvent containing a fluorine-based solvent, diluting the solution in which the polymer is dissolved with a non-fluorinated solvent to prepare a polymer diluent, The present invention also provides a method for producing a water / oil repellent powder for cosmetics, which comprises a step of treating with a combined diluent.

An example of the fluorine-based monomer is a polyfluoroalkyl group-containing (meth) acrylate. The polyfluoroalkyl group-containing (meth) acrylate has the general formula (I):

Embedded image [Wherein, Rf is a polyfluoroalkyl group having 6 to 16 carbon atoms, A is an alkylene group having 1 to 4 carbon atoms,

Embedded image (However, 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

Embedded image X is a hydrogen atom or a methyl group. ].

Specific examples of the polyfluoroalkyl group-containing (meth) acrylate are as follows. CF ₃ (C
F ₂ ) ₇ (CH ₂ ) OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₆ (C
H ₂ ) OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF 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 OC
OCH = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂
OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (C
_{H 2) 2 OCOC (CH 3} ) = CH 2, (CF 3) 2 CF (CF 2) 6
CH ₂ CH (OH) CH ₂ OCOCH ＝ CH ₂ Two or more polyfluoroalkyl group-containing (meth) acrylates may be mixed and used.

In the present invention, the non-fluorinated monomers copolymerized with the polyfluoroalkyl group-containing (meth) acrylate can be roughly classified into two types: non-fluorinated alkyl (meth) acrylates and non-fluorinated alkyl (meth) acrylate macromonomers. Is a seed.

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

Embedded image Wherein X is a hydrogen atom or a methyl group, and n is 12
~ 22. ]

Specific examples of the non-fluorinated alkyl (meth) acrylate include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

The non-fluorinated alkyl (meth) acrylate macromonomer has, for example, the following structural formula:

Embedded image [In the formula, each of X and Y is a hydrogen atom or a methyl group, n is 12 to 22, and 1 is 5 to 100.] ]

Specific examples of the non-fluorine-based alkyl (meth) acrylate macromonomer are as follows.

Embedded image A mixture of two or more non-fluorinated monomers may be used.

In the present invention, preferred combinations of monomers constituting the polymer are as follows. (1) Polyfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate (2) Polyfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate macromonomer (3) Polyfluoroalkyl group-containing (meth) acrylate , Alkyl (meth) acrylate and alkyl (meth)
Acrylate macromonomer

Other monomers may be used in combination to improve the feeling of use or to adjust the bonding strength with the powder. Specific examples of other monomers include glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, vinyl chloride, vinylidene chloride, (meth) acrylic acid, and the like. The amount of the other monomers is 0.1 to 0.1 with respect to the copolymer.
It is preferably 10% by weight, more preferably 1 to 5% by weight.

The polymerizable monomer comprises at least 60% by weight of a fluorine-based monomer based on the total polymerizable monomer.
In the copolymer composed of a fluorine-based monomer and a non-fluorine-based monomer, the content of the fluorine-based monomer is 60% by weight or more, more preferably 60 to 95% by weight, and particularly preferably 70 to 95% by weight.
Preferably it is 90% by weight. In the copolymer,
The greater the proportion of the non-fluorinated monomer, the better the feeling of use when blended in cosmetics, that is, the "puff" by puffing and the "expansion" when applied to the skin. If the proportion of the non-fluorine-based monomer exceeds 40% by weight, sufficient oil repellency cannot be imparted to the powder.

The fluoropolymer is preferably used in an amount of 1 to 10 parts by weight, more preferably 3 to 7 parts by weight, based on 100 parts by weight of the powder. If the amount is less than 1 part by weight, water and oil repellency cannot be imparted. If the amount is more than 10 parts by weight, the feeling of use will be poor.

The fluorinated polymer is polymerized in a polymerization solvent containing a fluorinated solvent. As the fluorine-based solvent, chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC), hydrofluorocarbon (HFC), hydrofluoroether (HFE), fluoroether, fluorocarbon (FC), nitrogen-containing fluorocarbon, and the like are used.

