JP2007210939A - Powder for cosmetic and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powder for cosmetic excellent in water and oil repellency and stability, and to provide a cosmetic excellent in makeup sustainability, feeling in use and stability. <P>SOLUTION: The invention relates to the powder for cosmetic and cosmetic comprising powder particles having fluorine containing copolymer (A) adhered on the surface, wherein the copolymer (A) comprises a monomer (unit for polymer), represented by (Z-Y)<SB>n</SB>X, [Z is a 1-6C R<SP>F</SP>group, etc., Y is an alkylene group, etc., n is 1 or 2, X is an unsaturated polymerizable group], a monomer represented by CH<SB>2</SB>=CR<SP>1</SP>-G-(R<SP>2</SP>O)<SB>q</SB>-R<SP>3</SP>, [R<SP>1</SP>is a hydrogen atom or a methyl group, R<SP>2</SP>is a 2-4C alkylene group, etc., q is 1-50, G is a -COO(CH<SB>2</SB>)<SB>r</SB>-, etc., r is 0-4, R<SP>3</SP>is a hydrogen atom, etc.], and a monomer represented by CH<SB>2</SB>=CR<SP>4</SP>-U [R<SP>4</SP>is a hydrogen atom or a methyl group, U is an organic group containing a functional group ionizing in water]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cosmetic powder and a cosmetic containing the powder.

Cosmetics may cause dirt, flow, makeup collapse, etc. due to sweat, sebum, oils of other cosmetics, etc., especially under high temperature and high humidity conditions in summer. As a result, the makeup becomes worse. Therefore, the cosmetic powder contained in the cosmetic material is required to have water and oil repellency for imparting water resistance, sebum resistance and oil resistance to the cosmetic material.
The following are known as conventional cosmetic powders.

(1) Cosmetic powder in which the surface of animals or plants or mineral powder is coated with a silicone resin, dried and baked to give lubricity to the powder surface (Patent Document 1).
(2) Cosmetic powder that imparts water repellency to the powder by simply attaching a silicone having hydrogen directly bonded to silicon in the molecular chain to the surface of a mineral powder such as talc by baking, etc. (Patent Document 2).
(3) Free contact with talc by baking with zinc octoate, which is a cross-linking catalyst for methylhydrogen polysiloxane, if necessary, after contacting and adhering an organic solvent solution of dimethylpolysiloxane or methylhydrogen polysiloxane to talc. Cosmetic powder with fluidity (Patent Document 3).

(4) Cosmetic powder in which titanium dioxide is coated with alkylpolysiloxane, and an ester compound having a total carbon number of 6 or more is used in combination, and is dried and baked to improve the dustiness and dispersibility of titanium dioxide. Body (Patent Document 4).
(5) Cosmetic powder obtained by mechanochemical cross-linking polymerization of methylhydrogen polysiloxane on the powder surface (Patent Document 5).
(6) The surface of the powder is R ^F (CH ₂ ) _n SiL ₃ [R ^F is a perfluoroalkyl group. L is a hydrolyzable group. A cosmetic powder treated with a fluoroalkylsilane represented by the formula (Patent Document 6).

(7) A cosmetic powder whose surface is treated with an R ^F group-containing phosphate ester (Patent Document 7).
(8) A cosmetic powder whose surface is treated with an R ^F group-containing carbonate (Patent Document 8).
(9) cosmetic powders the powder surface was surface-treated with R ^F group-containing polymer (Patent Documents 9 and 10).

However, the cosmetic powders (1) to (6) are all insufficient in water and oil repellency.
In the cosmetic powders (7) and (8), a low molecular weight component containing an R ^F group may be generated due to hydrolysis of the treatment agent, and there is a problem in stability.

The cosmetic powder (9) has the following problems.
-When the polymer which is a processing agent is a homopolymer of an R ^F group-containing monomer, the compatibility with the silicone oil contained in the cosmetic is poor.
If and processing agent in a polymer is a copolymer of a R ^F group-containing monomer, an alkyl acrylate or silicone-containing monomer, the oil repellency is lowered.
Japanese Patent Publication No.41-9890 Japanese Patent Publication No. 45-2915 Japanese Patent Publication No. 45-18999 Japanese Patent Publication No.49-1769 Japanese Examined Patent Publication No. 56-43264 JP-A-2-218603 JP-A-62-250074 JP 2001-122893 A JP 55-167209 A JP-A-9-12428

  Accordingly, an object of the present invention is to provide a cosmetic powder excellent in water and oil repellency and stability, and a cosmetic having a good feeling when used and excellent in stability.

  The cosmetic powder of the present invention has, on the powder surface, 60 to 98% by mass of polymerized units based on the following monomer (a), 1 to 20% by mass of polymerized units based on the following monomer (b), and It is a cosmetic powder to which a fluorine-containing copolymer (A) containing 1 to 30% by mass of polymerized units based on the following monomer (c) is attached.

Monomer (a):
(ZY) _n A compound represented by X.
However, the symbols in the formulas have the following meanings.
Z: an R ^F group having 1 to 6 carbon atoms or C _m F _{2m + 1} O (CFWCF ₂ O) _d CFK— [m is an integer of 1 to 6. d is an integer of 1 to 4. W and K are each independently a fluorine atom or —CF ₃ . ] The group represented by this.
Y: Divalent organic group or single bond.
n: 1 or 2.
X: a polymerizable unsaturated group, -CR = CH ₂ when n is _{1, -COOCR = CH 2, -OCOCR} = CH 2, -OCH 2 -φ-CR = CH 2 or -OCH = CH _2, and when n is _{2 = CH (CH 2) p} CR = CH 2, = CH (CH 2) p COOCR = CH 2, = CH (CH 2) p OCOCR = CH 2 or -OCOCH = CHCOO -[R is a hydrogen atom, a methyl group or a halogen atom. φ is a phenylene group. p is an integer of 0-4. ].

