JP2011088850A - Surface-treated powder and cosmetic comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-treated powder which cannot be easily eluted with water and a solvent such as ethanol. <P>SOLUTION: The surface treated powder is obtained by coating the surface of a powder particle to be surface-treated with a specific surface treating agent and the surface treating agent contains a fluoroalkyl acrylate/polyalkylene glycol acrylate polymer obtained by copolymerizing a monomer including (a) a fluorine-containing monomer represented by formula (I), CH<SB>2</SB>=C(-X)-C(=O)-Y-[-(CH<SB>2</SB>)<SB>m</SB>-Z-]<SB>p</SB>-(CH<SB>2</SB>)<SB>n</SB>-Rf, and (b) an alkoxy group-containing monomer represented by formula (II), CH<SB>2</SB>=C(X3)-C(=O)-O-(RO)<SB>q</SB>-X4, as essential components, and a treating auxiliary of (c) a polyvalent acidic substance or a polyvalent basic substance as essential components. In the formulas, each symbol has a special definition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a powder treated with a fluorine-containing copolymer (hereinafter referred to as fluorine alkyl acrylate / polyalkylene glycol acrylate polymer), more specifically, at least a part of the surface of the powder (particles) is a fluorine alkyl acrylate / polyalkylene. The present invention relates to a surface treatment (coating) powder that essentially contains a glycol acrylate polymer and a polyvalent acidic substance or a polybasic basic substance as a processing aid, and a cosmetic or the like containing the same.

  Conventionally, surface treatment powders of fluorine-containing copolymers of perfluoroalkyl acrylate and polyalkylene glycol acrylate have been used as fluorine compounds to repel sebum even in systems where sweat and sebum coexist in the presence of sebum and sweat in the air. (Patent Document 1). Patent Document 2 discloses a surface-treated powder of another copolymer of perfluoroalkyl acrylate and polyalkylene glycol acrylate. These fluoropolymers are characterized in that they do not have chemically reactive groups in their molecules and are coated by physical adsorption.

  On the other hand, the fluorine compound having a chemically reactive group in the molecule includes a perfluoroalkyl phosphate ester and a fluorine-containing copolymer or fluoroalkyl having excellent water and oil repellency considering the environment having a fluoroalkyl group having 6 or less carbon atoms. Silanes are disclosed (Patent Documents 3 and 4).

WO95 / 18194 JP 2007-210939 A US 3,632,744 JP-A-2-218603

  However, these fluorine-containing polymers shown in Patent Documents 1 and 2 do not have a chemical bonding group in the molecule, so they are only physically adsorbed on the surface of the powder particles. There were problems with water and oil repellency persistence and hydrophilic oil repellency persistence. These materials have a problem of solvent resistance durability in which part of the physical adsorption is easily extracted when the surface-treated powder is contacted or dispersed with a solvent such as water or ethanol.

The present inventors have proposed a powder surface-treated with a specific fluorine alkyl acrylate / polyalkylene glycol acrylate polymer as referred to in the present invention in application number Japanese Patent Application No. 2008-133521. Had. Powders surface-treated with these fluoropolymers are more water-repellent than surface-treated powders with a fluorine compound having a chemical bond group in the molecule. There was room for improvement in the durability of oil repellency and hydrophilic oil repellency, formulation stability in preparations, and makeup sustainability.

  The present invention is a surface-treated powder that essentially contains a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer having no chemical bonding group in the molecule and a specific processing aid, and can be easily treated with a solvent such as water or ethanol. Provided is a surface-treated powder that is not eluted.

  As a result of intensive studies to solve the above problems, the present inventors have found that a surface-treated powder containing a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a polyvalent acidic substance or polyvalent basic substance as a processing aid. Found that this goal could be achieved.

(1) That is, the present invention is a surface-treated (coating) powder essentially containing a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a polyvalent acidic substance or a polybasic basic substance as a processing aid, A monomer whose surface treating agent essentially comprises (a) a fluorine-containing monomer represented by the following general formula (I) and (b) an alkoxy group-containing monomer represented by the following general formula (II) Characterized in that it comprises at least a fluoroalkyl acrylate / polyalkylene glycol acrylate polymer obtained by copolymerization with a processing aid, and the processing aid essentially contains a polyvalent acidic substance or a polybasic substance. A surface-treated powder is provided.

[Wherein, X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (wherein X1 and X2 are a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group. A linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, —S— or —SO ₂ —;
Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]

[Wherein X3 is a hydrogen atom or a methyl group;
x4 represents a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms;
R is an alkylene group having 2 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
q is an integer of 1-50. ]

  Preferred embodiments of the surface-treated powder according to the present invention include the following. Any combination thereof is also a preferred embodiment of the surface-treated powder according to the present invention unless particularly inconvenient.

(2) As the processing aid to be contained, the polybasic substance is selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, molybdenum, titanium, silicon A hydroxide or a metal salt thereof selected from the group containing a polyvalent metal, wherein the polyvalent acidic substance is sulfonic acid, nitric acid, phosphoric acid, aluminate, silicic acid, oxalic acid, It is a compound consisting of any one or more selected from the group consisting of free forms of succinic acid, malic acid, citric acid, tartaric acid, dicarboxylic acid and tricarboxylic acid and salts thereof.

(3) The ratio of the processing agent and the processing aid of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer is 0.5 to 0.001 when the processing agent is 1.0 (part by weight). , and the and the powder 100 parts by weight of the surface treatment, the total of the processing agent and the processing aid is 0.01 to 40 parts by weight.

(4) The surface treatment agent may further contain other fluorine-containing compounds other than the fluorine-containing copolymer, reactive organopolysiloxane, alkylsilane, polyether-modified silane, organic titanate, polyolefin, hydrogenated lecithin (salt form ), Acylated amino acids (including those in the form of salts or compositions), acidic ester oils, fatty acids (including those in the form of salts), dextrin fatty acid esters, and fructooligosaccharides. It is also effective when combined with a surface treatment agent containing one or more compounds selected from the group consisting of fatty acid esters. Examples of other fluorine-containing compounds other than the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer include perfluoroalkyl phosphate ester, perfluoropolyether phosphate ester, perfluoropolyether silane, and perfluoroalkyl silane.

(5) In another viewpoint of this invention, the cosmetics characterized by containing the powder manufactured by the said surface treatment method can be provided. In addition to such a surface-treated powder, the cosmetic of the present invention preferably further contains at least one of an oily component, an aqueous component, and a surfactant as a constituent component.

(6) The cosmetic of the present invention is any of skin care cosmetics, hair cosmetics, makeup cosmetics, antiperspirant cosmetics, UV protective cosmetics, foot cosmetics, neck cosmetics, and body cosmetics. It is preferable that
(7) The form of the product is any of liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, and spray.

  The surface-treated powder essentially containing the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer and the processing aid of the present invention is compared with the conventional powder surface-treated with only the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer. Since the surface of the powder particles and the present polymer treatment agent are firmly adsorbed, the amount of the surface treatment agent eluted with water, ethanol or the like is considerably suppressed, and the solvent resistance is improved. Therefore, compared to conventional powder surface-treated only with the present polymer, it has excellent water and oil repellency or hydrophilic oil repellency, excellent usability and adhesion to the skin, and excellent cosmetics. A surface-treated powder can be provided.

  Furthermore, using the surface-treated powder, it is possible to easily and simply produce a cosmetic material having a good feeling of use, a cosmetic finish, and a makeup persistence. In addition, in the surface-treated powder and a cosmetic containing the powder, the quality stability and safety of the cosmetic are greatly improved. Therefore, the present invention is extremely useful industrially, particularly in the cosmetic field.

  Hereinafter, the surface-treated powder of the present invention will be described in detail with respect to the best mode for carrying out the present invention, particularly when cosmetics are used. However, the present invention is not limited thereto. In the present invention, "powder to be surface-treated" (the surface-treated powders) include any form of powder and particles.

(1) Surface-treated powder of the present invention (1.1) Surface-treated powder The powder used in the present invention (powder before being surface-treated) is a powder that can be used in various fields. When a cosmetic is selected as an application, a powder that can be used for the cosmetic is selected. Note that either inorganic powder or organic powder may be selected. The surface-treated powder of the present invention is preferably a surface-treated powder for cosmetics, and the surface of the powder particles to be surface-treated is coated with a specific surface treatment agent. There may be.

  For example, inorganic powders include boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, talc, open talc, kaolin, bentonite, smectite, calcium carbonate, magnesium carbonate, calcium phosphate Silica, magnesium oxide, tin oxide, iron oxide, yttrium oxide, chromium oxide, titanium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, bitumen, ultramarine, calcium phosphate, aluminum hydroxide, sulfuric acid Barium, magnesium sulfate, silicic acid, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, Magnesium luminate, magnesium aluminate metasilicate, chlorohydroxyaluminum, clay, zeolite, hydroxyapatite, ceramic powder, spinel, mullite, cordierite, aluminum nitride, titanium nitride, silicon nitride, lanthanum, samarium, tantalum, terbium, coropium, neodymium , Mn-Zn ferrite, Ni-Zn ferrite, silicone carbide, cobalt titanate, barium titanate, iron titanate, lithium cobalt titanate, cobalt aluminate, tin containing antimony tin containing indium oxide, magnetite, aluminum powder, gold powder , Silver powder, platinum powder, copper powder, precious metal colloid, iron powder, zinc powder, cobalt blue, cobalt violet, cobalt green, low order titanium oxide, fine Titanium dioxide, butterfly barium sulfate, petal-like zinc oxide, tetrapotted zinc oxide, fine zinc oxide, pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, titanium oxide-coated synthetic mica, titanium oxide-coated silica, oxidation Pearl pigments such as titanium-coated synthetic mica, titanium oxide-coated talc, zinc oxide-coated silica, titanium oxide-coated colored mica, Bengala-coated mica titanium, Bengala / black iron oxide-coated mica titanium, carmine-coated mica titanium, and kojyo-coated mica titanium Can be mentioned. Specifically, MERCK's IRIODIN (registered trademark) series, TIMIRON (registered trademark) series, COLORONA series (registered trademark) series, DICHRONA (registered trademark) series, XIRONA (registered trademark) series, RONASSTAR (registered trademark) series , BASF's DESREF REFTIONS series, TIMICA series, FLAMENCO series, CLOIZONNE series, DUOCROME series, GEMTONE series, CELLINI series, MEARLMID series, REFECKS series, CHROMA-LITE series, COSMICA series, ECKSART VISIONAIRE (registered trademark) series, IRAGE series, Nippon Sheet Glass's Metashine (registered trademark), Nippon Koken's PROMINENCE (registered trademark) GENESTAR (registered trademark) TWINCLE PEARL (registered trademark), CQV's Cosmetic White Pearl series, sharon Pearl series, etc. Taizo's Preciso White Pearlescent Pigments series and the like. Effect pigments such as aluminum flakes, silica flakes, alumina flakes, glass flakes, Bengala coated mica, carmine, titanium oxide coated borosilicate (sodium / calcium), titanium oxide coated borosilicate (calcium / aluminum), bismuth oxychloride, fish scale foil , Stainless powder, tourmaline powder, powder crushed gemstones such as sapphire and ruby, mango violet, glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, β-wollastonite, zonolite, potassium titanate fiber, aluminum borate fiber , Basic magnesium sulfate fiber, silicon nitride fiber and the like.