As CFC, 1,1,2-trichloro-
1,2,2-trifluoroethane (CFC-113),
2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane (CFC-316) and the like.
As HCFC, dichloropentafluoropropane (H
CFC-225), dichlorofluoroethane (HCFC
-141b). As HFC 1,1,
1,2,2,3,4,5,5,5-decafluoropentane (H
FC-4310), benzotrifluoride, m-xylenehexafluoride and the like.

Examples of the HFE general _{formula: C n H m F l OC} x H y F z [ wherein, n number of 1 to 12, m is 0 to 25 the number of, l is 0
11 is a number, m + 1 = 2n + 1, x is a number from 1 to 12, and y is 0
The number of ２５25, z is the number of 0１１11, y + z = 2x + 1 (however, m and y are not simultaneously zero, and l and z are not simultaneously zero). ]. Specific examples of the HFE include C ₄ F ₉ OCH ₃ and C ₄ F ₉ OC ₂ H ₅ . Formula The _{fluoroether: (C n F 2n + 1} ) in ₂ O [wherein, n is a number of 3-5. ]. As the fluoroether, specifically, (C ₃ F ₇ ) ₂ O, (C ₄
F ₉ ) ₂ O and the like.

Examples of FC include perfluorohexane, perfluorooctane, perfluorononane, perfluorobenzene, perfluorotoluene, perfluoroxylene, perfluorodecalin, and perfluoromethyldecalin. The nitrogen-containing fluorocarbon general formula _{(C n F 2n + 1)} 3 N [ wherein, n is a number from 1 to 5. ]. Specific examples of the nitrogen-containing fluorocarbon include perfluorotripropylamine and perfluorotributylamine. These fluorinated solvents may be used alone or as a mixture.

The content of the fluorine-based solvent in the polymerization solvent is preferably at least 30% by weight. When the amount of the fluorine-based solvent is less than 30% by weight, even if the reaction solution coagulates during or after the polymerization or does not coagulate, sufficient oil repellency is obtained when the treated powder is produced using the same. May not be expressed.

The polymer is produced by solution polymerization. The polymerizable monomer is dissolved in a polymerization solvent containing a fluorine-based solvent that dissolves the polymerizable monomer.
A method of stirring and polymerizing for several hours in the range of -80 ° C is employed. The polymerization initiator is azobisisobutyronitrile,
Benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, 2,2'-azobis (2-methylpropanenitrile) An oil-soluble material such as the above is used. The polymerization initiator is 0.01 to 100 parts by weight of the polymerizable monomer.
Used in the range of 5 parts by weight. At the time of polymerization, a chain transfer agent may be added as necessary. The molecular weight of the polymer obtained after the polymerization is 5,000 to 500,000, for example, 10,000 to 100,000.

In the present invention, in order to adhere the polymer to the surface of the powder, the polymer solution is diluted with a non-fluorinated solvent and mixed with the powder. The polymer solution used here includes the following two types. That is, (i) a case where the reaction solution after polymerization is used as it is, and (ii) a case where a solution obtained by dissolving the polymer isolated from the reaction solution in a solvent containing 30% by weight or more of a fluorine-based solvent is used. Usually, the former method is used, but the latter method is applied when it is not convenient to mix components other than the polymer and the solvent in the reaction solution (for example, unreacted monomers and initiators) into the treated powder. You. In any case, the polymer having a high fluorine concentration used in the present invention does not dissolve or disperse even when added to a non-fluorinated solvent as it is, so that the powder surface cannot be treated.

The polymer is dissolved in a solvent containing at least 30% by weight of a fluorinated solvent and diluted by adding it to a non-fluorinated solvent to prepare a polymer diluent. Non-fluorinated solvents may be, for example, chlorinated solvents, aliphatic hydrocarbons, aromatic hydrocarbons, esters and ketones. Examples of the chlorine-based solvent include 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, perchloroethylene, and trichloroethylene. Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane and n-hexane.
Examples include dodecane, isohexane, isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, liquid paraffin, and the like.

Examples of the aromatic hydrocarbon include toluene, benzene, xylene and the like. As esters,
Examples thereof include butyl acetate, ethyl acetate, amyl acetate, and acyl acetate. Examples of the ketone include methyl isobutyl ketone, acetone, and methyl ethyl ketone.