Monomer (b):
^{_{CH 2 = CR 1 -G- (R}} 2 O) compound represented by _q -R ^3.
However, the symbols in the formulas have the following meanings.
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which part or all of the hydrogen atoms are substituted with hydroxyl groups.
q: An integer from 1 to 50.
_{G: -COO (CH 2) r} - or -COO (CH _{2) t} -NHCOO- [r is 0-4 integer. t is an integer of 1 to 4. ].
R ³ : hydrogen atom, methyl group, acryloyl group, methacryloyl group or allyl group.

Monomer (c):
A compound represented by CH ₂ = CR ⁴ -U.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
U: An organic group containing a functional group that can be ionized in water.

  The monomer (c) is preferably the following monomer (c1) or the following monomer (c2).

Monomer (c1):
^{_{CH 2 = CR 4 -M-Q}} 1 -NR 5 R 6 or ^{_{CH 2 = CR 4 -M-Q}} 1 -N (O) a compound represented by R ⁵ R ^6.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
M: —COO— or —CONH—.
Q ¹ : an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with hydroxyl groups.
R ⁵ and R ⁶ : each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 3 carbon atoms in which a part of hydrogen atoms is substituted with a hydroxyl group. Alternatively, R ⁵ , R ⁶ and the nitrogen atom may form a morpholino group, piperidino group or pyrrolidinyl group.

Monomer (c2):
CH ₂ = CR ⁴ compound represented by -M-Q ² -V.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
M: —COO— or —CONH—.
Q ² : contains a single bond, an alkylene group having 2 to 4 carbon atoms, an alkylene group having 2 to 3 carbon atoms in which part or all of the hydrogen atoms are substituted with a hydroxyl group or a halogen atom, or an etheric oxygen atom An alkylene group having 4 to 18 carbon atoms;
V: —COOH, —SO ₃ H or —P (O) (OH) ₃

  The fluorine-containing copolymer (A) further includes polymer units based on the following monomer (d), and is 60 to 97.9% by mass of the polymer units based on the monomer (a), the monomer (b). Fluorine-containing containing 1 to 20% by mass of polymerized units based on 1 to 20% by mass of polymerized units based on monomer (c) and 0.1 to 10% by mass of polymerized units based on monomer (d) A copolymer is preferred.

Monomer (d):
Monomers excluding monomer (b), monomer (c1) and monomer (c2), which are isocyanate groups, blocked isocyanate groups, urethane bonds, alkoxysilyl groups, epoxy groups, N- A (meth) acrylate having one or more functional groups selected from the group consisting of a methylol group and an N-alkoxymethyl group and having no polyfluoroalkyl group (hereinafter referred to as R ^f group).

  The fluorine-containing copolymer (A) is preferably a fluorine-containing copolymer obtained using the following polymerization initiator (e).

Polymerization initiator (e):
An azo compound or an azoamidine compound, which has an acute oral toxicity in a rat or a mouse of 1000 mg / kg or more and a 10-hour half-life temperature of 30 ° C. or more.

  The cosmetic of the present invention is characterized by including the cosmetic powder of the present invention.

The cosmetic powder of the present invention is excellent in water and oil repellency and stability.
The cosmetic composition of the present invention has a good makeup and feel when used, and is excellent in stability.

<Cosmetic powder>
The cosmetic powder of the present invention is a cosmetic powder in which the fluorine-containing copolymer (A) is attached to the powder surface. The fluorine-containing copolymer (A) may be attached to a part of the powder surface, or may be attached so as to cover the entire surface of the powder.

(powder)
As the powder, inorganic powder, organic powder, or composite powder of inorganic powder and organic powder is preferable.

  Inorganic powders include silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, fine particle titanium oxide, oxidation Examples thereof include aluminum, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, bitumen, chromium oxide, chromium hydroxide, calamine, carbon black, and composites thereof.

  Organic powders such as polyamide such as nylon, polyester, polyethylene, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene・ Styrene copolymers, other copolymers, celluloid, acetylcellulose, cellulose, chitin, chitosan, polysaccharides, protein, CI pigment yellow, CI pigment orange, CI pigment red, CI pigment violet, CI pigment blue, CI pigment Green, CI pigment brown, and sugar.

One type of powder may be used alone, or two or more types may be used in combination.
Examples of the shape of the powder include a plate shape, a lump shape, a scale shape, and a porous spherical shape. The powder may have pores on the surface.

(Fluorine-containing copolymer (A))
The fluorine-containing copolymer (A) is based on 60 to 98% by mass of polymerized units based on the monomer (a) in the fluorine-containing copolymer (A) (100% by mass), based on the monomer (b). A polymer containing 1 to 20% by mass of polymerized units and 1 to 30% by mass of polymerized units based on monomer (c); 70 to 90% by mass of polymerized units based on monomer (a) A polymer containing 4 to 20% by mass of polymerized units based on the monomer (b) and 6 to 25% by mass of polymerized units based on the monomer (c) is preferred. The fluorine-containing copolymer (A) has excellent adsorptivity to the powder surface and excellent water and oil repellency.

The fluorinated copolymer (A) is preferably a fluorinated copolymer (A1) further comprising polymerized units based on the monomer (d). The fluorine-containing copolymer (A1) is further excellent in water and oil repellency.
The fluorine-containing copolymer (A1) is 60 to 97.9% by weight of the polymer units based on the monomer (a) in the fluorine-containing copolymer (A1) (100% by weight), and the monomer (b). A polymer comprising 1 to 20% by weight of polymerized units based on 1%, 1 to 20% by weight of polymerized units based on monomer (c) and 0.1 to 10% by weight of polymerized units based on monomer (d) 70 to 89.8% by mass of polymerized units based on monomer (a), 4 to 20% by mass of polymerized units based on monomer (b), polymerized units based on monomer (c) A polymer containing 6 to 25% by mass and 0.2 to 10% by mass of polymerized units based on the monomer (d) is preferred.

