JP2000309509A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic having high water resistance and durability of makeup, high uniformity of a cosmetic film, excellent stability with time and smooth and good touch by making the cosmetic include powder treated with a compound containing a specific perfluoropolyether group and a silicone resin. SOLUTION: This cosmetic comprises (A) 2-95 wt.% of powder (e.g. titanium oxide, red iron oxide, etc.), subjected to surface treatment with 0.1-50 wt.% of a compound containing a perfluoropolyether group having >=300 molecular weight, selected from a perfluoropolyether alkyl phosphate, its salt, a perfluoropolyether alkyl sulfate, its salt, a perfluoropolyether alkyl carboxylate and its salt and (B) 0.5-50 wt.% of silicone resin solid or semisolid at a normal temperature (e.g. trimethylsiloxysilicic acid resin). The cosmetic has improved stability, etc., by including an amphiphilic silicone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics, and more particularly, to cosmetics that are excellent in water resistance, cosmetic durability and powder dispersibility so that the product itself and the cosmetic film at the time of use are uniform. It is an object of the present invention to provide a cosmetic having excellent stability over time and having a smooth and good feel.

[0002]

2. Description of the Related Art Conventionally, in order to improve the water resistance of cosmetics and the durability of the cosmetics, a technique of strengthening the decorative film by subjecting powder to water repellent treatment or combining oil-soluble resin and volatile oil in combination. It has been known. In particular, a treated powder using a perfluoroalkyl phosphate ester and a salt thereof can impart high water repellency, and thus is useful as a powder to be blended into a cosmetic that requires high water resistance and long lasting makeup. It is.

[0003]

A cosmetic powder treated with a perfluoroalkyl phosphate or a salt thereof is a powder useful for cosmetics that require water resistance and long-lasting makeup. However, on the other hand, since it is also provided with high oil repellency, the wettability is very poor depending on the medium,
In some cases, the dispersibility is not good, and in order to obtain a uniform and stable cosmetic composition over time, a powder dispersing step that is powerful and long in time is often required. in addition,
Poor dispersibility adversely affects the cosmetic film on the skin when used, so that in order to obtain a uniform cosmetic film, there were cases where formulation restrictions were imposed during product preparation. Also,
When a water-repellent / oil-repellent cosmetic powder is obtained using a perfluoroalkyl phosphate or a salt thereof, a perfluoroalkyl group having 8 or more carbon atoms is required to obtain a sufficient effect. Become. In that case, the compound to be treated on the powder surface is in a solid state, and the smoothness of the powder itself may be lost. Therefore, it has a moderate wettability to the medium, in other words, has a suitable oil repellency and is easy to disperse. It has been desired to develop a cosmetic composition which is excellent in uniformity and stability over time due to excellent powder dispersibility, and has a smooth and good feel.

[0004]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a silicone resin containing a compound-treated powder having a specific perfluoropolyether group and a silicone resin have high water resistance. With cosmetic persistence, high uniformity of the product itself and the makeup film when used,
The present inventors have found that a cosmetic composition having excellent stability over time and having a smooth and good feel can be obtained, and the present invention has been completed. That is, the present invention provides the following components (a) and (b): (a) perfluoropolyether alkyl phosphate and its salt, perfluoropolyether alkyl sulfate and its salt, perfluoropolyether alkyl carboxylic acid and Having a molecular weight of 30 selected from its salts
Having a perfluoropolyether group of 0 or more, 1
An object of the present invention is to provide a cosmetic which is characterized by containing (b) a silicone resin whose cosmetic surface is treated with one or more compounds.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The component (a) used in the present invention is obtained by treating a base powder with a compound having a specific perfluoropolyether group,
Examples described in JP-A-8-133928 are exemplified. The compound having a perfluoropolyether group constituting the treated powder is selected from perfluoropolyether alkyl phosphoric acid and salts thereof, perfluoropolyether alkyl sulfate and salts thereof, and perfluoropolyether alkyl carboxylic acid and salts thereof. Is done. These compounds contain a perfluoropolyether group and have a polar group selected from a phosphate group, a sulfate group and a carboxyl group to have an affinity for the powder surface. Further, a perfluoropolyether group refers to a group having at least two or more ether oxygens bonded to perfluoroalkylene or perfluoroalkyl. Therefore, the perfluoropolyether alkyl phosphoric acid and salts thereof according to the present invention are described in JP-A-5-3920.
Compounds containing a perfluorooxyalkyl group having only one ether oxygen as described in JP-A No. 9 and JP-A-5-58841 are not included. The molecular weight of the perfluoropolyether group is 300 or more, preferably 500 or more, and a preferable upper limit is about 7,000. If it is less than 300, it is difficult to sufficiently impart water / oil repellency, and it is difficult to exhibit the effects of the present invention.

Preferred examples of the perfluorooxyalkylene group constituting the perfluoropolyether moiety include a perfluorooxymethylene group, a perfluorooxyethylene group, a perfluorooxyisopropylene group and a perfluorooxy n-propylene group. Can be At least one of them is selected and polymerized to form a perfluoropolyether group. Among them, particularly preferred perfluoropolyether groups are groups represented by the following general formulas (1) and (2).