The polymer is attached to the surface of the powder by a wet method using an organic solvent. Mix the powder with the polymer diluent,
The solvent is distilled off. That is, the liquid obtained by diluting the polymer solution with the above non-fluorinated solvent is mixed with the powder, and the mixture is stirred at room temperature or under heating until the powder is uniformly wetted with the liquid. For the stirring at this time, a Henschel mixer, a vibrating ball mill,
A stirring device such as a rotary ball mill, a super mixer, and a planetary mixer is used. When stirring on a lab scale, a household juicer mixer may be used.

The polymer diluent is a dispersion of the polymer.
When the polymer solution is diluted with a non-fluorinated solvent, the treated powder cannot be provided with sufficient oil repellency unless the polymer is not dissolved but dispersed in the non-fluorinated solvent. Dissolution and dispersion can be evaluated by the appearance when the polymer solution is diluted with a non-fluorinated solvent. That is, when dissolved, it is completely transparent, but when it is dispersed, it becomes translucent or more turbid. The volume of the polymer solution is not particularly limited, but is preferably 20% or less, for example, 10% or less of the non-fluorinated solvent. When the volume of the polymer solution is more than 20%, the polymer may be dissolved. After stirring, vacuum, or heating to remove the organic solvent,
The treated powder (water-repellent and oil-repellent powder) is uniformly dispersed by the above stirring device. When stirring on a laboratory scale, a household juicer mixer or a speed cutter may be used.

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

The powder to be treated with the polymer is not particularly limited as long as it is generally used for cosmetics. Examples thereof include talc, kaolin, mica, mica titanium, titanium oxide, iron oxide, magnesium oxide, and zinc monoxide. , Zinc dioxide, heavy or light calcium carbonate, dibasic calcium phosphate, aluminum hydroxide, barium sulfate, silica, alumina,
Inorganic powders such as silica gel, carbon black, antimony oxide, magnesium aluminate silicate, magnesium aluminate metasilicate, synthetic mica; protein powder, fish scale foil, metal soap, polyvinyl chloride, nylon 12, microcrystalline fiber powder, tar Organic powders such as dyes and lakes are exemplified. The powder may be surface-treated with two or more polymers. Further, two or more kinds of water-repellent and oil-repellent powders may be blended in cosmetics.

In the cosmetic of the present invention, the water- and oil-repellent powder accounts for 1 to 100% by weight, preferably 10 to 1% by weight of the total powder.
It may be contained at 00% by weight and used in combination with untreated powder or silicone-treated powder. If the amount is less than 1% by weight, water and oil repellency cannot be imparted to the cosmetic. The components other than the water- and oil-repellent powder of the cosmetic of the present invention are selected from the raw materials to be added to ordinary cosmetics, depending on the type of the desired cosmetic, in a range that does not impair the water- and oil-repellency of the cosmetic. Can be blended. Such raw materials include, for example, solid and semi-solid oil components such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids and higher alcohols; squalane, liquid paraffin, ester oil, diglyceride, triglyceride, Fluid oils such as silicone oils; fluorinated oils such as perfluoropolyether, perfluorodecalin and perfluorooctane; water-soluble and oil-soluble polymers, surfactants, inorganic and organic pigments, inorganics treated with silicone or fluorine compounds And organic pigments, coloring agents such as organic dyes, ethanol, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, ultraviolet absorbers,
Examples include humectants, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, and the like.

The cosmetic of the present invention is produced according to a usual method, and can be used for finishing cosmetics such as foundation, whitening, teak color and eye color, and basic cosmetics such as emulsion and cream. It can also be used as a body powder.

[0034]

EXAMPLES Examples of the present invention will be specifically described, but the description does not limit the present invention. The water / oil repellency of the water / oil repellent powders (ie, powders treated with a fluorine compound) or cosmetics obtained in the following Examples and Comparative Examples was evaluated as follows.