  Examples of organic powders include metal soaps, N-mono long chain acyl basic amino acids, amidosulfonic acid polyvalent metals, salt powder, carbon black, tar pigments, and natural pigments , Polyamide powder, Polyester powder, Polyethylene powder, Polyurethane powder (Plastic powder D400 (average particle size: about 12 μm; manufactured by Toyo Pigment), Polypropylene powder, Polystyrene powder, Penzoguanamine powder, Polymethylpenzoguanamine powder, PTFE powder , Cellulose powder, silk powder, silicone powder (KSP-100, KSP-101, KSP-102, KSP-105, KSP-300; manufactured by Shin-Etsu Chemical Co., Ltd., Trefil E506S, E508, E 05, E506, E701; manufactured by Toray Dow Corning, Tospearl 2000B, 150KA, 120A, 105, 145A; manufactured by Momentive Performance Materials Japan) divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenol Resin, fluorine resin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin and other synthetic resin powder, nylon fiber, polyester fiber and other microcrystalline fiber powder, starch powder, CI pigment yellow, CI pigment orange, etc. Examples of tar pigments include Red No. 3, Red No. 10, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227 and Red No. 228. , Red 230, Red 40 No., Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green 201, green 204, green 205, orange 201, orange 203, orange 204, orange 206, orange 207, etc .; natural pigments include carmine, laccaic acid, calsamine, bradylin, crocin, chlorophyll , Β-carotene, powders of natural pigments such as safflower powder, etc. The shape of the powder may be powder or fiber.When cosmetics are selected for use, the particle size is about 1 nm to 2000 μm. It is sufficient if it can be blended in cosmetics within the range of.

In the present invention, the powder (powder before surface treatment) may be a composite powder of two or more types. For example, powder (Excel Mica JP-2 or Excel Pearl: Miyoshi Kasei Co., Ltd.) with aluminum hydroxide on the surface of mica or pearl pigment particles, or hydroxyapatite and zinc oxide on the surface of sericite or pearl pigment. Powder (Powder Ravi: Miyoshi Kasei Co., Ltd.), powder in which fine titanium oxide and fine zinc oxide are dispersed and mixed (TZ-POWDER TYPE1: Miyoshi Kasei), powder in which talc, fine zinc white and fine particle titanium oxide are dispersed and mixed Body (TZ-POWDER TYPE2: Miyoshi Kasei Co., Ltd.), powder in which talc, magnesium oxide and fine particle titanium oxide are dispersed and mixed (TM-POWDER
TYPE: Miyoshi Kasei Co., Ltd.), powders in which talc and fine particle titanium oxide are combined (TTC-30: Miyoshi Kasei Co., Ltd.), and the like.

  In addition, the powder to be surface-treated in the present invention, for example, aluminum, calcium, magnesium, cerium, silicon, zirconium, titanium, zinc, iron, cobalt, etc. It may be previously coated with at least one oxide or hydrated oxide of manganese, nickel and tin.

(1.2) Surface Treatment Agent The surface treatment agent used in the present invention essentially contains a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a processing aid. The fluorine alkyl acrylate / polyalkylene glycol acrylate polymer comprises (a) a fluorine-containing monomer represented by the following general formula (I) and (b) an alkoxy group-containing monomer represented by the following general formula (II). It is obtained by copolymerizing a monomer essentially containing.

  The fluorine-containing monomer (a) is represented by the following general formula (I).

[Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a CFX1X2 group (where X1 and X2 are , A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or An unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, —S— or —SO ₂ —;
Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]

[Wherein X3 is a hydrogen atom or a methyl group;
X4 represents a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms.
R is an alkylene group having 2 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
q is an integer of 1-50. ]

  In the general formula (I), p is preferably 0. A preferred example of X is a hydrogen atom.

  The fluorine-containing monomer (a) generally has a perfluoroalkyl group and / or a partially fluorinated fluoroalkyl group. A perfluoroalkyl group is preferred. The Rf group has 1 to 6 carbon atoms. The number of carbon atoms in the Rf group is preferably 4, 5, or 6, particularly 6. Examples of Rf groups are -CF3, -CF2CF3, -CF2CF2CF3, -CF (CF3) 2, -CF2CF2CF2CF3, -CF2CF (CF3) 2, -C (CF3) 3,-(CF2) 4CF3,-(CF2) 2CF (CF3) 2, -CF2C (CF3) 3, -CF (CF3) CF2CF2CF3,-(CF2) 5CF3, and the like.

  The fluorine-containing monomer (a) it is of course used alone or may be used in combination of two or more.

Examples of the fluorine-containing monomer (a) include the following.
CH2 = C (-X) -C (= O) -O- (CH2) m-S- (CH2) n-Rf
CH2 = C (-X) -C (= O) -O- (CH2) m-SO2- (CH2) n-Rf
CH2 = C (-X) -C (= O) -O- (CH2) n-Rf
CH2 = C (-X) -C (= O) -NH- (CH2) n-Rf
[Wherein, X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (wherein X1 and X2 are a hydrogen atom, a fluorine atom or a chlorine atom), cyano. A group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group;
Rf is a 1-6 fluoroalkyl group;
m is 1 to 10, and n is 0 to 10. ]

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, for example, the following.
CH2 = C (-H) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-H) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-H) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-H) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-H) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-H) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-H) -C (= O) -OCH2CH2N (C2H5) SO2-Rf
CH2 = C (-H) -C (= O) -OCH2CH2N (CH3) SO2-Rf
CH2 = C (-H) -C (= O) -OCH2CH (OCOCH3) CH2-Rf
CH2 = C (-CH3) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-CH3) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-CH3) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-CH3) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-CH3) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-CH3) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-CH3) -C (= O) -OCH2CH2N (C2H5) SO2-Rf
CH2 = C (-CH3) -C (= O) -OCH2CH2N (CH3) SO2-Rf
CH2 = C (-CH3) -C (= O) -OCH2CH (OCOCH3) CH2-Rf

CH2 = C (-F) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-Cl) -C (= O) -NH- (CH2) 2-Rf

CH2 = C (-CF3) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-CF3) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-CN) -C (= O) -NH- (CH2) 2-Rf

CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-S-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-S- (CH2) 2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-SO2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-Rf
CH2 = C (-CF2CF3) -C (= O) -NH- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 3-SO2- (CH2) 2-Rf
CH2 = C (-F) -C (= O) -O- (CH2) 3-Rf
CH2 = C (-F) -C (= O) -NH- (CH2) 3-Rf

CH2 = C (-Cl) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-Cl) -C (= O) -O- (CH2) 3-SO2- (CH2) 2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-CF3) -C (= O) -O- (CH2) 3-SO2- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-CF2H) -C (= O) -O- (CH2) 3-SO2- (CH2) 2-Rf

CH2 = C (-CN) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-CN) -C (= O) -O- (CH2) 3-SO2- (CH2) 2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 3-S-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 3-S- (CH2) 2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 3-SO2-Rf
CH2 = C (-CF2CF3) -C (= O) -O- (CH2) 2-SO2- (CH2) 2-Rf
[In the above formula, Rf is a 1-6 fluoroalkyl group. ]

  The alkoxy group-containing monomer (b) is a non-fluorine monomer and is a compound (alkylene glycol (meth) acrylate) represented by the following general formula (II).

[Wherein X3 is a hydrogen atom or a methyl group;
X4 represents a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms;
R is an alkylene group having 2 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
R is an alkylene group having 2 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
q is an integer of 1-50. ]

  In the alkoxy group-containing monomer (b), q is preferably 1 to 30, for example, 2 to 10, particularly 2 to 5.

  In the general formula (II), R is preferably ethylene or propylene, particularly ethylene. R in the general formula (II) may be a combination of two or more types of alkylene. In that case, at least one of R is preferably ethylene. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.

  The alkoxy group-containing monomer (b) may be a mixture of two or more types.

Specific examples of the alkoxy group-containing monomer (b) include, for example, the following, but are not limited thereto.
CH2 = CHCOO- (CH2CH2O) 9-H
CH2 = C (CH3) COO- (CH2CH2O) 9-H
CH2 = C (CH3) COO- (CH2CH2O) 23-H
CH2 = C (CH3) COO- (CH2CH2O) 50-H
CH2 = C (CH3) COO- (CH2CH (CH3) O) 9-H
CH2 = CHCOO- (CH2CH (CH3) O) 9-H
CH2 = C (CH3) COO- (CH2CH (CH3) O) 9-H
CH2 = C (CH3) COO- (CH2CH2O) 5- (CH2CH (CH3) O) 2-H
CH2 = C (CH3) COO- (CH2CH2O) 8- (CH2CH (CH3) O) 6-H
CH2 = CX3- (CH2CH2O) n-CH3
CH2 = CX3COO- (CH2CH (CH3) O) n-CH3
CH2 = CX3COO- (CH2CH2O) 5- (CH2CH (CH3) O) 3-CH3

  The weight average molecular weight of the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer of the present invention is about 1,000 to 1,000,000, preferably about 5,000 to 500,000. The weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.