Monomer (a):
The monomer (a) is a compound represented by (ZY) _n X.
Z is an R ^F group having 1 to 6 carbon atoms or C _m F _{2m + 1} O (CFWCF ₂ O) _d CFK— [m is an integer of 1 to 6. d is an integer of 1 to 4. W and K are each independently a fluorine atom or —CF ₃ . ] Is a group represented by
Z is preferably an R ^F group having 1 to 6 carbon atoms, and F (CF ₂ ) ₂ —, F (CF ₂ ) ₃ —, F (CF ₂ ) ₄ —, F (CF ₂ ) ₅ —, F (CF ₂ ) ₆ —, (CF ₃ ) ₂ CF (CF ₂ ) ₂ — are more preferable, and F (CF ₂ ) ₄ —, F (CF ₂ ) ₅ —, and F (CF ₂ ) ₆ — are particularly preferable.

Y is a divalent organic group or a single bond. “Organic group” means a group containing carbon atoms.
Y is preferably a divalent organic group, and -R ^M -T-R ^N- [R ^M and R ^N may each independently contain a single bond or one or more etheric oxygen atoms. A saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms; T is a single bond, -OCONH -, - CONH -, - SO 2 NH -, - SO 2 NR '- (. R' is an alkyl group having 1 to 6 carbon atoms) or -NHCONH-. The divalent group represented by these is more preferable. “Hydrocarbon group” means a group consisting of only a carbon atom and a hydrogen atom unless otherwise described, such as “including an etheric oxygen atom”. The hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably an alkyl group.

-R ^M -T-R ^N -, as the divalent group represented by an alkylene group having 1 to 10 carbon _{atoms, -CH = CHCH 2 -, -} (CH 2 CHR''O) j CH 2 CH _2- [j is an integer of 1-10. R ″ is a hydrogen atom or a methyl group. _{], -C 2 H 4 OCONHC 2 H} 4 -, - C 2 H 4 OCOOC 2 H 4 - or -COOC ₂ H ₄ -, more preferably an alkylene group having 1 to 10 carbon atoms, -CH ₂ - _{, -CH 2 CH 2 -, -} (CH 2) 11 - or _{-CH 2 CH 2 CH (CH 3} ) - is particularly preferred.

n is 1 or 2.
X is a polymerizable unsaturated group, and when n is 1, -CR = CH ₂ , -COOCR = CH ₂ , -OCOCR = CH ₂ , -OCH ₂ -φ-CR = CH ₂ or -OCH = It is CH _2, and when n is _{2 = CH (CH 2) p} CR = CH 2, = CH (CH 2) p COOCR = CH 2, = CH (CH 2) p OCOCR = CH 2 or -OCOCH = CHCOO- [R is a hydrogen atom, a methyl group or a halogen atom. φ is a phenylene group. p is an integer of 0-4. ].
X is preferably —OCOCR═CH ₂ or —OCOCH═CHCOO—, more preferably —OCOCR═CH ₂ , since it has excellent solubility in a solvent and can be easily subjected to emulsion polymerization.
R is preferably a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.) or an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group because of excellent polymerizability.

As the monomer (a), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 3,3,4,4,5 5,6,6,6-nonafluorohexyl methacrylate is preferred.
A monomer (a) may be used individually by 1 type, and may use 2 or more types together.

Monomer (b):
Monomer (b) is a compound represented by ^{_{CH 2 = CR 1 -G- (R}} 2 O) q -R 3.
R ¹ is a hydrogen atom or a methyl group.
R ² is an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with hydroxyl groups. R ² is preferably an alkylene group having 2 to 4 carbon atoms.

q is an integer of 1 to 50, preferably 1 to 30, and more preferably 1 to 15. When q is 2 or more, — (R ² O) _q — may be composed of one alkylene group or may be composed of a plurality of alkylene groups having different numbers of carbon atoms. When — (R ² O) _q — is composed of a plurality of alkylene groups having different numbers of carbon atoms, — (R ² O) _q — may be block-shaped or random.
G is —COO (CH ₂ ) _r — or —COO (CH ₂ ) _t —NHCOO— [r is an integer of 0 to 4; t is an integer of 1 to 4. ]. G is —COO (CH ₂ ) _r — [r is an integer of 0-4. ] Is preferable.

R ³ is a hydrogen atom, a methyl group, an acryloyl group, a methacryloyl group or an allyl group. R ³ is preferably a (meth) acryloyl group. When R ³ is a (meth) acryloyl group, the fluorinated copolymer (A) tends to have a three-dimensional network structure, and the fluorinated copolymer (A) is firmly adhered to the powder and has excellent durability. .
As the monomer (b), a combination of a compound in which R ³ is a (meth) acryloyl group and a compound in which R ³ is a hydrogen atom is more preferable.

  As the monomer (b), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyoxyethylene glycol mono (Meth) acrylate, polyoxypropylene glycol mono (meth) acrylate, methoxypolyoxyethylene glycol (meth) acrylate, trioxyethylene glycol di (meth) acrylate, tetraoxyethylene glycol di (meth) acrylate, polyoxyethylene glycol di (Meth) acrylate, acryloyloxypolyoxyethylene glycol methacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, poly (oxypro Len - oxybutylene) glycol di (meth) acrylate, poly (oxyethylene - oxypropylene) glycol di (meth) acrylate, poly (oxyethylene - oxybutylene) glycol di (meth) acrylate are preferable,

Polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trioxyethylene glycol Di (meth) acrylate, tetraoxyethylene glycol di (meth) acrylate, polyoxyethylene glycol di (meth) acrylate, poly (oxyethylene-oxypropylene) glycol di (meth) acrylate are more preferable,
Polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trioxyethylene glycol di (meth) acrylate, tetraoxyethylene glycol di (meth) acrylate, poly ( Oxyethylene-oxypropylene) glycol di (meth) acrylate and polyoxyethylene glycol di (meth) acrylate are particularly preferred.
A monomer (b) may be used individually by 1 type, and may use 2 or more types together.