(X) CFO (CF₂CF (CF₃) O)_l(CF₂CF₂O)_m(CF₂O)_nCF (X) -... (1)-(X) CFO (CF₂CF₂CF₂O)_l(CF₂CF₂O)_m(CF₂O) _n CF (X)-(2) (however, the molecular weight is 300 or more, more preferably 5
00 or more, l and m each represent an integer of 0 or more, and n is 1
Where l = m ≠ 0 and 1 / n = 1 to 1
00, more preferably 20 to 40, and m / n
= 0.1 to 50, more preferably 0.2 to 20
X may be the same or different, and F or CF₃In
You. In addition, a perfluoropolyether group having two or more perfluoropolyether groups
In the case of containing an oxyoxyalkylene group,
This is not limited to the case where the same type is continuously polymerized.
Random polymerization or block polymerization may be used.

Further, from the viewpoint of the adhesion between the compound having a perfluoropolyether group according to the present invention and the substrate powder, it is necessary that the polar group having an affinity for the powder is not easily detached from the compound. It is necessary, and therefore, the compound preferably contains at least one or more oxyalkylene groups. More preferably, it is 1-2. This is because the presence of three or more oxyalkylene groups results in poor water / oil repellency of the compound. Similarly, an alkylene group may be contained in addition to the oxyalkylene group in terms of the fixing force. The preferred carbon number of the alkylene group is 2
It is as follows.

Examples of the compound having a perfluoropolyether group include perfluoropolyether alkyl phosphoric acid and salts thereof, perfluoropolyether alkyl sulfate and salts thereof, and perfluoropolyether alkyl carboxylic acid and salts thereof. Among them, perfluoropolyether alkyl phosphoric acid or a salt thereof is preferable.
More preferred are compounds represented by the following general formulas (3) and (4) and amine salts thereof such as diethanolamine salts and triethanolamine salts.

[0010] _{[C a F 2a + 1 O} (C 3 F 6 O) l (CF 2 O) n CF (X) (CH 2) d - - (OCH 2 CH 2) r] q OP (= O) (OH _3-q (3) (provided that the molecular weight of the perfluoropolyether group is 300)
Or more, more preferably 500 or more, and 1 / n
= 1 to 100, more preferably 20 to 40, a is 1 to 10, d is 0 to 2, q is 1 or 2, r is 1 to 2, and X is F or CF ₃ . )

(HO) ₂ (O =) PO (CH ₂ CH ₂ O) _r CH ₂ CF ₂ O (CF ₂ CF ₂ O) _m (CF ₂ O) _n CF ₂ CH ₂ (OCH ₂ CH ₂ ) _r OP (＝ O) (OH) ₂ (4) (However, the molecular weight of the perfluoropolyether group is 300
Or more, more preferably 500 or more, and m / n
= 0.1-50, more preferably 0.2-20, and r is 1-2. )

As the powder to be treated with the compound having a specific perfluoropolyether group of the component (a) of the present invention, any powder conventionally used as a cosmetic powder may be spherical or plate-shaped. , Such as needle-like, fume-like, fine particles, pigment-grade particle size, porous and non-porous particle structure, etc., inorganic powders, glitter powders, organic powders , Pigment powders, metal powders, composite powders and the like. Specific examples include white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate; colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, navy blue, and ultramarine blue; talc; Phlogopite, mica, biotite, synthetic mica, sericite (sericite), synthetic sericite, kaolin, silicon carbide, bentonite, smectite, silicic anhydride, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, silica Saw soil,
Aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, white powder such as boron nitride, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride , Titanium oxide mica titanium, navy blue treated mica titanium, carmine treated mica titanium, brilliant powder such as bismuth oxychloride, fish scale foil, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin,
Cellulose resin, polystyrene resin, copolymer resin such as styrene-acrylic copolymer resin, organic polymer resin powder such as polypropylene resin, silicone resin, urethane resin, etc., organic low molecular weight such as zinc stearate, N-acyl lysine Powder, starch, silk powder, natural organic powder such as cellulose powder, Red No. 201, Red No. 202, Red No. 2
No. 05, Red No. 226, Red No. 228, Orange No. 203,
Organic pigment powders such as Orange No. 204, Blue No. 404, Yellow No. 401, Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, etc. Organic pigment powder such as zirconium, barium or aluminum lake or metal powder such as aluminum powder, gold powder and silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coated mica titanium and titanium oxide Composite powders such as silicon dioxide and zinc oxide-containing silicon dioxide can be used, and these powders can be used alone or in combination of two or more.