  The fluoroalkyl acrylate / polyalkylene glycol acrylate polymer may include a crosslinkable monomer. The crosslinkable monomer can be a compound that has at least two reactive groups and / or carbon-carbon double bonds and does not contain fluorine. The crosslinkable monomer can be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanates, carboxyl groups, and the like. In the present invention, a monomer having an amino group is not used.

  The crosslinkable monomer is preferably a non-fluorine crosslinkable monomer, and more preferably di (meth) acrylate.

  The crosslinkable monomer has the general formula:

Wherein each X5 is a hydrogen atom or a methyl group;
R10 is an alkylene group having 2 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
q is an integer of 1-50. ]
It is particularly preferable that the compound represented by the formula (alkylene glycol di (meth) acrylate). In addition, it is preferable that the carbon number of R10 is 2-10, for example, 2-6, especially 2-4. R1 is preferably an ethylene group.

  For example, when the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer contains 100 parts by weight of the fluorine-containing monomer (a), the amount of the alkoxy group-containing monomer (b) is preferably 10 to 400 parts by weight, preferably May be 25 to 150 parts by weight, more preferably 43 to 100 parts by weight. This is because if it is less than 10 parts by weight, hydrophilicity cannot be obtained, and if it is more than 400 parts by weight, the oil repellency may be lowered. When the crosslinkable monomer is contained, the amount of the crosslinkable monomer is 30 parts by weight or less, for example, 0.1 to 20 parts by weight, particularly 100 parts by weight of the fluorine-containing monomer (a). The amount can be 0.5 to 10 parts by weight. This is because if it is larger than 30 parts by weight, a hard film is formed and the feeling of use may be deteriorated. The fluorine alkyl acrylate / polyalkylene glycol acrylate polymer used in the present invention can be synthesized by, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2000-290640, but is not limited thereto. For example, the polymerization of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected. For example, solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent and water in combination is generally selected. Generally, it is prepared into a treatment liquid by diluting with water after polymerization or emulsifying in water by adding an emulsifier.

  The fluoroalkyl acrylate / polyalkylene glycol acrylate polymer, which is a surface treatment agent used in the present invention, is water-soluble or soluble in an alcohol solution such as isopropyl alcohol or ethanol, depending on the blending ratio of each monomer. The surface treatment agent is preferably in the form of a solution, an emulsion or an aerosol. The surface treatment agent comprises, for example, a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a medium (for example, a liquid medium such as an organic solvent and water). In the surface treatment agent, the concentration of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymers, for example, be a 0.01 to 50 wt%.

  The coating amount (surface treatment amount) on the surface treated powder is the chemical composition of the powder to be surface treated (powder before surface treatment), its particle size, presence or absence of porous property, oil absorption, water absorption. Depending on the specific surface area, the total coating amount of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer and the polyvalent acidic substance or polyvalent basic substance as a processing aid is 100 parts by weight of the surface-treated powder. 0.01 to 40 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 30 parts by weight. At this time, the ratio of the processing agent and the processing aid of the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer is 0.5 to 0.001 when the processing agent is 1.0 (part by weight). , Preferably 0.2 to 0.001. If it is less than this, a sufficient effect cannot be obtained, and if it is more than this, the function of the present polymer as a surface-treated powder will be lowered and the effect in cosmetics will be insufficient and it will be uneconomical.

  Improvement in feeling of use and adhesion to the skin of the surface-treated powder essentially containing a polyalkyl acid substance or a polybasic basic substance as a processing aid and the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer of the present invention, cosmetics In order to improve the affinity with an oil agent and the like, and to improve the feeling of use of cosmetics formulated with these surface-treated powders, cosmetic finish and makeup sustainability, the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer compositely can be surface treated with said fluorinated alkyl acrylate / polyalkylene glycol acrylates other surface treatment agent compounds other than polymers. That is, the surface treatment agent is effective to further contain other compounds other than the fluorine-alkyl acrylate / polyalkylene glycol acrylate polymer. Other compounds other than the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer include, for example, fluorine-containing compounds such as perfluoroalkyl phosphate ester, perfluoropolyether phosphate ester, perfluoropolyether silane, and perfluoroalkyl silane, reaction Organic organopolysiloxane, alkylsilane, organic titanate, polyolefin, hydrogenated lecithin (including its salt), N-acylamino acid (including its salt or composition), acidic ester oil, fatty acid (including its salt). ), dextrin fatty acid esters, one or more compounds selected from the fructooligosaccharides fatty acid esters.

  Fluoroalkyl acrylate / polyalkylene glycol acrylate polymer, polyvalent acidic substance or polybasic basic substance (referred to as treating agent A) as a processing aid, and other components (compounding agent B and surface treating agent) combined with this Other fluorine-containing compounds other than the fluorine-containing copolymer such as perfluoroalkyl phosphate ester, perfluoropolyether phosphate ester, perfluoropolyether silane, perfluoroalkyl silane, and reactive organopoly Siloxane, alkylsilane, organic titanate, polyolefin, hydrogenated lecithin (including its salt), N-acylamino acid (including its salt or composition), acidic ester oil, fatty acid (including its salt), dextrin Selected from fatty acid esters and fructooligosaccharide fatty acid esters Mixing ratio of the one or more compounds, A: B is from 39.95 to 0.05 parts: from 0.05 to 39.95 parts is preferred. More preferably, A: B is 29.95 to 0.05 parts: 0.05 to 29.95 parts. Although it differs depending on the type of powder, the type of cosmetic, and the blending amount in the cosmetic, if these ratios are exceeded, the effect on the cosmetic tends to decrease.

  In the present invention, at least a part of the surface of the surface-treated powder (before surface treatment) is treated with a polyvalent acidic substance or polybasic basic substance using the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a processing aid. When the treatment is performed by containing a substance as an essential component, the surface-treated powder exhibits water / oil repellency or hydrophilic oil repellency depending on the type of polyvalent acidic substance or polyvalent basic substance.

  In order to impart solvent resistance, water and oil repellency can be obtained when a polyvalent acidic substance is contained as a processing aid in the surface-treated powder, and hydrophilic oil repellency can be obtained when a polybasic substance is contained.

  Specific examples of the polybasic substance that is a processing aid for the surface treatment agent used in the present invention include calcium hydroxide, calcium acetate, calcium chloride, calcium formate, calcium sulfate, calcium butyrate, barium acetate, barium sulfate, Barium phosphate, barium oxalate, barium butyrate, manganese chloride, manganese acetate, manganese formate, manganese sulfate, cupric chloride, copper dihydrate, copper sulfate, copper butyrate, copper oxalate, copper citrate, gluconic acid Copper, cobalt chloride, cobalt sulfate, cobalt acetate, nickel sulfate, nickel chloride, nickel acetate, nickel ammonium sulfate, aluminum sulfate, aluminum sulfite, polyaluminum chloride, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum lactate, sodium aluminate, Ferrous chloride, salt Ferric, ferrous sulfate, ferric sulfate, iron citrate, iron lactate, zinc bromide, zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, zinc lactate, zirconium acetate, zirconium chloride, chromium acetate, sulfuric acid Chromium, hydroxy zirconium chloride, magnesium hydroxide, magnesium acetate, zinc gluconate, magnesium gluconate, calcium gluconate, iron gluconate, copper gluconate, aluminum gluconate, magnesium oxalate, magnesium sulfate, magnesium chloride, magnesium citrate , Sodium phosphotungstate, sodium tungsten citrate, 12 tungstosilicate 26 hydrate, sodium silicate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, alum, potassium alum, iron alum, ammonium alum, basic Li aluminum hydroxide, titanium chloride, titanium sulfate, water glass. One or a combination of two or more of these may be used. Examples of the polycarboxylic acid dicarboxylic acid and tricarboxylic acid include free forms of oxalic acid, succinic acid, tartaric acid, malic acid, malonic acid, citric acid, and metal salts thereof.

(2) Production method In the present invention, a surface treatment agent, that is, a surface treatment agent that essentially contains a polyalkyl acid substance or a polybasic substance as a processing aid, and a fluoroalkyl acrylate / polyalkylene glycol acrylate polymer is used as a powder. There is no particular limitation on the method for coating the film, and it can be carried out by a known method. Surface treatment methods are roughly classified into dry methods and wet methods. For example, using agitation mixers, ball mills, jet mills, kneaders, planetary mixers, pony mixers, sand mills, attritors, ribbon blenders, disper mixers, homomixers, extruders, etc. The surface treatment agent used in the present invention, the treatment aid and the powder are mixed and contacted for a predetermined time. At this time, the treatment may be performed while applying energy such as mechanochemical mechanical force, plasma, flame, ultraviolet ray, electron beam, superheated steam, laser beam, electromagnetic wave or the like. As the wet method, the treatment can be performed by dispersing the powder, the surface treatment agent, and the processing aid in water, a solvent, a supercritical fluid (water, CO 2, etc.), bringing them into contact with each other, and then evaporating the solvent.

  In addition, the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer used in the present invention, a polyvalent acidic substance or polyvalent basic substance as a processing aid, and a perfluoroalkyl phosphate or perfluoro as a surface treating agent to be combined. Fluorine-containing compounds such as polyether phosphate ester, perfluoropolyether silane, perfluoroalkyl silane, organopolysiloxane, alkyl silane, organic titanate, polyolefin, hydrogenated lecithin (including salts thereof), N-acylamino acid ( Including a salt or a composition thereof), an acidic ester oil, a fatty acid (including a salt thereof), and a compound surface treatment with one or more compounds selected from dextrin fatty acid esters. Fluoroalkyl acrylate / polyur Similarly to the case where the surface treatment is carried out by essentially containing a polyvalent acidic substance or a polybasic substance as a processing aid, a surface treatment agent and a processing aid further containing the compound Surface treatment can be carried out by mixing contact. Powders to be coated with the properties (liquid, solid, gel, etc.) and physical properties (melting point, boiling point, glass transition temperature, solubility, reactivity, etc.) of the compound selected for composite surface treatment What is necessary is just to select the optimal coating manufacturing method according to the kind of this, and there is no restriction | limiting in particular by a manufacturing method.