Monomer (c):
Monomer (c) is a compound represented by CH ₂ = CR ⁴ -U.
R ⁴ is a hydrogen atom or a methyl group.
U is an organic group containing a functional group that can be ionized in water. The “functional group that can be ionized in water” means a functional group that ionizes in water and generates a charge in an alkaline region having a pH of 7 or higher or an acidic region having a pH of 7 or lower. Examples of the functional group include a carboxyl group, a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a sulfuric acid group, and an amino group.
As the monomer (c), the monomer (c1) or the monomer (c2) is preferable.

Monomer (c1):
Monomer (c1) is a compound represented by ^{_{CH 2 = CR 4 -M-Q}} 1 -NR 5 R 6 or ^{_{CH 2 = CR 4 -M-Q}} 1 -N (O) R 5 R 6 .
R ⁴ is a hydrogen atom or a methyl group.
M is -COO- (ester bond) or -CONH- (amide bond). As M, -COO- is preferable.

Q ¹ is an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with hydroxyl groups. Q ¹ is preferably an alkylene group having 2 to 4 carbon atoms.
R ⁵ and R ⁶ are each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 3 carbon atoms in which a part of hydrogen atoms are substituted with a hydroxyl group; or R ⁵ , R ⁶ and the nitrogen atom may form a morpholino group, piperidino group or pyrrolidinyl group. R ⁵ and R ⁶ are preferably an alkyl group having 1 to 8 carbon atoms.

As the monomer (c1), N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (Meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpiperidine, N, N-dimethylamino Oxidoethyl (meth) acrylate is preferred, and N, N-dimethylaminoethyl methacrylate or N, N-diethylaminoethyl methacrylate is more preferred.
A monomer (c1) may be used individually by 1 type, and may use 2 or more types together.

Monomer (c2):
Monomer (c2) is a compound represented by ^{_{CH 2 = CR 4 -M-Q}} 2 -V.
R ⁴ is a hydrogen atom or a methyl group.
M is —COO— or —CONH—.
Q ² represents a single bond, an alkylene group having 2 to 4 carbon atoms, an alkylene group having 2 to 3 carbon atoms in which part or all of the hydrogen atoms are substituted with a hydroxyl group or a halogen atom, or an etheric oxygen atom. An alkylene group having 4 to 18 carbon atoms.
V is —COOH, —SO ₃ H or —P (O) (OH) ₃ .
As the monomer (c2), acrylic acid, methacrylic acid, phosphoric acid ester monomers shown in the following formulas (1) to (3), sulfonic acid monomers shown in the following formulas (4) and (5) The body is preferred. However, s is an integer of 4-5.
A monomer (c2) may be used individually by 1 type, and may use 2 or more types together.

Monomer (d):
The monomer (d) is a monomer excluding the monomer (b), the monomer (c1) and the monomer (c2), and is an isocyanate group, a blocked isocyanate group, a urethane bond, an alkoxy It is a (meth) acrylate having one or more functional groups selected from the group consisting of a silyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group, and having no R ^f group.
As the monomer (d), the following compounds are preferable.

Compound having an isocyanate group:
2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate.

Compounds with blocked isocyanate groups:
2-isocyanatoethyl (meth) acrylate 2-butanone oxime adduct, 2-isocyanatoethyl (meth) acrylate pyrazole adduct, 2-isocyanatoethyl (meth) acrylate 3,5-dimethylpyrazole adduct, 2-isocyanate 3-methylpyrazole adduct of ethyl (meth) acrylate, ε-caprolactam adduct of 2-isocyanatoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatepropyl (meth) acrylate, 3-isocyanatepropyl (meta ) Pyrazole adduct of acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatepropyl (meth) acrylate, 3 Ε-Caprolactam adduct of isocyanate propyl (meth) acrylate, 2-butanone oxime adduct of 4-isocyanatobutyl (meth) acrylate, pyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate 3,5-dimethylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3-methylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate ε-caprolactam adduct.

Compound having urethane bond:
Triallyl isocyanurate, tolylene diisocyanate adduct of 3-phenoxy-2-hydroxypropyl acrylate, hexamethylene diisocyanate adduct of 3-phenoxy-2-hydroxypropyl acrylate, hexamethylene diisocyanate adduct of pentaerythritol triacrylate.

Compound having alkoxysilyl group:
^{_{CH 2 = CR 10 -D-E}} -SiR a R b R c [D is -OCO -, - COO- or a single bond. E is an alkylene group having 1 to 4 carbon atoms. R ^a , R ^b and R ^c are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R ¹⁰ is a hydrogen atom or a methyl group. It is a compound represented by this. Specific examples include 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldiethoxyethylsilane, vinyltrimethoxysilane, and the like. .

Compound having epoxy group:
Glycidyl (meth) acrylate, polyoxyalkylene glycol monoglycidyl ether (meth) acrylate.

Compound having N-methylol group or N-alkoxymethyl group:
N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide.

As the monomer (d), 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyl Triethoxysilane and 3-methacryloyloxypropyldiethoxyethylsilane are preferred.
A monomer (d) may be used individually by 1 type, and may use 2 or more types together.

