JP2006008554A - Polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming polymer composition which is excellent in water repellency, oil repellency, rub resistance and surface non-adhesive property, can be dissolved or uniformly dispersed in a silicone solvent, shows a high makeup-lasting property and is flexible, and a cosmetic containing the same. <P>SOLUTION: The polymer composition contains (A) a fluoropolymer having an ionic group and (B) a silicone having an ionic group with a charge opposite to that of component (A). The cosmetic contains the polymer composition and the silicone solvent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer composition used in cosmetics and a cosmetic containing the polymer composition.

  In general, the disappearance of the effects of cosmetic ingredients such as pigments and active ingredients is called makeup collapse. Cosmetic disintegration is caused by stickiness, shininess, oil floatation, color due to external factors such as skin movement, drop-out due to contact with hands, clothing, water, etc. and human secretions such as sebum, sweat, tears, etc. There are internal factors that cause dullness and distortion. In order to solve such problems, a method of blending a cosmetic with a film-forming agent excellent in water repellency, oil repellency, friction resistance, surface non-adhesiveness, flexibility and the like has been adopted.

  For example, Patent Document 1 proposes a cosmetic containing a waxy fluorine-containing polymer. A copolymer of a long-chain alkyl (meth) acrylate exemplified as this waxy fluorine-containing polymer and an alkyl (meth) acrylate in which at least one hydrogen atom is substituted with fluorine is water-repellent and oil-repellent. Excellent in friction resistance, surface non-adhesiveness and flexibility and high makeup durability, but does not dissolve in silicone solvents, so it is necessary to use hydrocarbon solvents, which reduces the feeling of use and makeup durability. End up.

Patent Document 2 proposes a cosmetic containing a homopolymer or copolymer containing a fluorine-containing polymerizable monomer as a constituent monomer as a film-forming fluorine-containing polymer substance. The document includes (1) a copolymer containing a fluoroalkyl group-containing polymerizable monomer and a dimethylpolysiloxane compound having a polymerizable group at the end of the molecular chain as constituent monomers, and (2) a fluoroalkyl group-containing polymerizable property. A copolymer comprising a monomer and a mercapto-modified dimethylpolysiloxane as constituent monomers; and (3) a polymer obtained by polymerizing a fluoroalkyl group-containing polymerizable monomer using a dimethylpolysiloxane compound having an azo group in the molecule as an initiator. Etc. are illustrated. However, these film-forming fluorine-containing polymeric substances have silicone chains in the polymer molecules, so they dissolve in silicone solvents, but their oil repellency and surface non-adhesiveness are not sufficient, resulting in reduced makeup persistence. Tended to be.
Japanese Patent Laid-Open No. 10-175817 Japanese Patent Laid-Open No. 11-322543

  An object of the present invention is to provide a flexible film-forming polymer composition that is excellent in water repellency, oil repellency, friction resistance and surface non-adhesion, is dissolved or uniformly dispersed in a silicone solvent, and has a high makeup durability. It is to provide a cosmetic containing the same.

The present invention provides a polymer composition containing the following component (A) and component (B), and a cosmetic containing the polymer composition and a silicone solvent (hereinafter referred to as component (C)).
Component (A): Fluorine-containing polymer having an ionic group Component (B): Silicone having an ionic group having a charge opposite to that of the component (A)

  Since the polymer composition of the present invention is dissolved or uniformly dispersed in a silicone solvent, it has a good feeling of use and forms a film excellent in water repellency, oil repellency, friction resistance and surface non-adhesiveness. When this polymer composition is used in a cosmetic, a flexible cosmetic film having a high makeup durability is obtained.

[Component (A): Fluorine-containing polymer having an ionic group]
The fluorine-containing polymer having an ionic group of the present invention is not particularly limited as long as it is a water-insoluble polymer having a fluorine atom in the molecule and having an ionic group. The term “water-insoluble” as used herein means that the solubility in water having a pH of 3 to 11 at 25 ° C. is 0.1% by weight or less, and it is not uniformly dispersed in water.

  The fluorine atom of component (A) is preferably present as a fluoroalkyl group. Examples of the fluoroalkyl group include a polyfluoroalkyl group and a perfluoroalkyl group, and a perfluoroalkyl group having 4 to 22 carbon atoms is particularly preferable from the viewpoint of oil repellency, surface non-adhesiveness, and the like. These fluoroalkyl groups are preferably introduced into the polymer by copolymerizing polymerizable monomers such as fluoroalkyl (meth) acrylate, fluoroalkyl (meth) acrylamide, fluoroalkyl vinyl ether, α-fluoroolefin and the like. Among these monomers, fluoroalkyl (meth) acrylate is particularly preferable. Specific examples include monomers described in JP-A No. 11-322543, page 3, right column, lines 7 to 15, and include 2-perfluorohexylethyl (meth) acrylate and 2-perfluorooctylethyl. (Perfluoroalkyl) alkyl (meth) acrylates such as (meth) acrylate and 2-perfluorodecylethyl (meth) acrylate are particularly preferred.