  In the case of composite surface treatment, a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and a polyvalent acidic substance or polyvalent basic substance as a processing aid are first coated, and then the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer. Other than the method of coating other surface treatment agent components, fluorine alkyl acrylate / polyalkylene glycol acrylate polymer and polyhydric acid substance or polybasic basic substance as treatment aid, other than the fluorine alkyl acrylate / polyalkylene glycol acrylate polymer Method of simultaneously coating other surface treatment agent components, after coating other surface treatment agent components other than fluorine alkyl acrylate / polyalkylene glycol acrylate polymer first, then fluorine alkyl acrylate / Method for coating a polyvalent acidic substance or polyvalent basic substance as polyalkylene glycol acrylate polymers and processing aids, and the like. A method with the best physical properties of the finally obtained surface-treated powder may be adopted.

  As a method of measuring the elution amount of the surface treatment agent with respect to a solvent such as water or ethanol of the surface treatment powder of the present invention, the weighed surface treatment powder is placed in a solvent 10 times the weight of the surface treatment powder. After stirring and dispersing for a certain period of time, the surface treatment agent eluted by filtration and concentration is recovered as a fluoroalkyl acrylate / polyalkylene glycol acrylate polymer. The elution amount (adsorption rate) is obtained from the surface treatment amount and the recovered amount.

(3) Cosmetics of this invention The surface treatment powder obtained by this invention can mix | blend 1 type (s) or 2 or more types with cosmetics.

  The cosmetic of the present invention is a cosmetic containing the surface-treated powder described above. That is, the surface-treated powder can be prepared as described above.

  In the present invention, there is no particular difficulty in formulating cosmetics, and the intended cosmetics are based on techniques that have been used in the past, in particular, techniques that incorporate surface-treated powders into cosmetics (for example, emulsification and the like). You can get a fee.

  When the surface-treated powder of the present invention is blended in a cosmetic, the blending amount varies depending on the type and dosage form of the cosmetic, but is preferably 0.1 to 100% by weight in the total cosmetic composition. . In addition, the surface-treated powder of the present invention can form a dispersion with a water-based component when the powder showing hydrophilic oil repellency is used, and the amount of the powder is not particularly limited when blended with cosmetics.

  The other components to be blended in the cosmetics of the present invention, for example, oil components, aqueous components, and surfactants.

  Oil components include safflower oil, soybean oil, evening primrose oil, grape seed oil, rosehip oil, cucumber nut oil, almond oil, sesame oil, wheat germ oil, corn oil, cottonseed oil, avocado oil, olive oil, camellia oil, persic oil , Castor oil, peanut oil, hazelnut oil, macadamia nut oil, medofoam oil, cocoa butter, shea fat, tree wax, coconut oil, palm oil, palm kernel oil, beef tallow, horse fat, mink oil, milk fat, egg yolk oil, turtle Oils and fats, beeswax, whale wax, lanolin, carnauba wax, candelilla wax, jojoba oil and other waxes, liquid paraffin, liquid isoparaffin, squalane, squalene, petrolatum, paraffin, ceresin, microcrystalline wax, α-olefin oligomer Hydrocarbons such as lauric acid, myristic acid, Fatty acid, stearic acid, behenic acid, oleic acid, linoleic acid, undecylenic acid, hydroxystearic acid, lanolin fatty acid and other fatty acids, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, jojoba Higher alcohols such as alcohol, batyl alcohol, cholesterol, phytosterol, lanolin alcohol, isostearyl alcohol, sterols such as cholesterol, sitosterol, phytosterol, lanosterol, ethyl oleate, isopropyl myristate, cetyl octanoate, diisostearyl malate , Esters such as glyceryl tricaprylate, dimethylpolysiloxane, methylphenylpolysiloxane Loxane, alkyl-modified silicone, cyclic silicone pentamer, cyclic silicone hexamer, methyltrimethicone, caprylylmethicone, dimethicone, diethicon, trimethicone, alkylmethicone, tocopheryltrisiloxane, fluorocarbon silicone and other silicones, perfluoropoly Fluorine oils such as ether oils, perfluorocarbons, hydrofluoroethers, organic solvents such as ethyl acetate, butyl acetate, and toluene, specifically dimerlinoleic acid and higher alcohols such as Plandour-S and Plandour-H Diesters with a mixture of dimer linoleic acid and dimer linoleyl alcohol such as Rusplan DD-DA5, Rusplan DD-DA7, Erdeu CL-202, Erdeu CL-301, Rudeyuu PS-203, Eldew PS-304, glutamic acid, etc. Eldew PS-306, a natural fatty acid and higher alcohol, cholesterol, etc. esters of phytosterols is illustrated.

Examples of the aqueous component include lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as 1,3-butylene glycol, propylene glycol, polyethylene glycol, glycerin, diglycerin, polyglycerin, trehalose, erythritol, mannitol, xylitol, sorbitol, and maltose. , As well as gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat), dextrin, dextran, alge colloid, trant gum, locust bean gum Plant-based water-soluble polymers such as xanthan gum, dextran, succinoglucan, pullulan, etc. Animal-based water-soluble polymers such as gen, casein, albumin and gelatin, starch-based water-soluble polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose and hydroxypropyl Cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose-based water-soluble polymers such as cellulose powder, alginic acid-based water-soluble polymers such as sodium alginate and propylene glycol alginate, polyvinyl methyl ether, carboxyvinyl polymer, etc. Vinyl water-soluble polymer, polyoxyethylene water-soluble polymer, polyoxyethylene poly Water-soluble polymers based on xylene-propylene copolymer, acrylic water-soluble polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, other synthetic water-soluble polymers such as polyethyleneimine and cationic polymers, bentonite, magnesium aluminum silicate Inorganic water-soluble polymers such as montmorillonite, beidellite, nontronite, saponite, hectorite, and silicic anhydride. These water-soluble polymers include film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone, polyacrylamide emulsion thickeners such as Sepigel 305 and 501 (manufactured by SEPPIC), sodium acrylate and sodium acryloyldimethyltaurate. Copolymers SIMULGEL EG, NS, A, FL (made by SEPPIC) and other acrylic acid emulsion thickeners, LIPIDURE HM-600, PBM (made by Nippon Oil & Fats Co., Ltd.) and other methacryloyloxyethyl phosphorylcholine water-soluble polymers, Carbopol 940, 941, 1342 (manufactured by Goodrich Chemical), ACUPE HV-505E, HV-501ER (manufactured by Sumitomo Seika), Pemulen TR-1, TR-2 (manufactured by NOVEON), Primal ASE-60 ( SAL, manufactured by Polymer Latex ARE
Microorganisms belonging to the genus Alkaligenes, such as SC81 (manufactured by Ciba Specialty Chemicals), ACULYN22, 28, 33A (manufactured by Rohm & Haas), STRUCTURE 2001, 3001 (manufactured by NSC Japan), etc. Polysaccharides produced are also included.

  Surfactants include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, condensates of amino acids and fatty acids, alkane sulfonates, alkene sulfonates, and fatty acid ester sulfones. Acid salts, sulfonates of fatty acid amides, formalin condensation sulfonates, alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates, sulfates of fatty acid esters, fatty acid alkylolamides Anionic surfactants consisting of sulfuric acid ester salts such as, sulfuric acid ester salts such as funnel oil, alkyl phosphates, ether phosphates, alkylallyl ether phosphates, amide phosphates, N-acyl amino acid based active agents, Alkylamine salt, polya Cationic surfactants composed of amine salts, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acids Ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly Oxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol Fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholesterol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, Polyoxyalkylene / alkyl co-modified organopolysiloxane, polyglycerin-modified organopolysiloxane, nonionic surfactant made of alkanolamide, sugar ether, sugar amide, etc., and amphoteric interface made of betaine, aminocarboxylate, imidazoline derivative, etc. An activator is mentioned.

  The cosmetics of the present invention have a feeling of use, cosmetic finish, cosmetic durability, excellent affinity with other ingredients blended in cosmetic preparations, as well as quality stability and a living body. Other components used in normal cosmetics, such as pigment dispersants, oils, surfactants, ultraviolet absorbers, preservatives, antioxidants, as long as they do not impair the safety of the products and the safety to the environment , Film forming agents, humectants, thickeners, dyes, pigments, various drugs (vitamins, astaxanthin, α-lipoic acid, Co enzyme Q10, etc.), flavors, and the like can be appropriately blended.

  For example, whitening agents include kojic acid and its derivatives, vitamin C and its derivatives (ascorbic acid glucoside, dipalmitic acid L-ascorbyl, tetraisopalmitic acid L-ascorbyl and other L-ascorbic acid alkyl esters, L-ascorbic acid Phosphate ester, ethyl L-ascorbate, sulfate L-ascorbate, etc.), arbutin, ellagic acid, linoleic acid and derivatives thereof, vitamin E and derivatives thereof, glycyrrhizic acid and derivatives thereof, tranexamic acid, placenta extract, grabrizine , Glabrene, liquiritin, isoliquiritin and licorice extract, yokuinin (barley) extract, koganebana (ogon) extract, seaweed extract (comb, macombu, wakame, hijiki, hibamata, sujime, trorocon , Ecklonia, Ecklonia stolonifera, Chigaiso, Sargassum, brown algae such as giant kelp; Gelidium, Chondrus, Suginori, Usubanori, Asakusanori, Matsunori, Tosakamatsu, funori, Gracilaria, Kaimensou, Igisu, red algae such Egonori; Chlorella, Enteromorpha, Dunaliella, Chlorococcus, Anaaaosa, Kawanori, Marimo, Shiogusa, Casanori, Fujuzumo, Tamajusmo, Aegumi, green algae; Spirulina and other cyanobacteria), Sempukuka extract, grape extract, wheat extract, tomato extract, carotenoid ( Carotene, lycopene, astaxanthin, etc.), agarose, oligosaccharide, hydroquinone and its derivatives, cysteine and its derivatives, Ibukitorano extract, Neubara (Ages) extract, Ezokogi extract , Pea extract, chamomile extract, caquette extract, orange extract, raspberry extract, kiwi extract, clara extract, coffee extract, sesame oil, sesame oil, gokahi extract, rice extract , Rice bran extract, Saisin extract, Hawthorn extract, Sunpens extract, Peonies extract, Shirayuri extract, Mulberry extract, Toki extract, Beech extract, Beech bud extract, Black Currant extract, hop extract, micaika (maika, hermanus) extract, mokka (bokeh) extract, yukinoshita extract, tea extract (Oolong tea, black tea, green tea, etc.), ganoderma extract, microbial fermentation metabolite, Examples include soybean extract, molasses extract, and rahan fruit extract. The names in parentheses are plant aliases, herbal medicine names, and the like.