Evaluation method of water and oil repellency The water and oil repellency is evaluated by applying a water or oil repellent powder or a cosmetic (powder foundation) uniformly on a filter paper and dropping water or a predetermined oil. did. The water repellency was evaluated according to the following evaluation criteria. ：: Water does not soak one minute after dripping. ×: Water is dripped and soaks 1 minute later. The oil repellency was determined by dropping eight kinds of oils having different surface tensions shown in Table 1 and dropping the oil one minute later.

[0036]

[Table 1] Table 1. Oil used in oil repellency test γ (mN / m) Points Type (25 ° C) 1 Liquid paraffin 31.2 2 Hexadecane / liquid paraffin (35/65) 29.6 3 Hexadecane 27.3 4 Tetradecane 26.7 5 Dodecane 25.0 6 Decane 23.5 7 Octane 21.8 8 Heptane 20.0

The makeup of the powdery foundation
Evaluation Method of Usability A powdery foundation was prepared according to Table 2 using titanium oxide, yellow iron oxide, red iron oxide, black iron oxide, talc, and sericite treated with a fluorine compound.

[0038]

[Table 2] Table 2. Powdery foundation formula and manufacturing method Name of raw material Compounding amount (% by weight) Treated powder Titanium oxide 10.00 Yellow iron oxide 2.30 Bengala 0.65 Black iron oxide 0.39 Talc 55.86 Serisite 20.00 Methyl benzoate 0.30 Perfluoropolyether fomblin HC / 04 10.5

Production method: The powder component and methyl benzoate were mixed and pulverized with an atomizer, transferred to a Henschel mixer, and Fomblin HC / 04 was added and uniformly mixed.
This was put into a mold and press-molded to obtain a powdery foundation.

On the other hand, the treated powders shown in Table 2 were replaced with commercially available silicone-treated powders having the same composition (silicone-treated titanium oxide, silicone-treated yellow iron oxide, silicone-treated black iron oxide, silicone-treated black iron oxide, silicone-treated talc, silicone-treated sericite). A powdery foundation consisting solely of a siliconized powder was prepared in exactly the same manner, except that the powdery foundation was replaced by

The makeup durability and feeling of use (spreading and removal) of the powdery foundation were evaluated according to the following evaluation criteria as compared with the powdery foundation consisting of only the silicone-treated powder. ：: Very good ：: Good Δ: Equal ×: Slightly poor XX: Very poor Evaluation was conducted by five panelists specialized in sensory evaluation, and the average was taken as the result.

Production Example 1 In a four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer, and a stirrer, CH ₂ ＣＨCHCOO (CH ₂ ) ₂ (CF ₂ C
32 g of F ₂ ) _n CF ₂ CF ₃ (abbreviated as FA, a mixture of compounds with n = 3, 4, 5 in a weight ratio of 5: 3: 1), 8 g of stearyl acrylate (StA), dichloropentafluoropropane (HCFC- 225) 79 g of perchlorethylene and 79 g of perchlorethylene are added, and the mixture is heated to 60 ° C. and stirred under a nitrogen stream for 30 minutes. 2 g of t-butyl peroxypivalate (trade name: Perbutyl PV, manufactured by NOF Corporation) was added thereto,
Polymerization was carried out for 6 hours to obtain a copolymer solution. A part of the obtained reaction solution was precipitated with ethanol and dried in vacuo to obtain a copolymer.
(Weight ratio FA / StA = 8/2) was isolated. Based on the weight of the isolated polymer, the conversion was 95%, and the polymer concentration in the reaction solution was 19%. When the molecular weight of the obtained FA / StA copolymer was measured by GPC, the weight average molecular weight was 50,000 (in terms of polystyrene).

Production Example 2 The procedure of Production Example 1 was repeated except that 8 g of stearyl methacrylate macromonomer (trade name: MM-8SMA (molecular weight: 9,000), manufactured by Toa Gosei Chemical Industry Co., Ltd.) was used instead of 8 g of StA. A polymer was prepared (FA / MM-8).
SMA weight ratio = 8/2). The polymerization rate was 95%, the polymer concentration in the reaction solution was 19%, and the weight average molecular weight was 40,000 (in terms of polystyrene).