  In the present specification, (meth) acrylate means acrylate or methacrylate, and (meth) acrylamide means acrylamide or methacrylamide.

  These fluoroalkyl group-containing monomers can be used alone or in combination of two or more, and are preferably contained in a proportion of 1 to 90% by weight, based on the total monomer component, It is particularly preferable that it is contained in a proportion.

  Examples of the ionic group of the component (A) include an anionic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, or a cationic group such as an amino group and an ammonium group. These ionic groups are preferably introduced into the polymer by copolymerizing polymerizable monomers such as (meth) acrylates, (meth) acrylamides, styrenes, vinyl ethers, and olefins having these ionic groups. Specifically, monomers described in JP-A 2002-201123, page 5, right column, lines 8 to 18 and page 4, left column, lines 14 to 29 are exemplified. Among these monomers having an ionic group, a monomer having a carboxyl group or an amino group is preferable from the viewpoint of ease of synthesis, blendability, stability, and the like. Specifically, a monomer having a carboxyl group such as (meth) acrylic acid, maleic acid, itaconic acid, styrene carboxylic acid; a total carbon number of 2 such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide Examples thereof include (meth) acrylic acid ester or (meth) acrylamide having 44 dialkylamino groups; styrene having a dialkylamino group having 2 to 44 total carbon atoms such as dimethylaminostyrene and dimethylaminomethylstyrene. Among these, (meth) acrylic acid, maleic acid, itaconic acid, and (meth) acrylic acid esters having a dialkylamino group having 2 to 8 carbon atoms are particularly preferable. These monomers having an ionic group can be used alone or in combination of two or more, and are preferably contained in a proportion of 0.01 to 20% by weight based on the total amount of monomers, It is particularly preferable that it is contained at a ratio of 10% by weight.

  The component (A) is preferably obtained by radical copolymerization of a polymerizable monomer from the viewpoint of ease of synthesis and freedom of composition. The polymerization is carried out in the presence of a general radical polymerization initiator (peroxide such as lauroyl peroxide or azo compound such as 2,2-azobis-2,4-dimethylvaleronitrile). It is synthesized by a solution polymerization method or the like. Specifically, in the case of a solution polymerization method, a method in which a monomer and an initiator are dissolved in an organic solvent, dissolved oxygen in the system is removed by replacement with an inert gas such as nitrogen, and then the temperature is raised and polymerization is performed. Is exemplified. The polymerization initiation temperature is usually about 30 to 90 ° C., and the reaction time is about 1 to 12 hours.

  When the component (A) is obtained by radical copolymerization, it is preferable to copolymerize a monomer copolymerizable with these in addition to a monomer having a fluoroalkyl group and a monomer having an ionic group. Specifically, an alkyl having a linear or branched alkyl group having 1 to 30 carbon atoms such as stearyl (meth) acrylate, lauryl (meth) acrylate, behenyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate ( (Meth) acrylates; alkyl (meth) acrylamides having a linear or branched alkyl group having 1 to 30 carbon atoms such as t-butyl (meth) acrylamide; styrenes such as styrene and α-methylstyrene; methyl vinyl ether, ethyl Examples include vinyl ethers having a linear or branched alkyl group having 1 to 30 carbon atoms such as vinyl ether and butyl vinyl ether; olefins such as ethylene, propylene and butadiene; vinyl acetate, vinyl chloride, acrylonitrile and the like. Among these, an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 30 carbon atoms is particularly preferable. These monomers can be used alone or in combination of two or more, and are preferably copolymerized at a ratio of 1 to 90% by weight based on the total amount of monomers.

  Examples of the main chain skeleton of component (A) include (meth) acrylates, (meth) acrylamides, styrenes, vinyl ethers, ethylenes, and the like, even if one or more of these skeletons are present. good. Among these, a polymer having a (meth) acrylate system in the main chain skeleton is particularly preferable.

As for the weight average molecular weight of polystyrene conversion in GPC of a component (A), 2000-1000000 are preferable and 5000-200000 are especially preferable.
In the present invention, one or more of these polymers can be used as the component (A).

[Component (B): Silicone having an ionic group having a charge opposite to that of Component (A)]
The component (B) of the present invention may be a silicone having a cationic group when the component (A) has an anionic group and a silicone having an anionic group when having a cationic group.