Other monomers:
The fluorine-containing copolymer (A) is further added to the monomers (a) to (a) in order to improve adhesion to the powder of the fluorine-containing copolymer (A), adhesiveness, durability against friction, and the like. Polymerized units based on monomers other than d) (hereinafter referred to as other monomers) may be included. The proportion of polymer units based on other monomers is preferably 30% by mass or less, more preferably 15% by mass or less, in the fluorinated copolymer (A) (100% by mass).

Other monomers include ethylene, vinylidene chloride, vinyl chloride, vinylidene fluoride, vinyl acetate, vinyl propionate, vinyl isobutanoate, vinyl isodecanoate, vinyl stearate, cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether. , 2-chloroethyl vinyl ether, styrene, α-methylstyrene, p-methylstyrene, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, vinylalkyl Ketone, butadiene, isoprene, chloroprene, benzyl (meth) acrylate, (meth) acrylate with polysiloxane, allyl acetate, N-vinylcarbazole, maleimi , N- methylmaleimide, and the like.
As other monomers, vinyl chloride, vinyl acetate, vinyl propionate, and vinylidene chloride are preferable because of excellent film forming properties and water resistance.

The fluorine-containing copolymer (A) can be obtained by performing a polymerization reaction of each of the above monomers in a solvent or water using a known method.
Solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols (isopropyl alcohol, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (diisopropyl ether, etc.), aliphatic hydrocarbons or aromatics. Group hydrocarbon, halogenated hydrocarbon (perchloroethylene, trichloro-1,1,1-ethane, trichlorotrifluoroethane, dichloropentafluoropropane, etc.), N, N-dimethylformamide, N-methyl-pyrrolidone-2 , Butyroacetone, dimethyl sulfoxide, glycol ether and derivatives thereof.

As a solvent, since it is excellent in workability in the subsequent steps, a solvent having a relatively low boiling point or a solvent that forms an azeotrope with water is preferable. Acetone, 2-propyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether Dipropylene glycol monomethyl ether or a mixed solvent thereof is preferable.
5-60 mass% is preferable in the sum total (100 mass%) of a solvent and a monomer, and, as for the density | concentration of a monomer, 10-40 mass% is more preferable.

In the polymerization reaction, it is preferable to use a polymerization initiator. As the polymerization initiator, peroxides such as benzyl peroxide, lauryl peroxide, succinyl peroxide, tert-butyl perpivalate, azo compounds and the like are preferable.
As for the usage-amount of a polymerization initiator, 0.1-1.5 mass parts is preferable with respect to the total amount (100 mass parts) of a monomer.

As the polymerization initiator, the polymerization initiator (e) is preferable because of excellent polymerizability and excellent safety.
The polymerization initiator (e) is an azo compound or an azoamidine compound, and the acute oral toxicity (hereinafter referred to as LD50) of the compound or a degradation product thereof in rats or mice is 1000 mg / kg or more, and 10 hours A compound having a half-life temperature of 30 ° C. or higher.

  As the polymerization initiator (e), 2,2′-azobis-2-methylbutyronitrile (LD50: 1316 mg / kg, 10 hour half-life temperature: 67 ° C.), dimethyl-2,2′-azobisisobutyrate Rate (LD50: 2369 mg / kg, 10-hour half-life temperature: 65 ° C.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (LD50: 2000 mg / kg or more, 10-hour half-life Temperature: 61 ° C.), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (LD50: 2900 mg / kg, 10 hour half-life temperature: 30 ° C.), 1,1′-azobis (2 -Cyclohexane-1-carbonitrile) (LD50: 11800 mg / kg or more, 10 hour half-life temperature: 88 ° C.), 2,2′-azobis (2,4-dimethylvaleroni) Lil) (LD50: 6000 mg / kg, 10-hour half-life temperature: 51 ° C.), 1,1′-azobis (1-acetoxy-1-phenylethane) (LD50: 5000 mg / kg or more, 10-hour half-life temperature: 61 ° C), dimethylazobisisobutyrate (LD50: 2000 mg / kg or more, 10 hour half-life temperature: 68 ° C), and the like. Dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] is more preferable.

In the polymerization reaction, it is preferable to use a chain transfer agent in order to adjust the degree of polymerization (molecular weight) of the fluorinated copolymer (A).
Examples of the chain transfer agent include alkyl mercaptans such as tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, aminoethanethiol, mercaptoethanol, 2,4-diphenyl-4-methyl-1-pentene, carbon tetrachloride and the like. It is done.
As for the usage-amount of a chain transfer agent, 0.05-1 mass part is preferable with respect to the total amount (100 mass parts) of a monomer.

The reaction temperature in the polymerization reaction is preferably in the range from room temperature to the boiling point of the reaction mixture. From the viewpoint of efficiently using the polymerization initiator, it is preferably at least the half-life temperature of the polymerization initiator, more preferably from 30 to 90 ° C.
The molecular weight of the fluorinated copolymer (A) is preferably 1000 or more in terms of number average molecular weight.

When the fluorine-containing copolymer (A) contains an amino group, it is preferable to amine-treat the amino group in order to improve storage stability. Examples of the amine chloride include (i) amine chloride using an acid and (ii) quaternary chloride. (I) is preferred, and amine chloride using an acid having a dissociation constant or primary dissociation constant of 10 ⁻⁵ or more is more preferable. preferable. As the acid, hydrochloric acid, hydrobromic acid, sulfonic acid, nitric acid, phosphoric acid, acetic acid, formic acid, propionic acid, lactic acid and the like are preferable, and acetic acid is more preferable. In (ii), methyl iodide, ethyl iodide, dimethyl sulfuric acid, diethyl sulfuric acid, benzyl chloride, trityl phosphoric acid, methyl p-toluenesulfonic acid and the like are used in place of the acid.