Antioxidants include butylhydroxyanisole (BHA), dibutylhydroxytoluene (BHT), vitamin E and its derivatives (dl-α (β, γ) -tocopherol, dl-α-tocopherol acetate, nicotinic acid-dl-α -Tocopherol, linoleic acid-dl-α-tocopherol, tocopherol and derivatives thereof such as succinic acid dl-α-tocopherol, ubiquinones, etc., vitamin A and derivatives thereof (retinol palmitate, retinol acetate, etc., and derivatives thereof, Retinal such as dehydroretinal and its derivatives), carotenoids (such as carotene, lycopene, astaxanthin), vitamin B and its derivatives (thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, pyridoxine di) Octanoate, flavin adenine dinucleotide, cyanocobalamin, folic acid, nicotinic acid amide, nicotinic acid such as benzyl nicotinate, choline, etc.), vitamin C and its derivatives (dipalmitate L-ascorbyl, tetraisopalmitate L-ascorbyl, etc.) L-ascorbic acid alkyl ester, L-ascorbic acid phosphoric acid ester, L-ascorbic acid sulfuric acid ester, etc.), vitamin D and its derivatives (ergocalciferol, cholecalciferol, dihydroxystannal etc.), rutin and its derivatives, Thiotaurine, taurine, hydroquinone and derivatives thereof, histidine, catechin and derivatives thereof, grabrizine, glabrene, liquiritin, isoliquiritin and licorice extract containing these, glutathione and Derivatives thereof, gallic acid and derivatives thereof, cholesterol and derivatives thereof, superoxide dismutase, mannitol, cucumber extract, quette extract, gentian (gentian) extract, Gennosho extract, hawthorn extract, peonies extract, ginkgo biloba extract , Koganebana (Ougon) extract, carrot extract, maikaika (maikai, hamanasu) extract, sunpens (kawara ketsumei) extract, tormentilla extract, parsley extract, grape extract, button (button pi) extract, mokka (bokeh) ) Extract, Melissa extract, Yashajitsu (Yasha) extract, Yukinoshita extract, Rosemary (mannenrou) extract, lettuce extract, tea extract (Oolong tea, black tea, green tea, etc.), microbial fermentation metabolites, seaweed extract , Reishi extract, eggshell membrane extraction Examples include extracts, placenta extracts, and rahan fruit extracts. The names in parentheses are plant aliases, herbal medicine names, and the like.

Anti-inflammatory agents include glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, vitamin B and its derivatives (thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, pyridoxine dioctanoate, flavin adenine dinucleotide , Cyanocobalamin, folic acid, nicotinic acid amide, nicotinic acid such as benzyl nicotinate, choline, etc.), aloe extract, ashitaba extract, altea extract, arnica extract, sulfur and its derivatives, nettle extract Kawamomogi) extract, Turmeric extract, Yellowfin extract, Hypericum extract, Chamomile extract, Comfrey extract, Honeysuckle extract, Watercress extract, Salvia (sage) extract, Lemoko extract, perilla extract, birch extract, elder extract, larva extract, mugwort extract, eucalyptus extract, mugwort extract, forsythia extract, chondroitin sulfate and its derivatives, zinc oxide Etc. The names in parentheses are plant aliases, herbal medicine names, and the like.

Examples of cell activators include carotenoids (such as carotene, lycopene, astaxanthin), vitamin A and derivatives thereof (retinol such as retinol palmitate and retinol acetate; and retinals such as dehydroretinal and derivatives thereof), vitamin C and its derivatives. Derivatives (L-ascorbic acid alkyl esters such as L-ascorbyl dipalmitate and L-ascorbyl tetraisopalmitate, L-ascorbic acid phosphate, L-ascorbic acid sulfate, etc.), vitamin B and its derivatives (thiamine hydrochloride) Salt, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, pyridoxine dioctanoate, flavin adenine dinucleotide, cyanocobalamin, folic acid, nicotinamide and benzyl nicotinate (Tinic acids, choline, etc.), ribonucleic acid and salts thereof, deoxyribonucleic acid and salts thereof, α- and γ-linolenic acid, xanthine and derivatives thereof (caffeine, etc.), amino acids and derivatives thereof (serine, glutamic acid, theanine, hydroxy) Proline, pyrrolidone carboxylic acid, etc.), docosahexaenoic acid and its derivatives, eicosapentaenoic acid and its derivatives, citric acid, lactic acid, malic acid, succinic acid, almond extract, apricot extract, ginkgo biloba extract, yellowfin ) Extract, Barley (Bakuga) extract, Kiwi extract, Cucumber extract, Shiitake extract, Japanese horse chestnut extract, Assembly extract, Soybean extract, Jujube extract, Rhizoma extract, Pepper extract, Tokachinka extract, tomato extract, garlic extract, garlic Extract, Bukuryu extract, Grape seed oil, Beech extract, Beech sprout extract, Peach extract, Eucalyptus extract, Lily extract, Lettuce extract, Lemon extract, Rosemary extract, Malt Root extract, animal-derived extract (mollusk and other mollusc extracts, shell extract, shellfish extract, fish extract, chicken crown extract, royal jelly, silk protein and its degradation products, placenta extract, serum deproteinization extraction Product, lactoferrin or its degradation product), yeast extract, microbial fermentation metabolite (derived from lactic acid bacteria, bifidobacteria, etc.), ganoderma extract and the like. The names in parentheses are plant aliases, herbal medicine names, and the like.

Antibacterial agents include benzoic acid, sodium benzoate, paraoxybenzoic acid ester, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol and the like.

  Anti-inflammatory agents include sulfur and its derivatives, glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, artea extract, ashitaba extract, arnica extract, ginseng extract, nettle extract, buckwheat extract, hypericum extract , Chamomile extract, goldfish extract, watercress extract, comfrey extract, salvia extract, sicon extract, perilla extract, birch extract, gentian extract and the like.

The active oxygen scavenger has an action such as suppression of lipid peroxide production, such as superoxide dismutase, mannitol, quercetin, catechin and derivatives thereof, rutin and derivatives thereof, button pi extract, yashajitsu extract, melissa Extracts, Rahan fruit extract, retinol and its derivatives, vitamin A such as carotenoid, thiamine and its derivatives, riboflavin and its derivatives, pyridoxine and its derivatives, vitamin B such as nicotinic acid and its derivatives, tocopherol and its derivatives, etc. Vitamin E, dibutylhydroxytoluene and butylhydroxyanisole.

As humectants, proteins such as elastin and keratin or derivatives thereof, hydrolysates and salts thereof, amino acids such as glycine, serine, aspartic acid, glutamic acid, arginine and theanine and derivatives thereof, sorbitol, erythritol, trehalose, Inositol, glucose, sucrose and derivatives thereof, dextrin and derivatives thereof, saccharides such as honey, D-panthenol and derivatives thereof, urea, phospholipid, ceramide, auren extract, camphor extract, diau extract, senkyu extract, They are mallow mushroom extract, gypsophila extract, dokudami extract, hamamelis extract, bodaige extract, maronier extract, quince extract and the like.

As UV absorbers, benzophenone derivatives: diethylaminohydroxybenzoylhexylbenzoate (amino-substituted hydroxybenzophenone derivatives) marketed under the trade name "Uvinul A Plus" by BASF, benzotriazole derivatives: "Tinosorb by Ciba Specialty Chemicals
Methylene bis (benzotriazolyl) tetramethylbutylphenol (methylene bis (hydroxyphenylbenzotriazole) derivative), a triazine derivative, commercially available in micronized form as an aqueous dispersion under the trade name M "" Uvinul T150 "by BASF Ethylhexyltriazone, which is commercially available under the trade name of 2,4-bis-{[4- (2-ethylhexyloxy) -2-hydroxy sold under the trade name "Tinosorb S" by Ciba Specialty Chemicals. ] Phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine benzimidazole derivative: phenylbenzimidazolesulfonic acid, benzalmalo, which is commercially available under the trade name "Eusolex 232" by Merck Nart derivatives: marketed under the trade name "Parsol SLX" by Hoffmann LaRoche, for example polysil Polyorganosiloxanes containing benzalmalonate functional groups, such as N-15, β, β-diphenyl acrylate derivatives: Octocrylene, other salicylic acid derivatives, especially marketed under the trade name “Univul N539” by BASF; Examples thereof include benzylidene camphor derivatives, p-aminobenzoic acid (PABA) derivatives, benzoxazole derivatives, 4,4-diarylbutanediene derivatives, and the like.

  There is no limitation in particular about the dosage form of the cosmetics of this invention. As the cosmetic dosage form, for example, conventionally known dosage forms such as emulsion, cream, solid, paste, gel, powder, multilayer, mousse, and spray can be selected. Specifically, as makeup cosmetics, makeup foundation, powder foundation, liquid foundation, oily foundation, stick foundation, pressed powder, face powder, white powder, lipstick, lipstick overcoat, lip gloss, concealer, blusher, eye shadow, Eyebrow, eyeliner, mascara, water-based nail enamel, oily nail enamel, emulsified nail enamel, enamel top coat, enamel base coat, etc.Skin care cosmetics include emollient cream, cold cream, whitening cream, milky lotion, lotion, beauty liquid, UV for packs, carmine lotions, liquid facial cleansers, facial cleansing foams, facial cleansing creams, facial cleansing powders, makeup cleansers, body gloss, sunscreens or sun creams Protective cosmetics and lotions, etc., hair gloss, hair cream, hair shampoo, hair rinse, hair color, hair brushing agent, etc., antiperspirant cosmetics such as cream, lotion, powder, spray type deodorant products, etc. Other examples include emulsions, soaps, bath preparations, perfumes and the like.

(Uses other than cosmetics)
About the surface-treated powder of the present invention, powders blended in not only cosmetics but also inks, paints, resin master batches, papers, ceramic materials, magnetic materials, rare earths, optical materials, conductive materials, voltage materials, etc. It can also be applied to powders used in various fields. In particular, when a powder that can be used for cosmetics is used in other fields, the surface-treated powder described for the above-mentioned cosmetics can be similarly applied to other fields.

  Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, the present invention is not limited to these examples.

[Production Examples 1 to 3]
Production examples of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer used in the present invention are shown below.