Production Example 3 In place of 8 g of StA, 4 g of StA and MM-8SMA4
A copolymer was produced by repeating the procedure of Production Example 1 except that g was used (weight ratio of FA / StA / MM-8SMA = 8/1/1). The polymerization rate was 95%, the polymer concentration in the reaction solution was 19%, and the weight average molecular weight was 45,000 (in terms of polystyrene).

Production Example 4 20 g FA, St instead of 32 g FA and 8 g StA
A copolymer was prepared by repeating the procedure of Preparation Example 1 except that 20 g of A was used [weight ratio of FA / StA = 5 /
5]. 95% polymerization rate, 19% polymer concentration in the reaction solution,
The weight average molecular weight was 45,000 (in terms of polystyrene).

Production Example 5 Dichloropentafluoropropane (HCFC-225)
A copolymer was produced by repeating the procedure of Production Example 1 except that 158 g of perchlorethylene was used instead of 79 g and 79 g of perchlorethylene. With this polymerization solvent, the reaction liquid coagulated during the polymerization, and the subsequent powder treatment could not be performed.

Production Example 6 Dichloropentafluoropropane (HCFC-225)
A copolymer was produced by repeating the procedure of Production Example 2 except that 158 g of toluene was used instead of 79 g and 79 g of perchlorethylene. Polymerization rate 95%, polymer concentration in the reaction solution 19%, weight average molecular weight 40,000
(In terms of polystyrene).

Production Example 7 In place of 32 g of FA and 8 g of StA, 40 g of FA was used, and 22579 g of HCFC and 7 g of perchlorethylene were used.
The procedure of Production Example 1 was repeated, except that 158 g of HCFC-225 was used instead of 9 g, to produce an FA homopolymer. Polymerization rate 95%, polymer concentration 19 in the reaction solution
%, And the weight average molecular weight was 60,000 (in terms of polystyrene).

[0049] Example 1 Production Example 1 FA / StA copolymer (FA / StA = 8/2
wt.) A polymer dispersion obtained by diluting 10.53 g of the reaction solution into 150 g of n-decane and 40 g of talc were mixed with a juicer mixer for 1 minute. After heating at 60 ° C. for several days to distill n-decane, pulverize with a speed cutter for 30 seconds.
Processed talc was manufactured.

Example 2 An FA / StA copolymer isolated from the FA / StA copolymer reaction solution obtained in Production Example 1 in place of 10.53 g of the FA / StA copolymer reaction solution of Example 1 2g and HCFC22
The procedure of Example 1 was repeated, except that a polymer solution consisting of 54 g and 4 g of perchrene was used to produce a treated talc.

Example 3 A process powder was produced by repeating the same procedure as in Example 1 except that titanium oxide was used instead of talc. Example 4 A process powder was produced by repeating the same procedure as in Example 1 except that yellow iron oxide was used instead of talc.

Example 5 A process powder was produced by repeating the same procedure as in Example 1 except that Bengala was used instead of talc. Example 6 A process powder was manufactured by repeating the same procedure as in Example 1 except that black iron oxide was used instead of talc. Example 7 A process powder was produced by repeating the same procedure as in Example 1 except that sericite was used instead of talc.

Example 8 Instead of talc, titanium oxide / iron oxide yellow / black iron oxide / black iron oxide / talc / sericite = 10.00 g / 2.30 g
/0.65g/0.39g/55.86g/20.00g/
Except that 0.30 g of the mixed powder was used, the same procedure as in Example 1 was repeated to produce a treated powder.

Example 9 In place of the FA / StA copolymer reaction solution obtained in Production Example 1, the FA / MM-8SMA (weight ratio 8/2) copolymer reaction solution obtained in Production Example 2 was used. A procedure similar to that of Example 8 was repeated, except that the powder was used, to produce a treated powder. Example 10 FA / StA / MM-8SMA obtained in Production Example 3 was replaced with the FA / StA copolymer reaction solution obtained in Production Example 1.
(Weight ratio: 8/1/1) The same procedure as in Example 8 was repeated except that the copolymer reaction liquid was used to produce a treated powder.

Example 11 The procedure of Example 8 was repeated, except that the FA homopolymer reaction solution obtained in Production Example 7 was used instead of the FA / StA copolymer reaction solution obtained in Production Example 1. Was repeated to produce a treated powder.