In the case where the fluorine-containing copolymer (A) contains a carboxyl group, a phosphoric acid group, or a sulfuric acid group, it is preferably salified with an organic amine in order to improve storage stability. As the organic amine, alkanolamines such as alkylamine, dialkylamine, trialkylamine, diethanolamine, and triethanolamine are preferable.
When the polymerization reaction is performed using a solvent, the solvent may be distilled off after the polymerization reaction. For example, after performing the above-mentioned chlorination, water is added and the solvent is distilled off under reduced pressure.

  0.1-50 mass parts is preferable with respect to 100 mass parts of powders, and, as for the adhesion amount of a fluorine-containing copolymer (A), 3-20 mass parts is more preferable. By making the amount of adhesion 0.1 mass part or more, the water and oil repellency is excellent. When the adhesion amount is 50 parts by mass or less, the feeling of use as a cosmetic is good. The adhesion amount of the fluorinated copolymer (A) can be appropriately changed according to the specific surface area of the powder.

(Manufacture of cosmetic powder)
The cosmetic powder can be obtained by treating the powder surface with the fluorine-containing copolymer (A).
Examples of the treatment method include known methods (for example, a method of treating powder with silicone, metal soap or the like to make the powder surface hydrophobic).

Specifically, while stirring the powder in the mixing and stirring device, the fluorine-containing copolymer (A) or a treatment liquid in which the fluorine-containing copolymer (A) is dispersed or diluted with a solvent is sprayed or dropped. And a method in which the mixture is uniformly dispersed and then subjected to room temperature or heat drying.
Examples of the mixing and stirring device include a Henschel mixer, a vibration ball mill, a rotary ball mill, a super mixer, and a V-blender.

Examples of the solvent include methanol, ethanol, isopropanol, chloroform, dichloromethane, volatile silicone, water and the like.
When the treatment liquid is obtained by dispersing the fluorinated copolymer (A) in an aqueous medium, the average particle size of the fluorinated copolymer (A) is preferably 30 nm or less, more preferably 20 nm or less, and most preferably 10 nm or less. preferable. By setting the average particle size to 10 nm or less, the powder surface can be coated more efficiently, so that the performance such as water and oil repellency is excellent and the durability is also excellent.

The aqueous medium preferably contains the solvent used in the polymerization reaction, and water or a mixture of water and propylene glycol monomethyl ether or dipropylene glycol monomethyl ether is more preferable from the viewpoint of handling and safety and health.
The surface treatment may be performed on the powder alone or on a mixture with other components described below.

<Cosmetics>
The cosmetic powder of the present invention may be used as it is as a cosmetic or may contain other components.
The following are mentioned as another component.

Solid or semi-solid oils such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids and higher alcohols.
Fluid oils such as squalane, liquid paraffin, ester oil, diglyceride, triglyceride and silicone oil.
Fluorinated oils such as perfluoropolyether, perfluorodecalin, and perfluorooctane.
Water-soluble or oil-soluble polymer, surfactant.
Coloring agents such as inorganic or organic pigments, tar pigments and natural pigments.
Ethanol, preservatives, antioxidants, pigments, thickeners, pH regulators, fragrances, UV absorbers, moisturizers, blood circulation promoters, cold agents, antiperspirants, bactericides, skin activators, water, etc.
Other components can be blended in a qualitative and quantitative range that does not impair the effects of the present invention.

The cosmetics of the present invention include powder foundations, creamy foundations, oily foundations, amphoteric foundations, makeup white cosmetics such as powdered white powder, blusher, eye shadow, eyebrow, and body cosmetics such as body powders and baby powders. Etc.
The amount of the cosmetic powder in the cosmetic is preferably 1 to 100% by mass, more preferably 1 to 99% by mass, and particularly preferably 5 to 95% by mass in 100% by mass of the cosmetic.

  The cosmetic powder of the present invention described above is excellent in water and oil repellency and stability because the fluorine-containing copolymer (A) adheres to the powder surface. That is, the fluorine-containing copolymer (A) is a polymer that is not easily affected by hydrolysis and the like, and has a polar group in the molecule, and this exhibits an interaction with the powder. The water / oil repellency of the fluorinated copolymer (A) can be continuously imparted over a long period of time.

  And since the cosmetic of the present invention includes cosmetic powders that are excellent in water and oil repellency, it is excellent in water resistance, sebum resistance, and oil resistance, and does not cause dirt, flow, makeup collapse, etc. Good makeup. Moreover, since the cosmetic powder which is excellent in stability is included, the sustainability of the effect is excellent. Moreover, since it is excellent also in the elongation on the skin, smoothness, adhesiveness, etc., the touch in use is also favorable.

The present invention will be described in detail by Examples (Examples 1 and 2) and Comparative Examples (Examples 3 to 5).
Evaluation in each example was performed as follows.
(Water repellency)
A teaspoon of powder was gently dropped into a 20 mL vial containing 10 mL of water. The state of the powder was observed, and it was evaluated as ○ if it did not settle after 5 minutes, △ when it was floating immediately after dropping, but △ when it settled after 5 minutes, and × when it settled immediately after dropping. .

(Oil repellency)
A teaspoon of powder was gently dropped into a 20 mL vial containing 10 mL of hexadecane. The state of the powder was observed, and it was evaluated as ○ if it did not settle after 5 minutes, △ when it was floating immediately after dropping, but △ when it settled after 5 minutes, and × when it settled immediately after dropping. .

(Stability)
Powder was added to a weak alkaline ethanol aqueous solution of pH 8 prepared by adding sodium carbonate to a mixture of ion-exchanged water / ethanol = 40/60 (volume%), and the mixture was shaken at room temperature for 15 minutes. Leave for hours. After collecting the powder by suction filtration and vacuum-drying the powder, the above-described evaluation of water and oil repellency is carried out.