  Examples of the anionic group of the component (B) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and examples of the cationic group include an amino group and an ammonium group. Among these ionic groups, an amino group or a carboxyl group is preferable from the viewpoints of blendability, stability, availability, and the like.

As a quantity of the ionic group of a component (B), 100-100000 g / mol is preferable and 200-50000 g / mol is especially preferable. Further, the binding site of the ionic group may be any of a side chain type, a single end type, a double end type, and a double end / side chain type.
The viscosity of component (B), at 25 ° C., preferably ^{10~100000mm 2 / s, 20~100000mm 2 /} s is particularly preferred.

The component (B) is preferably a dimethylpolysiloxane having an ionic group as described above, and specifically, KF-8004, KF-8005, KF-8015, KF-865, KF-867S, KF-868. , KF-880, X-22-162C, X-22-3701E, X-22-3710 (manufactured by Shin-Etsu Chemical Co., Ltd.), SF8417, SF8418, SF8451C, SF8452C, SF8457C, BY16-850, BY16- 872, BY16-880 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), XF42-B1989, TSF4700, TSF4701, TSF4702, TSF4703, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709 (or more, G Over Toshiba Silicone Co.) and the like.
In the present invention, one or more of these silicones can be used as the component (B).

[Component (C): Silicone solvent]
Examples of the component (C) of the present invention include general silicone oils used in cosmetics and the like whose main chain skeleton is dimethylpolysiloxane, specifically, dimethylpolysiloxane, cyclic dimethylpolysiloxane, Examples include polyether-modified silicone, silicone resin, silicone grease, methylstyryl-modified silicone, alkyl-modified silicone, higher fatty acid ester-modified silicone, methylphenylpolysiloxane, fluorine-modified silicone, and the like.

  Among these silicone solvents, at least one selected from fluorine-modified silicone and dimethylpolysiloxane is preferable, and dimethylpolysiloxane having a boiling point of 250 ° C. or less at atmospheric pressure is particularly preferable from the viewpoint of film properties. . Specific examples of the fluorine-modified silicone include fluorine-modified silicones described in paragraph numbers 0018 to 0020 of JP-A No. 2000-281791 and fluorine-modified silicones described in JP-A No. 6-184212. As the dimethylpolysiloxane, any of cyclic and acyclic dimethylpolysiloxane can be preferably used. Specifically, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, octamethylcyclotetrasiloxane, Examples include decamethylcyclopentasiloxane.

  These silicones can be used alone or in combination of two or more. Among them, it is particularly preferable to use at least both fluorine-modified silicone and (cyclic) dimethylpolysiloxane having a boiling point of 250 ° C. or less at atmospheric pressure.

[Polymer composition]
In the polymer composition of the present invention, the component (A) and the component (B) can be blended at an arbitrary mixing ratio. In the present invention, the component (B) interacts with the component (A). It is preferable that the molar ratio (A) / (B) of the ionic groups of the component (A) and the component (B) is 3/7 to 9/1. It is particularly preferred that it is ˜8 / 2. Further, the weight ratio (A) / (B) of the component (A) to the component (B) is preferably 1/9 to 8/2, particularly preferably 2/8 to 7/3.

  The polymer composition of the present invention can be used as it is without containing other components, but contains a solvent capable of dissolving component (A) and component (B) in addition to component (A) and component (B). can do. In this case, the viscosity of the polymer composition can be lowered, and it is advantageous in handling such that mixing can be easily performed.

Examples of the solvent include a silicone solvent of component (C) of the present invention, a fluorine solvent such as trifluorotoluene, a halogen solvent such as chloroform, a hydrocarbon solvent such as toluene or hexane, and a solubility parameter at 25 ° C. of 6 A solvent of ˜9.5 has good solubility and is preferably used. The solubility parameter here refers to a value obtained as (molar evaporation heat [cal] / molar volume [cm ³ ]) ^1/2 obtained by calculating the molar evaporation heat and molar volume at 25 ° C. The silicone solvent can be preferably used when it is used as a blend without removing the solvent. Moreover, when removing and using a solvent, hexane etc. can be used preferably.

The total content of the component (A) and the component (B) in the polymer composition of the present invention is preferably 1 to 100% by weight, and preferably 1 to 50% by weight when containing a solvent, and 5 to 50% by weight. % Is more preferable, and 5 to 40% by weight is still more preferable.
Further, other components may be further contained within a range not impeding the effects of the present invention.

[Cosmetics]
The cosmetic of the present invention contains the polymer composition of the present invention and a component (C). The content of the polymer composition of the present invention in the cosmetic of the present invention is preferably 0.05 to 50% by weight, more preferably 0.1 to 20% by weight. Moreover, 0.1-99 weight% is preferable and, as for content of a component (C), 0.5-80 weight% is still more preferable.