The method of surface-treating the powder with a compound having a specific perfluoropolyether group is not particularly limited, and a usual powder surface coating method can be applied. For example, a method of dissolving or dispersing a compound having a perfluoropolyether group in a solvent (an organic solvent or a polar solvent), mixing with a powder, and then removing and drying the solvent;
Alternatively, the powder is dispersed in water, and a salt solution of a compound having a perfluoropolyether group is added to the dispersion, and the liquid property of the system is made acidic to thereby form a compound having a perfluoropolyether group on the surface of the powder. A treated powder can be easily obtained by a method of precipitating and fixing, for example. After the above treatment, the powder may be baked at a high temperature in order to more strongly adsorb the compound having a perfluoropolyether group to the powder. In the surface treatment, two or more kinds of powders can be mixed and treated at the same time. Furthermore, as long as the effects of the present invention are not impaired, other fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin,
N-long chain acyl amino acids, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes,
The coating may be performed simultaneously or with a known coating agent such as a surfactant. When performing multiple treatments, the order of known surface treatment and treatment with a compound having a perfluoropolyether group does not matter. The amount of treatment with the compound having a perfluoropolyether group varies depending on the type of the compound and the powder, but from the viewpoint of achieving the effect, it is preferably 0.1 to 50% by weight of the powder (hereinafter simply referred to as “%”). ), More preferably 0.5 to 20%.
The blended amount of the treated powder of the component (a) in the cosmetic is preferably 2 to 95%, more preferably 5 to 85%. When used in this range, the intended effect can be more sufficiently obtained.

In the cosmetics of the present invention, cosmetic powders treated with a fluorine compound having a specific perfluoropolyether group exhibit high water repellency, and thus are required to have water resistance and cosmetic durability. Suitable for blending into ingredients. In addition, compared to those treated with a fluorine compound having a perfluoroalkyl group, the wettability to the medium is excellent and the dispersibility is good, so that the cosmetic and the cosmetic film containing the powder are uniform. It can be. In addition, the product has excellent stability over time. Furthermore, the powder for cosmetics of the present invention provides a compound having a smooth and good feel even when blended in a cosmetic, because the compound to be treated on the powder surface is not a solid but a liquid. be able to.

The cosmetic of the present invention is produced by essentially blending a cosmetic powder, which has been surface-treated with the above-mentioned fluorine compound having a perfluoropolyether group, as a powder component. With respect to other powder components, it is preferable to mix a powder component previously treated with an oil agent or the like in order not to hinder the effects of the present invention. Blending is also possible.

The silicone resin of the component (b) used in the present invention is a solid or soft solid silicone resin which can be dissolved or uniformly dispersed in a volatile silicone oil at room temperature. Specific examples include a trimethylsiloxysilicate resin, an acrylic-silicone-based graft copolymer, and a partially crosslinked organopolysiloxane polymer.

The trimethylsiloxysilicate resin is represented by (R
_{3 SiO 1/2) x · (SiO} 4/2) y (R is represented by a hydrocarbon group or a phenyl group) to 6 carbon atoms, x
/ Y is an organic silicone resin present in the range of 1/8 to 6/1. Commercially available trimethylsiloxysilicate resins include those dissolved in silicone oil, for example,
KF7312F, KF7312J, KF7312K, K
F9001, KF9002, X-21-5249, X-
21-5250, (Shin-Etsu Chemical Co., Ltd.), D
C593, BY11-018 (both manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF4600 (manufactured by Toshiba Silicone Co., Ltd.) and the like.

The acrylic-silicone-based graft copolymer is a radical polymer of an organopolysiloxane compound having a radical polymerizable group at one end of a molecular chain and a radical polymerizable monomer mainly composed of acrylate and / or methacrylate. And JP-A-2-25411, JP-A-2-132141, and the like. For example, an organopolysiloxane compound having radical polymerizability at one end of a molecular chain is represented by the following general formula (5)

[0019]

Embedded image

R1: methyl group or hydrogen atom R2: carbon atom having a linear or branched carbon chain optionally interrupted by one or two ether bonds
10 divalent saturated hydrocarbon groups R3: a methyl group or a butyl group l: 3-300.

On the other hand, the radically polymerizable monomer mainly composed of acrylate and / or methacrylate means a compound having one radically polymerizable unsaturated bond in a molecule. The acrylate and / or methacrylate used includes: Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate,
Stearyl (meth) acrylate, behenyl (meth) acrylate, triacontanyl (meth) acrylate,
Alkyl (meth) acrylates such as Hentriacontanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, and fluorocarbon chains 1 to 10 Fluoroalkyl (meth) acrylate, cholesteryl (meth) acrylate, alkyl cholesteryl (meth) acrylate,
(Meth) acrylic acid amide can be exemplified. In addition, various polymerizable monomer compounds other than the above-mentioned acrylate and / or methacrylate can be used as needed. These compounds include styrene,
Substituted styrene, vinyl acetate, (meth) acrylic acid, maleic anhydride, maleic ester, fumaric ester,
Vinyl chloride, vinylidene chloride, ethylene, propylene,
Butadiene, acrylonitrile, fluorinated olefin, N
-Vinylpyrrolidone and the like. Also,
In order to adjust the resin hardness of the acrylic-modified silicone resin, a crosslinking agent such as ethylene glycol di (meth) acrylate or pentaerythritol tetra (meth) acrylate may be contained as a radical polymerizable monomer.

A dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain, an acrylate and / or
Alternatively, the copolymerization with a radical copolymerizable monomer mainly composed of methacrylate can be carried out in a polymerization ratio of 1/19 to 2/1 by a usual radical such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, or the like. The polymerization is performed in the presence of a polymerization initiator, and any of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be applied. Commercially available acrylic-modified silicone resins include KP540, KP561, and KP541, KP543, KP545 (all manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in a solvent.

The partially crosslinked organopolysiloxane polymer is an organopolysiloxane polymer having a three-dimensional crosslinked structure which is insoluble in benzene but can contain benzene in an amount equal to or more than its own weight, and is disclosed in JP-B-8-6035. What is described in a gazette etc. is illustrated. The partially crosslinked organopolysiloxane polymer is a polymer obtained by crosslinking an organopolysiloxane, partially has a three-dimensional crosslinked structure, is composed of R ₂ SiO units and RSiO _1.5 units, _It may contain _0.5 SiO ₃ units and / or SiO ₂ units. However, R in each structural unit is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, or a propyl group;
Examples include an aryl group such as a phenyl group and a tolyl group, and an aliphatic unsaturated group such as a vinyl group, which may be the same or different. Commercially available products include silicone oils mixed with partially crosslinked organopolysiloxane polymers, for example, KSG15, KSG16, KS
G18 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the cosmetic of the present invention, the silicone resin functions to improve water resistance and cosmetic durability. The amount of the silicone resin in the cosmetic of the present invention varies depending on the type of the silicone resin, but is preferably 0.5 to 50%, more preferably 2 to 25% in the cosmetic.
%. When used in this range, the intended effect can be more sufficiently obtained. As a method of compounding the silicone resin into the cosmetic, for example, the compound can be dissolved or uniformly dispersed in a volatile silicone oil and compounded, but the compounding method is not limited thereto. Specific examples of the volatile silicone oil include a cyclic silicone oil such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, and a linear dimethylpolysiloxane having a boiling point of 300 ° C. or lower.

The cosmetic of the present invention is produced by essentially blending the silicone resin described above, but oil-soluble resins other than the silicone resin can be blended as long as the effects of the present invention are not impaired. Oil-soluble resins other than silicone resins include alkyl (meth) acrylate, polyvinylpyrrolidone,
Examples thereof include organic polymer resins such as polyvinylpyrrolidone / vinyl acetate copolymer, polyester and polyisobutylene, and rosin resins such as pentaerythritol rosinate.

The cosmetic of the present invention further comprises a product itself and a cosmetic film when used by containing, as a component (c), an amphiphilic silicone compound containing a hydrophilic segment and an organopolysiloxane segment in the molecule. And the stability with time are significantly improved. The amphiphilic silicone compound containing a hydrophilic segment and an organopolysiloxane segment in the molecule used in the present invention is a silicone derivative having a hydrophilic segment and an organopolysiloxane segment in the molecule, and is a side of the organopolysiloxane. It has a hydrophilic segment at the chain and / or at the end. To exemplify hydrophilic segment, an amino group _{(-NH 2,} -NHRNH 2), a hydroxyl group (-OH), a carboxyl group (-COOH), a polyoxyalkylene group (- _{(OR) n -)} and the like.

More specifically, the amphiphilic silicone compound used in the present invention is exemplified by KF-86 as an amino-modified organopolysiloxane (-NH ₂ side chain type).
4, KF-865, KF-868, KF-8003 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-801 as an amino-modified organopolysiloxane (-NH ₂ both terminal type)
2, X-22-161A, X-22-161B, X-2
2-161AS (same as above), KF-86 as amino-modified organopolysiloxane (-NHRNH ₂ side chain type)
0, KF-861, KF-880, KF-8002, K
F-8004, KF-8005, KF-858 (same as above), X-22-4015 (same as above) as a carbinol-modified organopolysiloxane (same as above), and KF- as a carbinol-modified organopolysiloxane (both terminals). 6001, KF-6002, KF-6003,
X-22-160AS (same as above), carboxy-modified organopolysiloxane (—COOH side chain type)
22-3701E (same as above), X-2 as a carboxy-modified organopolysiloxane (-COOH both terminal type)
2-162A, X-22-162C (same as above), polyoxyalkylene-modified organopolysiloxane (-(OR)
_n -side chain type) as KF-6011, KF-601
2, KF-6013, KF-6015, KF-601
6, KF-6017 (same as above), X-22-4991 (same as above) as a polyoxyalkylene-modified organopolysiloxane (-(OR) _n -both terminal type), and KF as a polyoxyalkylene-alkyl co-modified organopolysiloxane. -6026 (same as above), ABILEM-90 (manufactured by Goldschmidt) and the like, and one or more of these can be used.