[Production Example 1]
18.6 g of fluorine-containing monomer CH2 = CHC (= O) O-CH2CH2C6F13 (hereinafter referred to as C6SFA (a)) was added to a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer. Polyethylene glycol acrylate
11.4g of CH2 = CHC (= O) O- (CH2CH2O) n-H (BLEMMER AE90, manufactured by NOF Corporation, the average value of n is 2, hereinafter referred to as AE90 (b)) is 0, and dodecanethiol is 0 .3 g and 45 g of isopropanol were charged, and nitrogen bubbling was performed for 30 minutes. After raising the internal temperature to 50-65 ° C. under a nitrogen stream, 0.4 g of perbutyl PV (hereinafter referred to as PV) was added and reacted at 60 to 65 ° C. for 10 hours. After isopropanol was distilled off at about 70 ° C. under reduced pressure conditions to obtain a pale yellow polymer residue, 122.4 g of water was added and the internal temperature was kept at about 80 ° C. for 1 hr or longer. An aqueous dispersion having a solid content concentration of about 20% by weight was prepared by cooling (compound a).

[Production Example 2]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer, 18.6 g of C6SFA (a), 5.7 g of AE90 (b), polyethylene glycol acrylate CH2 = CHC (= O) O -(CH2CH2O) n-H (BLEMMER AE200, manufactured by NOF Corporation, the average value of n is 4.5, hereinafter referred to as AE200 (b)) is 5.7 g, dodecanethiol is 0.3 g, and isopropanol is 45 g. Then, the same polymerization reaction as in Production Example 1 was carried out to prepare an aqueous dispersion having a solid concentration of about 20% by weight (compound b).

[Production Example 3]
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.6 g of C6SFA (a), 10.5 g of AE350 (b), polyethylene glycol diacrylate CH2 = CHC (= O) 0.9-g O- (CH2CH2O) n-C (= O) CH = CH2 (BLEMMER ADE300, manufactured by NOF Corporation, the average value of n is 7), 0.3 g dodecanethiol and 45 g isopropanol, The same polymerization reaction as in Production Example 1 was carried out to prepare an aqueous dispersion having a solid content concentration of about 20% by weight (compound c).

(Contact angle test of water and dodecane)
A double-sided tape is affixed to the slide glass, and the surface-treated powder is applied to the other tape surface with a decorative puff until the tape surface is no longer sticky. Dropping water and dodecane onto the powder coating surface with a contact angle meter (CA-D) manufactured by Kyowa Interface Science Co., Ltd. The angle (contact angle) formed by was measured. If the contact angle cannot be measured because the droplets are absorbed by the powder

(Elution test of water or ethanol)
20 g of powder and 200 ml of purified water or ethanol are placed in a 300 ml glass beaker and stirred for 20 minutes (three-one motor 400 rpm). The stirred solution is filtered through a Menplan filter (PTFE 0.1 μm Pore). At this time, the filtered powder cake is repeatedly washed with 20 ml of ethanol twice to collect the filtrate. Ethanol was distilled off from the filtrate using an evaporator (under reduced pressure at 60 ° C.) to recover an ethanol-eluting polymer. The recovered amount was divided by the theoretical treatment amount of the surface treatment agent of the treated powder to obtain the ethanol elution amount.

  In the surface-treated powder of the present invention, those having water / oil repellency and ethanol elution amount of 9% or less are hereinafter treated with FA, those having hydrophilic oil repellency and water elution amount of 9% or less are as follows. FAW treatment was performed. The surface-treated powder excellent in water and oil repellency referred to in the present invention has a contact angle between water and dodecane of 110 ° or more in the measurement result of the contact angle, and the surface-treated powder excellent in hydrophilic oil repellency is water and However, it is a powder having a contact angle of 110 ° or more.

(Manufacture of surface-treated powder)
(Example 1 and Comparative Example 1)
100 g of sericite FSE (Sanshin Mining Co., Ltd.) was charged into a high-speed mixer, and each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Production Examples 1 to 3 was mixed in a solid content of 3 g, IPA (isopropyl alcohol) and water. (50:50 wt%) 50 g and 0.015 g of tartaric acid as a processing aid were added and kneaded for 30 minutes. The kneaded product was dried at 80 ° C. for 3 hours, and further dried at 110 ° C. for 10 hours. Each FA-treated sericite was obtained by pulverizing the atomizer. As a comparative example, each surface-treated sericite was obtained by a production method in which the processing aid was not blended. The results are shown in Table 1.

  The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 2 and Comparative Example 2)
The sericite used in Example 1 and Comparative Example 1 was replaced by Mica Y-2300 (Yamaguchi Mica Co., Ltd.), and each FA treatment and each surface-treated mica of Comparative Example were produced in the same manner as in Example 1 and Comparative Example 1. Obtained. The results are shown in Table 2.

  The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 3 and Comparative Example 3)
Instead of sericite used in Example 1 and Comparative Example 1 with talc JA-46R (Asada Flour Milling Co., Ltd.), each FA treatment and each surface-treated talc of Comparative Example were produced in the same manner as in Example 1 and Comparative Example 1. Obtained. The results are shown in Table 3.

  The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 4 and Comparative Example 4)
1 g of tetratriethoxysilane (Shin-Etsu Chemical Co., Ltd.) is diluted with 10 ml of IPA to 100 g of titanium CR-EL (Ishihara Sangyo Co., Ltd.), superheated steam at 250 ° C. is introduced and stirred for 10 minutes. Each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Production Examples 1 to 3 was diluted to 2 g in solid content and 0.1 g of aluminum sulfate as a processing aid to 6 g of a mixed solution of IPA and water (50:50 wt%). added. After mixing with a mixer for 20 minutes, 250 ° C. superheated steam was introduced, and when the interior of the mixer reached 200 ° C., stirring was stopped to obtain each FA surface-treated titanium. As a comparative example, each surface-treated titanium was obtained by a manufacturing method in which the processing aid was not blended. The results are shown in Table 4.

  The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Examples 5-7 and Comparative Examples 5-7)
Example 1 and Comparative Example 1 were replaced with yellow LL-100P (titanium industry), red R-516PS (titanium industry), and black BL-100P (titanium industry), respectively. And surface treatment was performed in the same manner as in Comparative Example 1 to obtain each surface treatment powder of each FA treatment and Comparative Example. The results are shown in Table 5.

The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 8 and Comparative Example 8)
100 g of fine particle titanium oxide (MT-100TV: Teica) was charged into 1500 ml of deionized water, and 5 g of each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Table 1 was used as a processing aid and ferrous sulfate 0 Add 0.03 g diluted to 500 ml IPA. The mixture was dispersed by circulation for 15 minutes in a sand grinder (DYNO-Mill: 1.4 L sirconia vessel and blade, 0.5 mmφ zirconia beads filled at 85%). This dispersion was heated to 80 ° C. with stirring. After dehydration by centrifugation, drying was performed at 120 ° C. for 16 hours, and pulverized with a JET atomizer to obtain each FA-treated fine particle titanium oxide. As a comparative example, each surface-treated fine particle titanium oxide was obtained by a production method in which the processing aid was not blended. The results are shown in Table 6.

The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 9 and Comparative Example 9)
100 g of pearl pigment (Flamenco Gold: Engelhart) is added to 1000 ml of deionized water, and 1.5 g of N-stearoyl glutamic acid 2Na (Ajinomoto Co .: Amisoft HS-21P) is added and dissolved and dispersed. Further, 3 g of each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Table 1 and 0.05 g of titanium sulfate as a processing aid were added, heated to 80 ° C., and kneaded in a kneader for 30 minutes. By drying at 170 ° C. for 8 hours, a pearl pigment combined with each FA treatment and acylated amino acid (NAI) was obtained. As comparative examples, each surface-treated pearl pigment was obtained by a production method in which the processing aid was not blended. The results are shown in Table 7.

  The FA / NAI-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 10 and Comparative Example 10)
100 g of red No. 202 (Hana Kasei Co., Ltd.) was put into a mixed solution of IPA / HFE (hydrofluoroether) / deionized water = 40 g / 15 g / 100 g and stirred with a propeller stirrer to an ultrasonic homogenizer (Nippon Siebel Hegner). To disperse. 5 g of each fluoroalkyl acrylate / polyalkylene glycol acrylate polymer shown in Table 1 and 0.1 g of succinic acid as a processing aid were dissolved in 5 g of IPA, dropped and aged, and then the solvent was distilled off by vacuum heating. Each fluorine-containing compound-treated red No. 202 was obtained by drying and grinding for a period of time. As a comparative example, each surface-treated red No. 202 was obtained by a manufacturing method in which the processing aid was not blended. The results are shown in Table 8.

The FA-treated powder obtained by the production method of the present invention was excellent in water and oil repellency, and the amount of ethanol elution was less than that of the conventional surface-treated powder.

(Example 11 (FAW treatment) and Comparative Example 11)
100 g of titanium CR-50 (Ishihara Sangyo Co., Ltd.) 3 g of each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Table 1 and 0.2 g of calcium hydroxide as a processing aid in water / IPA (50:50 wt%) ) Dilute to 10 ml of solution and add. After mixing with a mixer for 30 minutes, it was dried at 105 ° C. for 16 hours and then pulverized with JET atomizer to obtain FAW-treated titanium oxide. As a comparative example, each surface-treated titanium oxide was obtained by a manufacturing method in which the processing aid was not blended. The results are shown in Table 9.

  The FAW-treated powder obtained by the production method of the present invention was excellent in hydrophilic oil repellency, and the amount of water elution was less than that of the conventional surface-treated powder.

(Example 12 (FAW treatment) and Comparative Example 12)
100 g of fine particle zinc oxide (MZ-300: Teika), 6 g of each fluorine alkyl acrylate / polyalkylene glycol acrylate polymer shown in Table 1, 0.3 g of sodium aluminate as a processing aid, and a triethoxy group at one end 3 g of linear dimethylpolysiloxane (SA treatment) having a polymerization degree of 15 was added to 15 g of HFE, 20 g of water and 50 g of IPA, and kneaded in a kneader for 30 minutes. Further, 10 g of deionized water was added, kneaded for 30 minutes, dried at 105 ° C. for 16 hours, and then pulverized with JET atomizer to obtain each composite-treated fine particle zinc oxide. As a comparative example, each surface-treated fine particle zinc oxide was obtained by a manufacturing method in which the processing aid was not blended. The results are shown in Table 10.