  The polymer composition of the present invention and the component (C) in the cosmetic of the present invention can be blended at an arbitrary mixing ratio, but the total weight of the component (A) and the component (B) and the component (C ) Weight ratio [(A) + (B)] / (C) is preferably 0.01 / 9.99-5 / 5, and 0.05 / 9.95-4 / 6. It is particularly preferred.

  In this invention, when mix | blending components other than a component (A) and a component (B) and manufacturing cosmetics, it is preferable to make a component (A) and a component (B) interact beforehand. For example, it is preferable that the component (A) and the component (B) are first mixed, and the mixture of the obtained component (A) and the component (B) is mixed with the component (C) and other components. . Moreover, it is preferable to use a cosolvent at the time of mixing.

  In addition to the above components, the cosmetics of the present invention include components used in normal cosmetics, such as oils, solid / semi-solid oils, solvents, water, water-soluble / hydrophobic polymers, inorganic / organic pigments, interfaces. Activators, preservatives, antioxidants, dyes, pH adjusters, fragrances, ultraviolet absorbers, moisturizers, bactericides, antibacterial agents, metal chelating agents, drugs, etc. are appropriately selected within a range that does not impair the effects of the present invention. Can be blended.

  The powders of inorganic and organic pigments used in the present invention are hydrophobized with a hydrophobizing agent on the surface of the hydrophobic powder or the mother powder from the viewpoint of cosmetic durability and dispersibility in silicone solvents. So-called hydrophobized powder is preferable. Of these, hydrophobized powder is particularly preferred.

  The hydrophobizing agent herein includes silicone oil, fatty acid metal salt, alkyl phosphoric acid, alkali metal salt or amine salt of alkyl phosphoric acid, N-mono long chain (carbon number 8 to 22) aliphatic acyl basic amino acid And fluorine compounds having a perfluoroalkyl group. Specific examples thereof include hydrophobizing agents described in paragraph Nos. 0016 to 0027 of JP-A-10-194912. The treatment amount of the hydrophobizing agent relative to the powder is preferably 0.05 to 20% by weight, more preferably 1 to 10% by weight. Within this range, sufficient hydrophobicity and dispersibility are obtained, which is preferable.

  The cosmetic composition of the present invention can be produced according to a conventional method, and its dosage form, type and the like are not particularly limited. For example, an oily cosmetic composition, a water-in-oil emulsified cosmetic composition, an oil-in-water emulsified cosmetic composition, and an aqueous cosmetic composition , Solid cosmetics, oily solid cosmetics, and the like. In particular, makeup cosmetics such as foundation, funny, lipstick, blusher and eye shadow, and skin protective cosmetics such as skin care cream, milky lotion, skin lotion and sunscreen agent are suitable.

  In the examples, “%” means “% by weight” unless otherwise specified.

Example 1
As a fluorine-containing monomer, 2-perfluorooctylethyl methacrylate (FLUOWET MAE800; manufactured by Clariant Japan Co., Ltd.) 36.00 g, and as a copolymerizable monomer, stearyl methacrylate (NK ester S; manufactured by Shin-Nakamura Chemical Co., Ltd.) 22.75 g, as an ionic monomer, 1.25 g of methacrylic acid (acrylic ester MAA; manufactured by Mitsubishi Rayon Co., Ltd.) and 54.0 g of n-hexane are uniformly mixed and placed in a 300 mL glass separable flask. The temperature was raised to around 60 to 65 ° C. with stirring in a nitrogen atmosphere. Thereto was added a solution prepared by dissolving 0.37 g of 2,2-azobis-2,4-dimethylvaleronitrile (V-65; manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator in 6.0 g of n-hexane. Polymerization and aging were carried out at around 60 to 65 ° C. for 6 hours. A part of this solution was sampled, and after drying, the weight average molecular weight was measured by GPC. As a result, it was 6000 in terms of polystyrene.

  After diluting by adding 120.0 g of n-hexane, 63.80 g of amino-modified silicone KF-865 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added dropwise as a silicone having an ionic group of reverse charge while stirring at around 60 ° C. And aged for 1 hour. The reaction solution was dropped into 2000.0 g of methanol and purified by reprecipitation, and the precipitate was dried to obtain polymer composition 1.

Example 2
In Example 1, stearyl methacrylate was changed to 20.55 g, methacrylic acid was changed to 4.00 g, and 2,2-azobis-2,4-dimethylvaleronitrile was changed to 0.42 g, and polymerization was performed in the same manner as in Example 1. Furthermore, the amino-modified silicone was changed to 64.10 g of XF42-B1989 (manufactured by GE Toshiba Silicone Co., Ltd.) and prepared in the same manner as in Example 1, to obtain a polymer composition 2. The weight average molecular weight at the end of the polymerization was 77,000.