These amphiphilic silicone compounds are
Although the displacement can be suitably used in the present invention, it is particularly preferable.
Is a polyoxyalkylene-modified organopolysilo
Xane, polyoxyalkylene / alkyl co-modified organo
Nopolysiloxane and the following general formulas (6), (7),
(Poly) glycerin-modified organopodium represented by (8)
Siloxane. Si (Ra)₃O_1/2-[Si (Ra)₂O_2/2]_n-[Si (Ra) XO _2/2 ]_m-Si (Ra)₃O_1/2 … (6) Si (Ra)_aX_3-aO_1/2-[Si (Ra)₂O_2/2]_n-Si (Ra)_aX_3-aO_1/2 … (7) Si (Ra)_aX_3-aO_1/2-[Si (Ra)₂O_2/2]_n-[Si (Ra) XO_2/2]_m-Si (Ra)_aX_3-aO_1/2 ... (8) (wherein, Ra has 1 to 6 carbon atoms which may be different from each other)
Part or all of monovalent hydrocarbon groups or halogen atoms
A is a hydrocarbon group in which a hydrogen atom is substituted;
Are 2, n and m are integers from 1 to 200, and X is different from each other.
May be represented by the following general formulas (9) and (10)
-Rb-O- (CH₂CH (OH) CH₂0)_p—H (9) —Rb—O—CH (CH₂OCH₂CH (OH) CH₂0H)₂ ... (10) (wherein Rb may be partially interrupted by an oxygen atom.
Divalent hydrocarbon group, p is an integer of 1 to 20)

The solubility of the above amphiphilic silicone compound in water changes depending on the ratio of the hydrophilic segment portion and the organopolysiloxane segment portion in the molecule. In the cosmetic of the present invention, an amphiphilic silicone compound can be blended irrespective of its solubility in water.However, in cosmetics requiring high water resistance such as cosmetics for midsummer, It is preferable to incorporate an amphiphilic silicone compound insoluble in water. In addition, the properties are preferably liquid in order not to reduce the adhesion to the skin, but are not particularly limited.

In the cosmetic of the present invention, the amphiphilic silicone compound is provided by a cosmetic powder which has been treated with a fluorine compound having a specific perfluoropolyether group and has improved dispersibility. It has the effect of further improving the uniformity of the product itself and the decorative film, and improving the stability over time.

The amount of the amphiphilic silicone compound in the cosmetic of the present invention varies depending on the type of the amphiphilic silicone compound and the form of the cosmetic to be prepared. % Is preferable, and more preferably 0.1 to 5%. When used in this range, the intended effect can be more sufficiently exhibited. The compounding method of the amphiphilic silicone compound in the cosmetic of the present invention,
Compounding can be carried out according to a conventional method such as mixing with an oily component, but a compounding method such as impregnating a powder in advance may be adopted, and the method is not limited. The amphiphilic silicone compound also functions as an emulsifier when the cosmetic of the present invention is emulsified cosmetic.

The cosmetic of the present invention may contain, in addition to the above-mentioned essential components, components commonly used in cosmetics, according to the purpose. In the present invention, by blending an oily component, it is possible to impart an emollient feeling, adjust the hardness of the dosage form, and adjust the feel during application. Furthermore, it can be used as an emulsified cosmetic to adjust the refreshing feeling and the moist feeling due to the aqueous component. In addition, the surfactant can improve the stability of the system and the dispersibility of the powder. Oily components include hydrocarbons, oils and fats, and waxes, regardless of the origin of animal oils, vegetable oils, synthetic oils, and the like commonly used in cosmetics, and solid oils, semi-solid oils, liquid oils, and volatile oils. , Hydrogenated oils, ester oils, fatty acids, higher alcohols,
Silicone oils other than the component (b), fluorinated oils, lanolin derivatives, oil-based gelling agents, and the like. Specifically, liquid paraffin, squalane, petrolatum, polybutene, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, mocro, montan wax, hydrocarbons such as Fischer-Tropsch wax, olive oil, castor oil,
Oils such as jojoba oil, mink oil, macadamian nut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, cetyl isooctanoate,
Isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamic acid di ( Esters such as cholesteryl, behenyl, octyldodecyl), fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, rosin acid, 12-hydroxystearic acid, stearyl alcohol, cetyl alcohol, lauryl Higher alcohols such as alcohol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol, and low polymerization degree dimethylpolysiloxane Dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, crosslinked organopolysiloxane, silicones such as fluorine-modified silicone, perfluorodecane, perfluorooctane, perfluoro Oily gels such as fluorinated oils such as polyethers, lanolin derivatives such as lanolin, lanolin acetate, isopropyl lanolin fatty acid and lanolin alcohol, dextrin fatty acid esters, sucrose fatty acid esters, starch fatty acid esters, aluminum 12-hydroxystearate, and aluminum stearate. Agents and the like, and one or more of these can be used.

The aqueous component may be water or any component soluble in water. In addition to water, for example, lower alcohols such as ethyl alcohol and isopropyl alcohol, propylene glycol and 1,3-butylene glycol Glycols such as dipropylene glycol and polyethylene glycol, glycerols such as glycerin, diglycerin and polyglycerin, aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender,
Examples of plant extracts such as rose include water-soluble polymers such as guar gum, sodium chondroitin sulfate, hyaluronic acid, arabic gum, sodium alginate, carrageenan, and other natural substances, such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose. Synthetic systems, such as carboxyvinyl polymers, alkyl-added carboxyvinyl polymers, polyvinyl alcohol, and sodium polyacrylate, can be mentioned.