[Example 1]
In a 1 L glass reaction vessel, 112.5 g of C ₆ F ₁₃ C ₂ H ₄ OCOC (CH ₃ ) ═CH ₂ (purity 99.6%, hereinafter referred to as C6FMA (a)), CH ₂ = C 15 g of (CH ₃ ) COO (C ₂ H ₄ O) _n H (the average value of n is 8, hereinafter referred to as MAEO 8 (b)), N, N-diethylaminoethyl methacrylate (hereinafter referred to as DEAEMA (c-1) 22.5 g), 450 g of methyl isobutyl ketone (hereinafter referred to as MIBK), and 1.2 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] are charged. The nitrogen substitution was repeated three times. The polymerization reaction was carried out at 65 ° C. for 16 hours at a stirring speed of 350 rpm to obtain a pale yellow solution having a solid content concentration of 24.2% by mass.

  The solid content concentration was almost the same as the charged monomer concentration, and it was confirmed that the polymerization rate was almost 100%. Therefore, the ratio of the charged monomer and the ratio of the polymerized unit based on each monomer contained in the fluorinated copolymer are substantially the same, and the polymerized unit based on C6FMA (a) is 75% by mass, MAEO8 (b ) Based on DEAEMA (c-1) was 10% by mass, and 15% by mass.

  To 100 g of the obtained pale yellow solution, 180 g of water and 1.76 g of acetic acid were added, mixed for 15 minutes using ultrasonic waves, and emulsified and dispersed. MIBK was distilled off at 65 ° C. under reduced pressure to obtain a pale orange transparent aqueous dispersion, and then a fluorinated copolymer (1) water having a solid content concentration of 20% by mass using ion-exchanged water. A dispersion was prepared.

Fluorine-containing copolymer (1) 58.2 g of ion-exchanged water was added to 1.8 g of the aqueous dispersion to prepare a powder processing solution. The powder treatment solution was added to 4.8 g of titanium dioxide (trade name STR-60C, manufactured by Sakai Chemical Co., Ltd.), and the mixture was sufficiently stirred until uniform, and then stirred at room temperature for 15 minutes. The contents were spread on a Teflon (registered trademark) sheet, sufficiently dried at 60 ° C., and then pulverized in a mortar to obtain a cosmetic powder. The tactile sensation of the obtained powder was good.
The resulting cosmetic powder was evaluated for water and oil repellency and stability. The results are shown in Tables 1 and 2.

[Example 2]
In a 1 L glass reaction vessel, 154.1 g of C6FMA (a) (purity 99.7%), 25.9 g of 2-hydroxyethyl methacrylate (hereinafter referred to as 2-HEMA (b)), methacrylic acid (Hereinafter referred to as MAA (c-2)) 16.0 g, acrylamide t-butylsulfonic acid (compound represented by formula (5); hereinafter referred to as AATBS (c-2)) 4.0 g 478.8 g of acetone, 119.7 g of methanol and 1.6 g of dimethyl-2,2-azobisisobutyrate (V-601.) Were charged, and the nitrogen substitution was repeated three times. The polymerization reaction was carried out at 65 ° C. for 20 hours at a stirring speed of 350 rpm to obtain a pale yellow solution having a solid content concentration of 24.9% by mass.

  The solid content concentration was almost the same as the charged monomer concentration, and it was confirmed that the polymerization rate was almost 100%. Therefore, the proportion of the charged monomer and the proportion of the polymerized units based on each monomer contained in the fluorinated copolymer are substantially the same, and the polymerized unit based on C6FMA (a) is 60% by mass, 2-HEMA. The polymerized unit based on (b) was 13% by mass, the polymerized unit based on MAA (c-2) was 8% by mass, and the polymerized unit based on AATBS (c-2) was 2% by mass.

  22.1 g of diethanolamine was added to 900 g of hot water at 50 ° C., and 750 g of the obtained pale yellow polymerization solution was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred as it was at 60 ° C. for 30 minutes for chlorination. Acetone and methanol were distilled off at 85 ° C. under reduced pressure to obtain a pale orange transparent aqueous dispersion, and then a fluorinated copolymer having a solid content concentration of 20% by mass using ion-exchanged water (2 ) A water dispersion was prepared.

A cosmetic powder was obtained in the same manner as in Example 1 except that the fluorinated copolymer (1) aqueous dispersion was changed to the fluorinated copolymer (2) aqueous dispersion. The tactile sensation of the obtained powder was good.
The resulting cosmetic powder was evaluated for water and oil repellency and stability. The results are shown in Tables 1 and 2.

[Example 3 (comparative example)]
48 g of C ₈ F ₁₇ C ₂ H ₄ OCOCH═CH ₂ (purity 90%), 12 g of stearyl acrylate, 150 g of ion-exchanged water, 24 g of acetone, 0.06 g of stearyl mercaptan, 1. 8 g and 4.2 g of polyoxyethylene nonylphenyl ether were mixed at 50 ° C., and the mixture was emulsified with a high-pressure homogenizer. The emulsified liquid was transferred to a 300 mL glass reactor, and 0.3 g of azobisisobutylamidine-2 hydrochloride (trade name V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added. Nitrogen substitution was repeated twice to initiate polymerization. The mixture was stirred at 60 ° C. for 8 hours to obtain a milky white polymer emulsion. It was 24.5 mass% when solid content concentration of the emulsion was measured. Ion exchange water was added to the emulsion to prepare an emulsion of a fluorinated copolymer (3) having a solid content concentration of 20% by mass.

A cosmetic powder was obtained in the same manner as in Example 1 except that the fluorinated copolymer (1) aqueous dispersion was changed to an emulsion of the fluorinated copolymer (3). The obtained powder had a slightly sticky feeling.
The resulting cosmetic powder was evaluated for water and oil repellency and stability. The results are shown in Tables 1 and 2.