Example 3
In Example 1, 23.10 g of stearyl methacrylate, 0.90 g of methacrylic acid, and 0.36 g of 2,2-azobis-2,4-dimethylvaleronitrile were changed, and polymerization was performed in the same manner as in Example 1. It was. Further, the amino-modified silicone was changed to 67.20 g of SF8452C (manufactured by Toray Dow Corning Silicone Co., Ltd.) and prepared in the same manner as in Example 1 to obtain a polymer composition 3. The weight average molecular weight at the end of the polymerization was 62,000.

Example 4
In Example 1, 39.50 g of 2-perfluorooctylethyl methacrylate, 19.75 g of stearyl methacrylate, 1.50 g of methacrylic acid, 0.36 g of 2,2-azobis-2,4-dimethylvaleronitrile, KF -865 was changed to 38.75g, it prepared by the same method as Example 1, and the polymer composition 4 was obtained. The weight average molecular weight at the end of the polymerization was 47,000.

Example 5
In Example 1, 34.80 g of 2-perfluorooctylethyl methacrylate, 22.80 g of stearyl methacrylate, and 0.37 g of 2,2-azobis-2,4-dimethylvaleronitrile were changed as ionic monomers, Polymerization was carried out in the same manner as in Example 1, using 2.50 g of 2-dimethylaminoethyl methacrylate (Wako Pure Chemical Industries, Ltd.) instead of methacrylic acid. Further, in the same manner as in Example 1, using 60.20 g of carboxyl-modified silicone X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd.) instead of amino-modified silicone as a silicone having a reversely charged ionic group. As a result, a polymer composition 5 was obtained. The weight average molecular weight at the end of the polymerization was 58,000.

Comparative Example 1
In Example 1, 24.00 g of 2-perfluorooctylethyl methacrylate, 12.00 g of stearyl methacrylate, and 0.21 g of 2,2-azobis-2,4-dimethylvaleronitrile were changed to be ionic monomers. In the same manner as in Example 1, using 24.00 g of dimethylpolysiloxypropyl methacrylate (Silaplane FM-0721 (average molecular weight 5000); manufactured by Chisso Corporation) which is a monomer having no ionicity instead of methacrylic acid. Polymerization was performed. Then, without performing operation which adds amino modified silicone, it prepared by the same method as Example 1, and obtained the polymer composition 6 after solvent refinement | purification. The weight average molecular weight at the end of the polymerization was 87,000.

Comparative Example 2
In Comparative Example 1, 2-perfluorooctylethyl methacrylate was changed to 36.00 g, stearyl methacrylate was not used, and 2,2-azobis-2,4-dimethylvaleronitrile was changed to 0.23 g to have no ionicity. Prepared in the same manner as in Comparative Example 1 using 24.00 g of Silaplane FM-0711 (dimethylpolysiloxypropyl methacrylate, average molecular weight 1000; manufactured by Chisso Corp.) instead of Silaplane FM-0721 as a monomer, After purification, polymer composition 7 was obtained. The weight average molecular weight at the end of the polymerization was 129000.

Comparative Example 3
In Example 1, without using 2-perfluorooctylethyl methacrylate which is a fluorine-containing monomer, 59.00 g of stearyl methacrylate, 1.00 g of methacrylic acid, and 2,2-azobis-2,4-dimethylvaleronitrile were used. 0.46g, KF-865 was changed to 38.80g, and it prepared by the same method as Example 1, and obtained the polymer composition 8 after solvent refinement | purification. The weight average molecular weight at the end of the polymerization was 103,000.

Comparative Example 4
In Example 1, except that the operation of adding amino-modified silicone was not performed, the polymer composition 9 was prepared in the same manner as in Example 1 and after solvent purification, a polymer composition 9 was obtained. The weight average molecular weight at the end of the polymerization was 60000.

Test Example About the polymer compositions 1-9 obtained in Examples 1-5 and Comparative Examples 1-4, the solubility in a silicone and oil repellency were evaluated with the following method. The results are shown in Table 1.

<Solubility in silicone>
To 9.0 g of octamethylcyclotetrasiloxane (SH244; manufactured by Toray Dow Corning Silicone Co., Ltd.), 1.0 g of the polymer composition is added and mixed well by stirring and heating, and the solubility at 25 ° C. Was visually evaluated according to the following criteria.

The weight ratio of the mixture of the component (A) and the component (B) (polymer composition) to the component (C) (octamethylcyclotetrasiloxane) is 1/9.
◯: Transparent and uniform solution Δ: Uniform solution with white turbidity x: Solution in which solid matter was precipitated / deposited Here, a solution that formed a uniform liquid was judged to be acceptable.