As the surfactant, other than the amphiphilic silicone compound of the component (c), any surfactant generally used in cosmetics can be used, and nonionic surfactants and anionic surfactants can be used. Surfactants, cationic surfactants, amphoteric surfactants and the like can be mentioned. Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol Adducts, fatty acid esters of sorbitol and alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyalkylene alkyl ethers, glycerin alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene hydrogenated castor oil,
An alkylene glycol adduct of lanolin and the like can be mentioned. Examples of the anionic surfactant include inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfate, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α
-Sulfonated fatty acid salt, acylmethyltaurine salt, N-
Methyl-N-alkyl taurine salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, N-acyl amino acid Salts, N-acyl-N-alkylamino acid salts, o-alkyl-substituted malates, alkylsulfosuccinates and the like. Examples of the cationic surfactant include an alkylamine salt, a polyamine and an alkanolamine fatty acid derivative, an alkyl quaternary ammonium salt, and a cyclic quaternary ammonium salt. Examples of the amphoteric surfactant include phospholipid-containing components such as lecithin and lysolecithin and hydrogenated products thereof, carboxylic acid type of amino acid type and betaine type, sulfate type, sulfonic acid type, and phosphate type. For example, N, N-dimethyl-
N-alkyl-N-carboxylmethylammonium betaine, N, N-dialkylaminoalkylenecarboxylic acid, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N-dialkyl-N, N
-Bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine and the like.

In the cosmetic of the present invention, various components such as an ultraviolet absorber, a humectant, a film-forming agent, an anti-fading agent, an antioxidant, and the like may be used, as long as the effects of the present invention are not impaired. Antifoaming agents, cosmetic ingredients, preservatives, fragrances, and the like can be appropriately compounded to impart various effects. Examples of the ultraviolet absorber include benzophenone-based, PABA-based,
Cinnamic acid, salicylic acid, 4-tert-butyl-
As humectants such as 4′-methoxydibenzoylmethane and oxybenzone, for example, proteins, mucopolysaccharides, collagen, elastin, keratin, etc .; as antioxidants, for example, α-tocopherol, ascorbic acid; Vitamins, anti-inflammatory agents, crude drugs, etc.
As preservatives, for example, paraoxybenzoate,
Phenoxyethanol and the like.

The cosmetic of the present invention essentially comprises a cosmetic powder treated with a fluorine compound having a specific perfluoropolyether group as the component (a) and a silicone resin as the component (b). In addition, it is produced by optionally blending the amphiphilic silicone compound of the component (c) in addition to the above two components. The cosmetics of the present invention include make-up cosmetics, skin care cosmetics, and hair cosmetics, and the form of the cosmetics is powder cosmetics or oily cosmetics comprising a powder for cosmetics and an oily component, Further, there are emulsified cosmetics to which an aqueous component is added, and the properties can be solid, creamy, milky, multi-layered (shaking at the time of use), etc., but the cosmetics that can best exhibit the effects of the present invention The dosage forms are oily cosmetics and water-in-oil type emulsifying cosmetics. As for cosmetics, the effects are more remarkable in makeup cosmetics such as foundations, foundations, concealers, white powder, blusher, lipstick, lip balm, eye color, eyeliner, eyebrow, and mascara.

[0037]

Next, the present invention will be further described with reference to examples. These do not limit the present invention in any way.

Production Example 1: 2-treated titanium oxide beaker
500 g of propanol and 5 g of perfluoropolyether alkylphosphoric acid shown below are added, and 95 g of titanium oxide (CR-50, Ishihara Sangyo Co., Ltd.) is added with stirring.
After sufficiently stirring at room temperature, the mixture was mixed at 80 ° C. for 1 hour and dried under reduced pressure to obtain a titanium oxide treated with a perfluoropolyether compound 5%. _{(HO) 2 (O =)} PO (CH 2 CH 2 O) r CH 2 CF 2 O (CF 2 CF 2 O) m (C F 2 O) n CF 2 CH 2 (OCH 2 CH 2) r OP ( ＯO) (OH) ₂ (11) (wherein m / n = 1.8, r = 1 to 2, the average molecular weight of the perfluoropolyether alkyl phosphoric acid is 1050, and Average molecular weight is 606
It is. )

Preparation Examples 2 to 8 The same treatment as in Preparation Example 1 was carried out to obtain a zinc oxide treated with 5% perfluoropolyether compound (Preparation Example 2: treated zinc oxide), and a red iron oxide treated with 5% perfluoropolyether compound ( Production Example 3: Treated red iron oxide, 3% perfluoropolyether compound treated yellow iron oxide (Preparation Example 4: treated yellow iron oxide), perfluoropolyether compound 3% treated black iron oxide (Production Example 5: treated black iron oxide ) Perfluoropolyether compound 1% treated talc (Production Example 6: treated talc), perfluoropolyether compound 3% treated mica (Production Example 7: treated mica), perfluoropolyether compound 1
% Treated mica titanium (Production Example 8: treated mica titanium) was obtained.