[Example 4 (comparative example)]
Fluorine-containing copolymer (1) 2.4 g of perfluoroalkyl phosphate ester ethanolamine salt (solid content concentration 15%, manufactured by Asahi Glass Co., Ltd., trade name Asahi Guard-530) and ion-exchanged water 57 A cosmetic powder was obtained in the same manner as in Example 1, except that the mixture was changed to 0.6 g. The tactile sensation of the obtained powder was good.
The resulting cosmetic powder was evaluated for water and oil repellency and stability. The results are shown in Tables 1 and 2.

[Example 5 (comparative example)]
Untreated titanium dioxide (trade name STR-60C, manufactured by Sakai Chemical Co., Ltd.) was evaluated for water and oil repellency. The results are shown in Table 1.

The cosmetic powder of the present invention is useful as a cosmetic powder contained in cosmetics that are required not to cause makeup collapse due to sweat, sebum, oils of other cosmetics, and the like.

Claims (6)

Based on 60 to 98% by mass of polymer units based on the following monomer (a), 1 to 20% by mass of polymer units based on the following monomer (b) and the following monomer (c) on the powder surface Cosmetic powder to which a fluorine-containing copolymer (A) containing 1 to 30% by mass of polymerized units is attached.
Monomer (a):
(ZY) _n A compound represented by X.
However, the symbols in the formulas have the following meanings.
Z: a perfluoroalkyl group having 1 to 6 carbon atoms or _{C m F 2m + 1 O (} CFWCF 2 O) d CFK- [m is an integer of 1 to 6. d is an integer of 1 to 4. W and K are each independently a fluorine atom or —CF ₃ . ] The group represented by this.
Y: Divalent organic group or single bond.
n: 1 or 2.
X: a polymerizable unsaturated group, -CR = CH ₂ when n is _{1, -COOCR = CH 2, -OCOCR} = CH 2, -OCH 2 -φ-CR = CH 2 or -OCH = CH _2, and when n is _{2 = CH (CH 2) p} CR = CH 2, = CH (CH 2) p COOCR = CH 2, = CH (CH 2) p OCOCR = CH 2 or -OCOCH = CHCOO -[R is a hydrogen atom, a methyl group or a halogen atom. φ is a phenylene group. p is an integer of 0-4. ].
Monomer (b):
^{_{CH 2 = CR 1 -G- (R}} 2 O) compound represented by _q -R ^3.
However, the symbols in the formulas have the following meanings.
R ¹ : a hydrogen atom or a methyl group.
R ² : an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with hydroxyl groups.
q: An integer from 1 to 50.
_{G: -COO (CH 2) r} - or -COO (CH _{2) t} -NHCOO- [r is 0-4 integer. t is an integer of 1 to 4. ].
R ³ : hydrogen atom, methyl group, acryloyl group, methacryloyl group or allyl group.
Monomer (c):
A compound represented by CH ₂ = CR ⁴ -U.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
U: An organic group containing a functional group that can be ionized in water. The cosmetic powder according to claim 1, wherein the monomer (c) is the following monomer (c1).
Monomer (c1):
^{_{CH 2 = CR 4 -M-Q}} 1 -NR 5 R 6 or ^{_{CH 2 = CR 4 -M-Q}} 1 -N (O) a compound represented by R ⁵ R ^6.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
M: —COO— or —CONH—.
Q ¹ : an alkylene group having 2 to 4 carbon atoms, or an alkylene group having 2 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with hydroxyl groups.
R ⁵ and R ⁶ : each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 2 to 3 carbon atoms in which a part of hydrogen atoms is substituted with a hydroxyl group. Alternatively, R ⁵ , R ⁶ and the nitrogen atom may form a morpholino group, piperidino group or pyrrolidinyl group. The cosmetic powder according to claim 1, wherein the monomer (c) is the following monomer (c2).
Monomer (c2):
CH ₂ = CR ⁴ compound represented by -M-Q ² -V.
However, the symbols in the formulas have the following meanings.
R ⁴ : hydrogen atom or methyl group.
M: —COO— or —CONH—.
Q ² : contains a single bond, an alkylene group having 2 to 4 carbon atoms, an alkylene group having 2 to 3 carbon atoms in which some or all of hydrogen atoms are substituted with a hydroxyl group or a halogen atom, or an etheric oxygen atom An alkylene group having 4 to 18 carbon atoms;
V: —COOH, —SO ₃ H or —P (O) (OH) ₃ The fluorine-containing copolymer (A) further contains a polymer unit based on the following monomer (d), and 60 to 97.9% by mass of the polymer unit based on the monomer (a), the monomer 1 to 20% by mass of polymerized units based on (b), 1 to 20% by mass of polymerized units based on the monomer (c) and 0.1 to 10% by mass of polymerized units based on the following monomer (d) The cosmetic powder according to any one of claims 1 to 3, which is a fluorine-containing copolymer containing 1%.
Monomer (d):
Monomers excluding monomer (b), monomer (c1) and monomer (c2), which are isocyanate groups, blocked isocyanate groups, urethane bonds, alkoxysilyl groups, epoxy groups, N- A (meth) acrylate having one or more functional groups selected from the group consisting of a methylol group and an N-alkoxymethyl group and having no polyfluoroalkyl group. The cosmetic powder according to any one of claims 1 to 4, wherein the fluorine-containing copolymer (A) is a fluorine-containing copolymer obtained by using the following polymerization initiator (e).
Polymerization initiator (e):
An azo compound or an azoamidine compound, which has an acute oral toxicity in a rat or a mouse of 1000 mg / kg or more and a 10-hour half-life temperature of 30 ° C. or more. Cosmetics containing the cosmetic powder according to any one of claims 1 to 5.