<Oil repellency>
The silicone solution of the polymer composition used to evaluate the solubility in silicone was applied on a low density polyethylene film (thickness 0.1 μm) so that the polymer content was 1 mg / cm ^2, and the solvent was completely dried. To obtain a polymer film. One drop of squalene (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped on this film, and the contact angle was measured after 1 minute. This measurement was performed three times, and the average value was taken as the contact angle. Here, the contact angle of 40 ° or more was regarded as acceptable.

Examples 6 to 10 and Comparative Examples 5 to 9 (water-in-oil emulsion foundation)
A water-in-oil emulsion foundation having the composition shown in Table 2 was produced by the following method, and the feeling of use, makeup sustainability, color transfer resistance, and friction color transfer resistance were evaluated by the following methods. The results are shown in Table 2.

<Production method>
The powder component was mixed and pulverized. After dissolving / dispersing the oil phase component at 70 to 80 ° C., the pulverized powder component was added and dispersed with a disper. Next, after the temperature was lowered to 20 to 30 ° C., the aqueous phase component was added and emulsified with stirring to obtain a water-in-oil emulsion foundation.

<Evaluation method>
(1) Feeling of use and persistence of makeup The sensory evaluation of the feel of use and the persistence of makeup when each foundation was used was conducted by 12 professional panelists based on the following criteria.
5; 10-12 judged good 4; 8-9 judged good 3; 6-7 judged good 2; 4-5 judged good 1; 3 or less Judged to be good.

(2) Color transfer resistance A certain amount of each foundation was uniformly applied to the artificial leather, and a pressure of 300 gf / cm ² was applied to the portion where the tissue was pressed for 10 seconds. At that time, the following criteria were used to evaluate the degree of coloring by the foundation transferred to the tissue.
◎: Almost not colored ○: Slightly colored △: Colored ×: Pretty colored

(3) Friction resistance color transfer property A certain amount of each foundation is uniformly applied to artificial leather, and the portion coated with cotton cloth is applied at a speed of 3000 mm / min using a surface property tester under a pressure of 30 gf / cm ^2. 3 reciprocations. The following criteria evaluated by the coloring degree of the color transfer by the foundation which moved then.
◎: Almost not colored ○: Slightly colored △: Colored ×: Very colored

Example 11 (creamy foundation)
The following components (6) to (9) were mixed and ground. Components (1) to (5) were dissolved / dispersed at 70 to 80 ° C., and then the pulverized components (6) to (9) were added and dispersed with a disper. Next, after the temperature was lowered to 20 to 30 ° C., the aqueous phase components (10) to (14) were added and emulsified with stirring, and the viscosity was adjusted with a homomixer to obtain a creamy foundation.

<Composition>
(1) Alkyl glyceryl ether-modified silicone 4.0%
(Silicone derivative produced according to Example 11 of JP-A-4-108795, m = 60, n = 4)
(2) Decamethylcyclopentasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-995) 20.0%
(3) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96A 10c) 7.5%
(4) Fluorine-modified silicone (Production Example 3 of JP-A-7-277914) 7.5%
(5) Polymer composition 1 0.5%
(6) 5% fluorinated titanium oxide 6.0%
(7) Fluorine-treated Bengala Cloisonne 0.9%
(8) 5% fluorinated yellow iron oxide 1.1%
(9) 5% fluorinated mica 4.0%
(10) Glycerol 3.0%
(11) Magnesium sulfate 0.8%
(12) Preservative appropriate amount (13) Fragrance amount (14) Remaining amount of purified water.

Example 12 (milky lotion)
The following components (1) to (5) were dissolved / dispersed at 70 to 80 ° C., and then component (6) was added and dispersed with a disper. Next, the temperature was lowered to 20 to 30 ° C., and then components (7) to (11) were added with stirring to emulsify to obtain an emulsion.

<Composition>
(1) Dimethylpolysiloxane polyoxyalkylene copolymer 2.0%
(SH3772M manufactured by Toray Dow Corning Silicone)
(2) Octamethylcyclotetrasiloxane 15.0%
(SH344 manufactured by Toray Dow Corning Silicone)
(3) Dimethylpolysiloxane 10.0%
(SH200C6c manufactured by Toray Dow Corning Silicone)
(4) Fluorine-modified silicone (Production Example 6 of JP-A-7-277914) 5.0%
(5) Polymer composition 1 3.0%
(6) 2% silicone-treated fine particle zinc oxide 1.0%
(7) tetrasodium edetate 0.1%
(8) L-ascorbic acid phosphate magnesium salt 3.0%
(9) Sodium citrate 1.0%
(10) Fragrance (11) Purified water remaining.