  The FAW / SA-treated powder obtained by the production method of the present invention was excellent in hydrophilic oil repellency, and the amount of water elution was less than that of the conventional surface-treated powder.

(Example 13 (FAW treatment) and Comparative Example 13)
100 g of pearl pigment (Flamenco Gold: Engelhardt) is added to 1000 ml of deionized water, 1.0 g of N-stearoyl glutamic acid 2Na (Ajinomoto Co .: Amisoft HS-21P) (NAI treatment) is added and dissolved and dispersed. / 6 g of polyalkylene glycol acrylate polymer in solid content and 0.2 g of water glass as a processing aid were added and heated to 80 ° C., and kneaded for 30 minutes. It dried at 140 degreeC for 8 hours, and obtained each composite processing pearl pigment of each fluorine-containing copolymer and acylated amino acid (NAI). Each surface-treated pearl pigment was obtained by a production method in which the processing aid was not blended. The results are shown in Table 11.

The FAW / NAI-treated powder obtained by the production method of the present invention was excellent in hydrophilic oil repellency and the amount of water elution was less than that of the conventional surface-treated powder.

(Example 14 and Comparative Example 14)
A powder foundation having the following composition was produced by the following method.
(Ingredient) (mass%)
1. FA processing sericite 35.0
2. 2. FA processing talc remaining amount FA-treated titanium oxide 8.5
4). FA-treated yellow iron oxide 3.5
5). FA-treated red iron oxide 1.8
6). FA-treated black iron oxide 0.2
7). Octyldodecyl myristate 4.0
8). Squalane
3.5
9. Methylphenylpolysiloxane 1.5
10. Preservative appropriate amount11. Perfume

(Manufacturing method)
A: Components 1 to 6 are uniformly dispersed with a Henschel mixer (Mitsui Miike).
B: Components 7 to 11 are heated to 70 ° C. and uniformly dispersed.
C: While stirring A with a Henschel mixer, B is added and dispersed uniformly to obtain a cosmetic base material.
D: The cosmetic base material was passed through a pulverizer and sieved to obtain a uniform particle size, and then compression molded on an aluminum dish at a surface press pressure of 10 MPa to obtain a 2WAY powder foundation.

(Evaluation)
The 2WAY powder foundation of the present example was a 2WAY powder foundation that was able to achieve a smooth finish and uniform finish and durability without application unevenness as compared with the comparative example.

(Example 15 and Comparative Example 15)
The following W / O type liquid foundation was manufactured by the following method.
(Ingredient) (mass%)
1. Decamethylcyclopentasiloxane 20.0
2. Vaseline 0.5
3. Methylphenylpolysiloxane 2.3
4). Squalane
4.2
5). Isotridecyl isononanoate 4.5
6). Dimethylpolysiloxane polyoxyalkylene copolymer (HLB = 4.5) 3.0
7). FA-treated red iron oxide 1.3
8). FA-treated yellow iron oxide 2.4
9. FA-treated black iron oxide 0.1
10. FA-treated titanium oxide 8.0
11. FA processing talc 2.5
12 Ethanol 5.0
13.1, 3 Butylene glycol 5.0
14 Sodium chloride 2.0
15. Purified water remaining amount 16. FA processing Amihope LL 5.0
17. Preservative appropriate amount 18. Perfume

(Manufacturing method)
A: Components 1 to 6 are uniformly dissolved, mixed and dispersed at 70 ° C.
B: Components 7 to 11 are mixed uniformly and pulverized.
C: Components 12 to 17 are uniformly dissolved and mixed at 70 ° C.
D: Add B component to A component and disperse uniformly with homomixer.
E: The C component was gradually added to the D component, uniformly dispersed with a homomixer, cooled, and the component 18 was added to prepare emulsion particles to obtain a W / O type liquid foundation.

(Evaluation)
The W / O type liquid foundation of this example was a 2 WAY powder foundation capable of providing a smooth finish spread, uniform finish and durability without application unevenness as compared with the comparative example. Also, in the quality over time stability test by acceleration, the liquid foundations of the examples had superior stability compared to the comparative examples.

(Example 16)
The following solvent slurry-filled eye color was produced by the following method.
(Component) (mass%)
1. FA-treated titanium oxide / silicic acid-coated mica (Note 1) 10.0
2. FA-treated titanium oxide coated glass powder (Note 2) 10.0
3. FA-treated polyethylene terephthalate / polymethyl methacrylate laminated film powder (Note 3) 20.0
4). FA-treated polyethylene terephthalate / polyolefin laminated film powder (Note 4) 10.0
5). FA-treated silicone powder (Note 5) 2.0
6). FA processing talc remaining amount 7. Bengala treated with dimethylpolysiloxane 0.05
8). Dimethylpolysiloxane-treated yellow iron oxide 0.05
9. Black iron oxide treated with dimethylpolysiloxane 0.05
10. Liquid paraffin 5.0
11. Glyceryl tri-2-ethylhexanoate 5.0
12 Polyethylene wax 2.0
13. Vaseline 2.0
14 Methyl paraoxybenzoate 0.2
15. Fragrance 0.01
Note 1: Sirona Indian Summer (Merck)
Note 2: Metashine 1080RC-Y (Nippon Sheet Glass Co., Ltd.)
Note 3: Aurora Flakes Blue (Kakuhachi Fish Scale)
Note 4: DC glitter pearl (Nikko Chemicals)
Note 5: KSP-300 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
A: Components 1 to 9 are uniformly dispersed with a Henschel mixer (Mitsui Miike).
B: Components 10 to 14 are heated to 70 ° C. and uniformly dispersed.
C: While stirring A with a Henschel mixer, B and component 15 are added and dispersed uniformly to obtain a cosmetic base material.
D: To 100 parts of the cosmetic base material, 50 parts of light fluid isoparaffin as a solvent is added and mixed to form a slurry.
E: D was filled in a metal pan, and the solvent was removed using a non-woven fabric as an absorbent while being compressed to obtain an eye color.

(Evaluation)
This eye color was an eye color with which smooth elongation and spread, finished gloss, uniform finish without unevenness of application and sustainability were obtained.

(Example 17)
The following oil-in-water type unevenness correction cosmetic was produced by the following method.
(Component) (mass%)
1.2% alkyl-modified carboxyvinyl polymer aqueous solution 3.0
2. Dipropylene glycol 3.0
3. Cross-linked silicone powder dispersion (Note 1) 30.0
4). Edetate disodium 0.05
5). Purified water remaining amount 6. Ethanol 10.0
7). 2-ethylhexyl paramethoxycinnamate 7.0
8). Dimethicone / Vinyl Dimethicone Cross Polymer (Note 2) 2.0
9. Methylpolysiloxane 4.0
10. Polyoxyalkylene (60) hydrogenated castor oil 1.0
11. Polysorbate-20 0.5
12 Polyglyceryl-10 laurate 1.0
13. 2-Amino-2-methyl-1-propanol 0.15
14 FA-treated methylsiloxane network polymer (Note 3) 8.0
15. FA treated fine particle titanium oxide 0.5
16.2% xanthan gum aqueous solution 15.0
Note 1: BY29-122 (contains about 63% by mass of cross-linked silicone powder, manufactured by Toray Dow Corning Silicone Co., Ltd.)
Note 2: KSG-16 (Shin-Etsu Chemical Co., Ltd.)
Note 3: Tospearl 145 (GE Toshiba Silicone Co., Ltd.)

(Manufacturing method)
A. Components 1 to 6 are mixed and dispersed.
B. A mixture of ingredients 7 to 15 is added to A and dispersed.
C. Component 16 was added to B and dispersed to obtain an oil-in-water type irregularity-corrected cosmetic.

(Evaluation)
This oil-in-water type irregularity correction cosmetic has good storage stability, good spread, and excellent skin irregularity correction effect and its sustainability.

(Example 18)
The following water-in-oil sunscreen was prepared by the following method.
(Component) (mass%)
1. FA-treated fine zinc oxide (Note 1) 15.0
2. Decamethylcyclopentasiloxane 10.0
3. 2-Ethylhexyl paramethoxycinnamate 7.5
4). Polyoxyethylene / methylpolysiloxane copolymer (HLB = 4.5) (Note 2) 4.0
5). Diethylaminohydroxybenzoylhexyl benzoate 0.5
6). Aqueous dispersion composition of methylenebis (benzotriazolyl) tetramethylbutylphenol (Note 3)
5.0
7). Perfume appropriate amount 8. Dipropylene glycol 12.0
9. Sodium chloride 0.5
10. Phenylbenzimidazolesulfonic acid 1.0
11. Paraben 0.3
12 Purified water remaining amount Note 1: 5% treated FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd.)
Note 2: Silicon KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 3: TINOSORB M (Ciba
(Made by Specialty Chemicals)

(Manufacturing method)
A: Components 1 to 5 are uniformly mixed and dispersed at room temperature.
B: Components 6 to 12 are uniformly mixed and dispersed at room temperature.
C: The B component was added to the A component and emulsified to obtain a sunscreen.

(Evaluation) The water-in-oil sunscreen has good storage stability, high transparency, good spread, and excellent ultraviolet shielding effect and durability.

(Example 19)
The following fluorinated oil-containing oily lipstick was produced by the following method.
(Component) (mass%)
1. Polyethylene wax 10.0
2. Candelilla wax 3.0
3. Microcrystalline wax 2.0
4). Isotridecyl isononanoate 20.0
5). Cetyl tri-2-ethylhexanoate 10.0
6). 6. Diisostearyl malate remaining amount Methylphenyl polysiloxane (Note 1) 3.0
8). Perfluoropolyether (Note 2) 5.0
9. Dimerlinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) (Note 3) 15.0
10. FA treatment red No. 202 0.5
11. FA-treated black iron oxide 0.05
12 FA processing sericite 2.0
13. FA-treated mica titanium 2.0
14 FA-treated titanium oxide 1.0
15. Smoke-like silicic acid 2.0
16. Yellow No. 4 aluminum lake 1.2
17. 2-Ethylhexyl paramethoxycinnamate 2.0
18. Tocopherol 2.0
19. Phenoxyethanol 0.2
20. Fragrance 0.01
Note 1: Silicone KF-56A (Shin-Etsu Chemical Co., Ltd.)
Note 2: Fomblin HC / 04 (manufactured by Solvay Solexis)
Note 3: Plandour-S (Nippon Seika Co., Ltd.)