Production Example 9: 500 ml of water was placed in a treated silica beaker and stirred with silica 4
Add 9.5 g and stir well at room temperature. This silica dispersion
Add the perfluoropolyether alkyl
2.5 g of diethanolamine 20% aqueous solution
And stirred and mixed for 3 hours after the addition. Medium with hydrochloric acid
After filtration, perform suction filtration, dry and
1% silica treated with an ether compound was obtained. CF₃O (CF₂CF (CF₃) O)_l(CF₂O)_nCF₂CH₂− − (OCH₂CH₂)_1.9OP (= O) [ONH₂(CH₂CH₂OH)₂] ₂ ... (12) (wherein 1 / n = 24.1, perfluoropolyether)
The average molecular weight of the alkyl phosphate diethanolamine salt is 1
195, the average molecule of the perfluoropolyether group
The quantity is 791. )

Production Examples 10 to 12 Nylon powder treated with 3% of a perfluoropolyether compound was treated in the same manner as in Production Example 9 (Production Example 10:
Treated nylon powder), perfluoropolyether compound 1% treated iron oxide treated fine particle titanium oxide (Production Example 1)
1: treated iron oxide-treated fine particle titanium oxide) and a 5% perfluoropolyether compound-treated organopolysiloxane elastomer powder (Production Example 12: treated organopolysiloxane elastomer powder).

Production Comparative Example 1: Treated titanium oxide 500 ml of water was placed in a beaker, 95 g of titanium oxide (CR-50, Ishihara Sangyo Co., Ltd.) was added with stirring, and the mixture was sufficiently stirred at room temperature. To this titanium oxide dispersion, 25 g of a 20% aqueous solution of a perfluoroalkylphosphoric acid diethanolamine salt represented by the following formula was gradually added with stirring, and the mixture was stirred for 2.5 hours after the addition. While further stirring, a 5% aqueous hydrochloric acid solution was gradually added to make the system acidic. The powder is collected by suction filtration, washed with water and dried to obtain a perfluoroalkyl compound 5
% -Treated titanium oxide was obtained. _{(C m F 2m + 1 CH} 2 CH 2 O) n P (= O) [ONH 2 (CH 2 CH 2 OH) 2] 3-n ... (13) ( wherein, m, n are each m = having 6 to 18 , 2 ≧ n ≧ 1, the average molecular weight is 954, and the average molecular weight of the perfluoroalkyl group is 619.)

Comparative Production Examples 2 to 8 A zinc oxide treated with 5% of a perfluoroalkyl compound (Comparative Production Example 2: treated zinc oxide), treated with the same method as in Comparative Production Example 1, and a red iron oxide treated with 5% of a perfluoroalkyl compound (Comparative Production Example 3: treated red iron oxide), perfluoroalkyl compound 3% treated yellow iron oxide (Comparative Production Example 4: treated yellow iron oxide), perfluoroalkyl compound 3% treated black iron oxide (Comparative Production Example 5: treated black Iron oxide) perfluoroalkyl compound 1% treated talc (Comparative Production Example 6: treated talc),
Perfluoroalkyl compound 3% treated mica (Comparative Production Example 7: treated mica), perfluoroalkyl compound 1%
A treated mica titanium (Comparative Production Example 8: treated mica titanium) was obtained.

Comparative Production Example 9: Silica treated with 1% perfluoroalkyl compound 5 g of the following perfluoroalkyl compound was uniformly dispersed in 500 ml of carbon tetrachloride, and 495 g of silica was added.
Stir for 1 hour. This was heated and dried under reduced pressure, further stirred at 105 ° C. for 1 hour, and then cooled to obtain silica treated with a 1% perfluoroalkyl compound. _{(C m F 2m + 1 CH} 2 CH 2 O) n P (= O) (OH) 3-n ... (14) ( wherein, m is having 6 to 18, n is 1.5, the average molecular weight of the perfluoroalkyl group Is 619.)

Comparative Production Examples 10 to 12 Nylon powder treated with 3% of a perfluoroalkyl compound (Comparative Production Example 1) was treated in the same manner as in Comparative Production Example 1.
0: treated nylon powder), 1% perfluoroalkyl compound-treated iron oxide-treated fine particle titanium oxide (Comparative Production Example 11: treated iron oxide-treated fine particle titanium oxide), 5% perfluoroalkyl compound-treated organopolysiloxane elastomer powder (comparative production) Example 12: A treated organopolysiloxane elastomer powder was obtained.

Examples 1 to 6 and Comparative Examples 1 to 3 Oily foundation An oily foundation having the formulation shown in Table 1 was prepared, and the following methods were used to determine smoothness during use, uniformity of a cosmetic film, water resistance, and cosmetic durability. Was evaluated. Table 1 also shows the results.

[0047]

[Table 1]

* 1-6: 5% treatment with methyl hydrogen polysiloxane * 7: Silicon KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.) * 8: Escalol 557 (manufactured by Van Dyke) * 9: ABIL EM-90 (Made by Goldschmidt)

(Production method) The component A group is mixed uniformly. 2. The component B group is heated and mixed uniformly. 3. Add 2 to 1 and knead with a roll mill. 4.3 was reheated and melt-filled in a container to obtain an oily foundation.