Example 13 (oil-in-water emulsion foundation)
The following components (7) to (11) were mixed and ground. Components (2) to (6) were dissolved / dispersed at 70 to 80 ° C., and then crushed components (7) to (11) were added and dispersed with a disper. Next, the temperature was lowered to 20 to 30 ° C., and then components (1) and (12) to (13) were added and emulsified with stirring to obtain an oil-in-water emulsion foundation.

<Composition>
(1) Water-soluble alkyl-modified polysaccharide derivative 0.5%
(NATROSOL Plus 339 made by Aqualon Company)
(2) Isostearyl glyceryl ether (HLB1.8) 0.5%
(3) Octamethylcyclotetrasiloxane 15.0%
(SH244 manufactured by Toray Dow Corning Silicone)
(4) Dimethylpolysiloxane (Production Example 7 of JP-A-7-277914) 12.0%
(5) Fluorine-modified silicone (ASA Glass FSL-300) 3.0%
(6) Polymer composition 1 0.7%
(7) 3% silicone-treated titanium oxide 3.0%
(8) 3% silicone treated Bengala cloisonne 0.3%
(9) 3% silicone-treated yellow iron oxide 1.0%
(10) 3% silicone-treated nylon powder 3.0%
(11) 3% silicone-treated mica 4.0%
(12) Ethanol 5.0%
(13) Remaining amount of purified water.

Example 14 (moisturizing cream)
After dissolving / dispersing the following components (1) to (8) at 70 to 80 ° C., the temperature is lowered to 20 to 30 ° C., components (9) to (15) are added and emulsified with stirring, and the viscosity is determined by homomicity. Adjusted to obtain a moisturizing cream.

<Composition>
(1) Isostearyl glyceryl ether (HLB1.8) 1.0%
(2) Sorbitan monooleate (SO-10R manufactured by Nikko Chemicals) 2.0%
(3) Polyoxyethylene hydrogenated castor oil (Nikko Chemicals HCO10) 2.0%
(4) Dimethylpolysiloxane polyoxyalkylene copolymer 1.5%
(SH3775M manufactured by Toray Dow Corning Silicone)
(5) Decamethylcyclotetrasiloxane 15.0%
(SH245 manufactured by Toray Dow Corning Silicone)
(6) Methylphenylpolysiloxane 7.0%
(SH556 manufactured by Toray Dow Corning Silicone)
(7) Fluorine-modified silicone (X-22-820, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.5%
(8) Polymer composition 2 3.0%
(9) Glycerol 3.0%
(10) Chamitles squalene extract 0.5%
(11) Magnesium sulfate 1.0%
(12) Citric acid 0.6%
(13) Trisodium citrate 0.4%
(14) Preservative appropriate amount (15) Purified water remaining.

Example 15 (sunscreen emulsion)
The following components (6) and (7) were mixed and ground. Components (1) to (5) were dissolved / dispersed at 70 to 80 ° C., and then the pulverized components (6) and (7) were added and dispersed with a disper. Next, after the temperature was lowered to 20 to 30 ° C., components (8) to (11) were added with emulsification and emulsified to obtain a sunscreen emulsion.

<Composition>
(1) Dimethylpolysiloxane polyoxyalkylene copolymer 0.7%
(SH3773M manufactured by Toray Dow Corning Silicone)
(2) Octamethylcyclotetrasiloxane 25.0%
(SH244 manufactured by Toray Dow Corning Silicone)
(3) Fluorine-modified silicone 10.0%
(FS-1265 manufactured by Toray Dow Corning Silicone)
(4) Polymer composition 3 10.0%
(5) Octyl methoxycinnamate 4.0%
(6) 2% silicone-treated fine particle titanium oxide 7.0%
(7) 2% silicone fine zinc oxide flower 5.0%
(8) Glycerin 1.5%
(9) Ethanol 9.5%
(10) Purified water remaining amount (11) Fragrance A trace amount.

Example 16 (powder foundation)
The following components (1) to (8) were mixed and ground. This was transferred to a high-speed blender, and further, components (9) to (13) mixed and dissolved at 80 ° C. were added and mixed uniformly, then ground again and passed through a sieve. This was compression molded into a metal pan.

<Composition>
(1) 5% silicone-treated titanium oxide 20.0%
(2) 5% silicone-treated sericite 25.0%
(3) 5% silicone-treated talc 30.0%
(4) 5% silicone-treated bengara 3.0%
(5) 5% silicone-treated yellow iron oxide 6.0%
(6) 5% silicone-treated black iron oxide 0.5%
(7) 5% silicone-treated silica 5.0%
(8) 5% silicone-treated nylon powder 5.0%
(9) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96A 6cs) 2.0%
(10) Fluorine-modified silicone (X-22-820, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0%
(11) Polymer composition 3 1.0%
(12) Preservative appropriate amount (13) Fragrance

Example 17 (blusher)
The following components (1) to (9) were mixed and ground. This was transferred to a high-speed blender, and further, components (10) to (14) mixed and dissolved at 80 ° C. were added and mixed uniformly, then ground again and passed through a sieve. This was compression molded into a metal pan.