(Manufacturing method)
A: Components 1 to 9 are uniformly dissolved at 110 ° C.
B: Components 10 to 19 are added to A and mixed uniformly, and then component 20 is added and mixed uniformly.
C: B was filled in a lipstick container to obtain a lipstick.

(Evaluation)
This lipstick was a lipstick that had a smooth spread, a glossy finish, a uniform finish with no coating unevenness, and durability.

(Example 20)
The following two-layer foundation was produced by the following method.
(Component) (mass%)
1. FA-treated titanium oxide 5.0
2. FA-treated fine particle zinc oxide 3.0
3. Bengala treated with dimethylpolysiloxane 0.15
4). Dimethylpolysiloxane-treated yellow iron oxide 0.6
5). Black iron oxide treated with dimethylpolysiloxane 0.03
6). Silicone surfactant (Note 1) 0.3
7). Silicone surfactant (Note 2) 0.5
8). Dipropylene glycol 5.0
9. Ethyl alcohol 12.0
10. Purified water remaining amount 11. Sodium chloride 0.3
12 UV absorber (Note 3) 1.0
Note 1: ABIL EM-90 (Gold Schmidt)
Note 2: KF-6111 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 3: UVINUL DS-49 (BASF)

(Manufacturing method)
A: Components 1 to 8 are sufficiently mixed and dispersed.
B: Components 9 to 12 are mixed and dissolved.
C: A was added to B and mixed and dispersed to obtain a two-layered foundation.

(Evaluation)
This double-layered foundation was excellent in redispersibility due to shaking during use, had a good feeling of use without powderiness and squeakiness, and provided a uniform finish and durability with no coating unevenness. .

(Example 21)
The following oily mascara was produced by the following method.
(Component) (mass%)
1. Hydrogenated rosin pentaerythrityl 10.0
2. Beeswax 3.0
3. Carnauba wax 3.0
4). Trimethylsiloxysilicic acid (Note 1) 2.0
5). Decamethylcyclopentasiloxane 2.0
6). Organically modified bentonite 5.0
7). FA processing talc 10.0
8). FA-treated black iron oxide 5.0
9. FA-treated silicone powder (Note 2) 0.5
10. Silicic anhydride 3.0
11. Light liquid isoparaffin remaining amount 12. Methyl paraoxybenzoate 0.1
Note 1: Silicon KF-56A (Shin-Etsu Chemical Co., Ltd.)
Note 2: SR1000 (made by Momentive Performance Materials Japan)

(Manufacturing method)
A: Components 1 to 4 are heated to 110 ° C. and mixed uniformly.
B: The ingredients 5 to 12 are heated and uniformly mixed with A.
C: B was filled into a container to obtain an oily mascara.

(Evaluation)
This mascara was a mascara that spreads smoothly, did not cause lumps, and had a uniform finish and durability without uneven coating.

(Example 22)
The following oil-in-water mascara was produced by the following method.
(Component) (mass%)
1. Beeswax 5.0
2. Carnauba wax 3.0
3. Polyethylene wax 2.0
4). Stearic acid 2.0
5). Cetanol 1.0
6). Sucrose fatty acid ester 2.0
7). Monooleic acid polyoxyethylene sorbitan (20E.O.) 1.5
8). Sorbitan monooleate 0.5
9. Triethanolamine 1.5
10. Alkyl acrylate copolymer emulsion 3.0
11. Polyvinyl acetate emulsion 10.0
12 Polyvinyl alcohol 0.5
13.1,3-Butylene glycol 6.0
14 Purified water remaining amount 15. Methyl paraoxybenzoate 3.0
16. Phenoxyethanol 0.5
17. FAW-treated black iron oxide 5.0
18. FA treatment urethane powder 3.0
19. Hydrophobized fumed silicic acid 2.0

(Manufacturing method)
A: Components 1 to 6 are heated to 90 ° C. and mixed uniformly.
B: Components 7 to 19 are heated to 80 ° C. and mixed uniformly.
C: Add B to A and heat to 80 ° C. to emulsify.
D: C was cooled to room temperature and filled into a container to obtain an oil-in-water mascara.

(Evaluation)
This mascara was a mascara that spreads smoothly, did not cause lumps, and had a uniform finish and durability without uneven coating.

(Example 23)
The following hair mascara (gel color for hair coloring) was produced by the following method.
(Ingredient) (mass%)
1. Polyethylene wax (Note 1) 2.0
2. Volatile hydrocarbon oil (Note 2) 65.0
3. Quotanium-18 hectorite (Note 3) 7.0
4). Propylene carbonate 1.5
5). Dextrin palmitate 8.0
6). Silicic anhydride (Note 4) 0.5
7). Silylated silica (Note 5) 0.5
8). FA processing talc remaining amount 9. FA-treated yellow iron oxide 0.3
10. FA-treated black iron oxide 8.0
11. FA-treated red iron oxide 0.2
12 p-Methoxycinnamic acid-2-ethylhexyl 3.0
13. Mica 0.1
14 Preservative appropriate amount15. Perfume appropriate amount Note 1: PERFORMALENE 500 POLYETHYLENE
(Melting point: 80-95 ° C made by New Phase Technology)
Note 2: IP solvent 1620 (made by Idemitsu Petrochemical Co., Ltd.)
Note 3: Benton 38 (Made by Elementis)
Note 4: AEROSIL R976S (Nippon Aerosil Co., Ltd. average particle size: 10 to 15 nm)
Note 5: AEROSIL 200 (Nippon Aerosil Co., Ltd. average particle size: 5 to 10 nm)

(Manufacturing method)
A: Components 1 and 2 are uniformly dissolved and mixed at 120 ° C.
B: Components 3 to 15 are added to component A and mixed uniformly.
C: B was filled into a tube and cooled to obtain a gel hair coloring agent.

(Evaluation)
The gel-like hair colorant was a good gel-like hair colorant that was excellent in smooth spreading at the time of application, feeling of use (non-stickiness), durability of coloring, and stability over time.

(Example 24)
The following oil-in-water lotion was produced by the following method.
(Component) (mass%)
1. Hydrogenated soybean phospholipid 1.0
2. Polyoxyethylene (30) cholesteryl ether (HLB18) 1.0
3. Cholesterol 0.2
4). Glycerin 20.0
5). Octyl methoxycinnamate 5.0
6). Diethylaminohydroxybenzoyl hexyl benzoate 1.0
7). Stearoyl methyl taurine sodium 0.1
8). Purified water remaining 9. Ascorbic acid glucoside 1.0
10. Tartaric acid 2.0
11. Sodium hydroxide 0.2
12.1,2-Pentanediol 2.0
13. Phenoxyethanol 1.0
14 Propylene glycol 10.0
15. FAW-treated titanium oxide 0.3
16. Glycerin 5.0

(Manufacturing method)
A. Ingredients 1 to 4 are heated and mixed and dissolved uniformly.
B. Ingredients 5-6 are dissolved by heating.
C. Ingredients 7-8 are dissolved by heating.
D. B is added to A and pre-emulsified and mixed uniformly.
E. Add C to D and emulsify and mix. After cooling E, ingredients 9-14 are added and mixed uniformly.
G. Components 15 to 16 were added to F and mixed uniformly to obtain an oil-in-water lotion.

(Evaluation)
The oil-in-water lotion of the present invention was an oil-in-water lotion that has no stickiness and does not feel powdery and has an excellent feeling of use and excellent makeup sustainability.

Claims (7)

A surface-treated powder in which the surface of powder particles to be surface-treated is coated with a specific surface treatment agent,
The surface treatment agent is, (a) the following general formula (I) a fluorine-containing monomer and (b) a monomer which indispensably comprising an alkoxy group-containing monomer represented by the following general formula (II) represented by A surface-treated powder characterized by essentially containing a fluorine alkyl acrylate / polyalkylene glycol acrylate polymer obtained by copolymerizing a body and (c) a processing aid shown below.

[Wherein, X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX1X2 group (wherein X1 and X2 are a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group. A linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, —S— or —SO ₂ —;
Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]

[Wherein X3 is a hydrogen atom or a methyl group;
X4 represents a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms.
R is an alkylene group having 2 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a hydroxyl group;
q is an integer of 1-50. ]
(C) The processing aid is a polyvalent acidic substance or a polyvalent basic substance.   The polybasic substance of the processing aid contains a polyvalent metal selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, molybdenum, titanium, and silicon. A compound comprising at least one selected from the group, wherein the polyvalent acidic substance is a free form of sulfonic acid, phosphoric acid, aluminate, silicic acid, dicarboxylic acid, tricarboxylic acid or a polyvalent metal salt thereof The surface-treated powder according to claim 1, wherein the surface-treated powder is a compound comprising at least one selected from the group consisting of:   The ratio of the processing agent and the processing aid of the fluoroalkyl acrylate / polyalkylene glycol acrylate polymer is 0.5 to 0.001 when the processing agent is 1.0 (part by weight). The surface-treated powder according to claim 1 or 2, wherein the total amount of the treatment agent and the treatment aid is 0.01 to 40 parts by weight with respect to 100 parts by weight of the surface-treated powder.   The surface treatment agent is further a fluorine-containing compound other than the fluorine-containing copolymer, a reactive organopolysiloxane, an alkylsilane, a polyether-modified silane, an organic titanate, a polyolefin, a hydrogenated lecithin (in the form of a salt) ), Acylated amino acids (including those in the form of salts or compositions), acidic ester oils, fatty acids (including those in the form of salts), dextrin fatty acid esters, and fructooligosaccharide fatty acid esters. surface treated powder according to any one of claims 1 to 3 comprising one or more compounds selected from the group consisting of.   A cosmetic comprising the surface-treated powder according to any one of claims 1 to 4.   The cosmetic according to claim 5, wherein the cosmetic is a skin care cosmetic, a hair cosmetic, a makeup cosmetic, an ultraviolet protective cosmetic, a foot cosmetic, a neck cosmetic, or a body cosmetic.   The form of the product is liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray, according to any one of claims 5 and 6. Cosmetics.