Comparative Example 1 In place of the FA / StA copolymer reaction solution obtained in Production Example 1, the FA / StA (5/5 weight ratio) copolymer reaction solution obtained in Production Example 4 was used. Except for the above, the same procedure as in Example 8 was repeated to produce a treated powder. Comparative Example 2 Except for using the FA / MM-8SMA (weight ratio 8/2) copolymer reaction solution obtained in Production Example 6 in place of the FA / StA copolymer reaction solution obtained in Production Example 1. Produced the treated powder by repeating the same procedure as in Example 8.

Comparative Example 3 The same procedure as in Example 8 was repeated, except that 150 g of perfluorohexane and 150 g of dichlorofluoroethane (HCFC-141b) were used instead of 150 g of n-decane as the diluting solvent. A powder was produced. The FA / StA copolymer was completely dissolved in this mixed solvent.

Comparative Example 4 Commercially available water- and oil-repellent emulsion [trade name: Unidyne TG
-410 (solid content 18%), manufactured by Daikin Industries] 11.1 g
Was diluted with 189 g of water and 40 g of the mixed powder used in Example 8 were mixed with a juicer mixer for 1 minute. After suction filtration of the mixed powder, it was dried by heating at 60 ° C. for several hours. The powder was pulverized with a speed cutter for 30 seconds to obtain a processed powder. As a result of analyzing the fluorine content of the treated powder, it was found that the water / oil repellent emulsion was hardly adsorbed to the powder.

Comparative Example 5 Commercially available perfluoroalkyl phosphate ester diethanolamine salt [trade name: Unidyne TG-101 (solid content: 15
%), Manufactured by Daikin Industries, Ltd.], and a dispersion obtained by diluting 13.3 g with 186 g of water and 40 g of the mixed powder used in Example 8 were mixed for 1 minute using a juicer mixer. Add diluted hydrochloric acid,
After the pH was adjusted to 3 or less, the solution was filtered by suction. It was dried by heating at 60 ° C. for several hours and pulverized with a speed cutter for 30 seconds to obtain a treated powder.

Table 3 shows the results of the water / oil repellency of the treated powders obtained in Examples 1 to 11 and Comparative Examples 1 to 5.

[0061]

[Table 3] Results of water and oil repellency Examples Fluorine compounds Polymerization solvent Diluent solvent Powder Water repellency Oil repellency 1 FA / StA = 8/2 225 / Perchloroethylene n-decane talc ○ 6 = 1/1 2 Single Separated FA / StA = 8/2 〃 〃 〃 ○ 63 FA / StA = 8/2 〃 黄 Yellow iron oxide ○ 54 〃 〃 〃 Bengala ○ 55 〃 〃 〃 Black iron oxide ○ 5.6 〃 〃 タ ル Talc ○ 〃 〃 〃 Sericite ○ 78 〃 〃 〃 Mixed powder ○ 69 FA / MM-8SMA = 8/2 〃 〃 〃 ○ 610 FA / StA / MM-8SMA 〃 〃 〃 ○ 6 = 8/1 / 1 11 FA alone 225 alone 〃 〃 ○ 6 Comparative Example 1 FA / StA = 5/5 〃 〃 〃 ○ 1 Comparative Example 2 FA / MM-8SMA = 8/2 Toluene n-decane mixed powder ○ 2 Comparative Example 3 FA / StA = 8/2 225 / Perchloroethylene PFH / 141b 〃 ○ 1 = 1/1 = 1/1 Comparative Example 4 Unidyne TG-410 Aqueous Aqueous 〃 ○ 0 Comparative Example 5 Unidyne TG-101 〃 〃 〃 ○ 5 Note) 225: HCFC-225 141b: HCFC-14 b PFH: Pas - fluoro-hexane

Example 12 A powdery foundation was prepared from the treated powders of Example 1 and Examples 3 to 7 according to the formulation and production method shown in Table 2. Example 13 A powdery foundation was prepared by repeating the procedure of Example 12 except that 89.2% by weight of the treated powder obtained in Example 8 was used.