<Composition>
(1) 3% fluorinated kaolin 40.0%
(2) 3% foot-treated mica 15.0%
(3) 3% fluorinated titanium oxide 18.0%
(4) 3% fluorinated yellow iron oxide 4.0%
(5) 3% Fluorine-treated Bengala Cloisonne 1.0%
(6) 3% fluorine-treated black iron oxide 0.1%
(7) 3% fluorinated zinc oxide 0.5%
(8) 3% fluorinated red 226 4.5%
(9) 3% fluorinated mica titanium 14.0%
(10) Dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd., KF-96A 10cs) 1.0%
(11) Fluorine-modified silicone (ASA Glass FSL-300) 0.5%
(12) Polymer composition 3 0.2%
(13) Preservative appropriate amount (14) Fragrance in a trace amount.

Example 18 (powder eye shadow)
The following components (1) to (9) were mixed and ground. This was transferred to a high-speed blender, and further, components (10) to (14) mixed and dissolved at 80 ° C. were added and mixed uniformly, then ground again and passed through a sieve. This was compression molded into a metal pan.

<Composition>
(1) 5% fluorinated mica titanium 18.0%
(2) 5% fluorinated sericite 22.0%
(3) 5% fluorinated mica 24.0%
(4) 5% Fluorine-treated Bengala 4.5%
(5) 5% fluorinated yellow iron oxide 1.0%
(6) 5% fluorine-treated black iron oxide 0.5%
(7) 5% Fluorine-treated District Blue 10.0%
(8) 5% fluorinated bitumen 6.0%
(9) 5% fluorinated nylon powder 7.0%
(10) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96A6c) 2.0%
(11) Fluorine-modified silicone (Production Example 7 of JP-A-7-277914) 2.0%
(12) Polymer composition 3 2.0%
(13) Preservative appropriate amount (14) Fragrance in a trace amount.

Example 19 (lipstick)
The following components (1) to (6) were dissolved by heating and mixed uniformly. Components (7) to (12) were added thereto, kneaded with a roll mill and uniformly dispersed, then re-dissolved and defoamed, then poured into a mold and rapidly cooled to be hardened. The solidified product was removed from the mold and filled into a container. The stick was then passed through the flame to make the surface uniform.

<Composition>
(1) Candelilla wax 14.0%
(2) Microcrystalline wax 11.9%
(Multi-Wax W-445, manufactured by Wicco)
(3) Alkyl-modified silicone wax 8.0%
(AMS-C30 manufactured by Toray Dow Corning Silicone)
(4) Fluorine-modified silicone (FSL-300 manufactured by Asahi Glass Co., Ltd.) 12.0%
(5) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96A6c) 20.0%
(6) Polymer composition 3 8.0%
(7) 5% silicone-treated titanium oxide 9.0%
(8) 5% silicone-treated red 226 1.0%
(9) 5% silicone-treated mica titanium 15.0%
(10) Antioxidant 0.1%
(11) Preservative appropriate amount (12) Aroma.

All the cosmetics obtained in Examples 11 to 19 were excellent in abrasion resistance and surface non-adhesiveness, and had high makeup sustainability.

Claims (9)

The polymer composition containing the following component (A) and component (B).
Component (A): Fluorine-containing polymer having an ionic group Component (B): Silicone having an ionic group having a charge opposite to that of the component (A)   The polymer composition according to claim 1, wherein the molar ratio of the ionic groups of component (A) and component (B), (A) / (B) is 3/7 to 9/1.   The polymer composition according to claim 1 or 2, wherein the component (A) contains a fluoroalkyl group.   The polymer composition in any one of Claims 1-3 whose ionic group of a component (A) is a carboxyl group or an amino group.   The polymer composition according to any one of claims 1 to 4, wherein the main chain skeleton of the component (A) is a (meth) acrylate type.   The polymer composition according to any one of claims 1 to 5, wherein the ionic group of the component (B) is an amino group or a carboxyl group.   A cosmetic comprising the polymer composition according to any one of claims 1 to 6 and a silicone solvent (hereinafter referred to as component (C)).   The cosmetic according to claim 7, obtained by first mixing the component (A) and the component (B) and mixing the resulting mixture and the component (C). The cosmetic according to claim 7 or 8, wherein the component (C) is at least one selected from fluorine-modified silicone and dimethylpolysiloxane.