Example 14 A powdery foundation was prepared by repeating the procedure of Example 12 except that 89.2% by weight of the treated powder obtained in Example 11 was used. Comparative Example 6 The procedure of Example 12 was repeated, except that 89.2% by weight of the treated powder obtained in Comparative Example 1 was used, to prepare a powdery foundation.

Comparative Example 7 A powdery foundation was prepared by repeating the procedure of Example 12 except that 89.2% by weight of the treated powder obtained in Comparative Example 4 was used. Comparative Example 8 A powdery foundation was prepared by repeating the procedure of Example 12 except that 89.2% by weight of the treated powder obtained in Comparative Example 5 was used. Table 4 shows the evaluation results of the powdery foundations of Examples 12 to 14 and Comparative Examples 6 to 8 for water repellency, oil repellency, long-lasting makeup, spreadability, and removal.

[0065]

[Table 4] Evaluation result of powdery foundation Example Fluorine dilution Water repellent Oil repellent Cosmetic No. Compound Polymerization solvent Solvent property Long lasting Example 12 FA / StA = 8/2 HCFC225 / n-decane ○ 6 ◎ △ △ PA ―Chloroethylene = 1/1 Example 13 FA / StA = 8/2 〃 〃 ○ 6 ◎ △ △ Example 14 FA alone HCFC225 alone 〃 ○ 6 ◎ ×-△ ×-△ Comparative Example 6 FA / StA = 5 / 5 〃 〃 ○ 1 △ △ △ Comparative Example 7 Unidyne TG-410 Aqueous Aqueous × 0 × × × Comparative Example 8 Unidyne TG-101 〃 〃 ○ 5 ○ × ×

Claims (9)

[Claims] A step of preparing a polymer solution by polymerizing a polymerizable monomer containing at least 60% by weight of a fluorine-based monomer in a polymerization solvent containing a fluorine-based solvent, A method for producing a water / oil repellent powder for cosmetics, comprising the steps of: diluting a polymer solution with a non-fluorinated solvent to prepare a polymer diluent; and treating the powder with the polymer diluent. 2. a step of preparing a polymer solution by polymerizing a polymerizable monomer containing at least 60% by weight of a fluorine-based monomer in a polymerization solvent containing a fluorine-based solvent; Dissolving the polymer isolated from the polymer solution in a solvent containing a fluorine-based solvent, diluting the solution in which the polymer is dissolved with a non-fluorine-based solvent,
A method for producing a water / oil repellent powder for cosmetics, comprising: a step of preparing a polymer diluent; and a step of treating the powder with the polymer diluent. 3. The fluorine-based monomer represented by the general formula (I): [In the formula, Rf is a polyfluoroalkyl 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 X is a hydrogen atom or a methyl group. 3. The method according to claim 1, wherein the polyfluoroalkyl group-containing (meth) acrylate is represented by the formula: 4. The polymerizable monomer comprises a fluorine monomer and a non-fluorine monomer, wherein the fluorine monomer has the general formula (I): [In the formula, Rf is a polyfluoroalkyl 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 X is a hydrogen atom or a methyl group. A polyfluoroalkyl group-containing (meth) acrylate represented by the general formula (II): Wherein X is a hydrogen atom or a methyl group, and n is 12
~ 22. An alkyl (meth) acrylate represented by the general formula (III): [In the formula, each of X and Y is a hydrogen atom or a methyl group, n is 12 to 22, and 1 is 5 to 100.] The method according to claim 1, wherein the compound is at least one compound selected from the group consisting of alkyl (meth) acrylate macromonomers represented by the formula: 5. The content of the fluorine-based solvent in the polymerization solvent is 30.
3. The method according to claim 1, wherein the amount is not less than% by weight. 6. The method according to claim 2, wherein the content of the fluorinated solvent in the solvent for dissolving the polymer isolated from the polymer solution is 30% by weight or more. 7. The method according to claim 1, wherein the amount of the polymer solution is 20% by volume or less of the non-fluorinated solvent for diluting the polymer solution. 8. A water / oil repellent powder for cosmetics obtained by the method according to claim 1. 9. A cosmetic comprising the water / oil repellent powder for cosmetics according to claim 8.