(Evaluation Method) Absolute evaluation was performed in the following seven grades (0 to 6 points) by a sensory test panel of 10 persons, and the average score was further divided into four grades. Water resistance was evaluated by swimming the pool (30 minutes) in a state where the foundation was actually applied, and evaluating the remaining state of the decorative film. (1) Absolute evaluation 6 points: Very good 5 points: Good 4 points: Somewhat good 3 points: Normal 2 points: Somewhat bad 1 point: Bad 0 points: Very bad (2) Four-level evaluation ◎: 5 points Exceeds ○: More than 3 points and 5 points or less △: More than 3 points and 3 points or less ×: 1 point or less

As is evident from the results in Table 1, the oily foundations of Examples 1 to 5 which are the products of the present invention show comparative examples 1 to 5 in all items such as feeling of use, film state, water resistance, and cosmetic durability. It can be seen that it has much better characteristics than No. 3. In particular, the product of the present invention had no powderiness and had a good emollient feeling.

Example 6: Oily solid foundation (formulation) (%) Treated titanium oxide (Production Example 1) 11.0 2. 2. Treated zinc oxide (Production Example 2) 2.0 Treated Bengala (Production Example 3) Appropriate amount 4. 4. Treated yellow iron oxide (Production Example 4) Appropriate amount 5. Treated black iron oxide (Production Example 5) Appropriate amount 6. Treated mica (Production Example 7) 20.0 Treated iron oxide-treated fine particle titanium oxide (Production Example 11) 5.0 8. Montan wax 3.0 9. 9. Candelilla wax 2.0 Silicone resin (* 7) 5.0 11. Silicone resin (* 10) 5.0 12. 12. Glycerin trioctanoate remaining amount 13. Ethylene glycol distearate 1.0 Diglycerin triisostearate 3.0 15. Fragrance appropriate amount * 10: Silicone KP-545 (Shin-Etsu Chemical Co., Ltd.) (Production method) 8 to 14 are mixed and melted, and 1 to 7 are added and kneaded with a cold roll mill. The mixture is again heated and melted, filled in a dish, and allowed to cool to give an oily solid foundation. The oily solid foundation of Example 6 had a uniform decorative film and was excellent in the durability of the cosmetic.

Example 7: W / O emulsified cream foundation (formulation) (%) Glycerin tribehenate 2.0 2. UV absorber (* 8) 3.0 3. Neopentyl glycol dioctanoate 8.0 4.0 Dextrin fatty acid ester (* 11) 1.55. Silicone KF-6026 (* 12) 3.0 6. 6. Sorbitan sesquioleate 1.0 Organically modified bentonite (* 13) 1.2 8. Silicone resin (* 7) 4.0 9. 9. Treated titanium oxide (Production Example 1) 9.5 Treated Bengala (Production Example 3) Appropriate amount 11. Treated yellow iron oxide (Production Example 4) Appropriate amount 12. Treated black iron oxide (Production Example 5) Appropriate amount 13. Treated mica titanium (Production Example 8) 0.5 Treated silica (Production Example 9) 1.0 15. Treated organopolysiloxane elastomer powder (Production Example 12) 2.0 16. 17. Propylene glycol dicaprate 7.0 Octamethylcyclotetrasiloxane 8.0 18. Decamethylcyclopentasiloxane balance 19. Ethanol 10.0 20. Purified water 20.0 * 11: Leopard KL (manufactured by Chiba Flour Milling) * 12: Manufactured by Shin-Etsu Chemical Co., Ltd. * 13: Benton 38 (NL Industries) (manufacturing method)
The mixture of 9 and 20 is added with stirring to produce.

Comparative Example 4: W / O emulsified cream foundation In Example 7, the powders treated with perfluoropolyether compounds of components (9) to (15) were replaced with powders treated with methyl hydrogen polysiloxane. Was prepared in the same manner as Comparative Example 4. In Comparative Example 4, the dispersibility of the powder was poor, the smoothness at the time of application was poor, and the uniformity of the decorative film and the durability of the decorative film were not sufficient. On the other hand, the W / O emulsified cream foundation of Example 7 according to the present invention has a smooth feeling of use, a uniform makeup film, and excellent water resistance and makeup durability. Met. Furthermore, since it contained an aqueous component, there was a refreshing sensation, and at the same time, the emollient effect was high.

Example 8: W / O emulsion type base (formulation) (%) 1. Treated titanium oxide (Production Example 1) 3.0 2. Treated iron oxide-treated fine particle titanium oxide (Production Example 11) 6.0 Treated talc (Production Example 6) 7.0 4. Nylon powder 3.0 5. 5. Polyoxyethylene / alkyl co-modified organopolysiloxane 3.0 Sorbitan sesquioleate 1.5 7. 7. Glycerin trioctanoate 16.0 8. Sucrose fatty acid ester (* 14) 1.0 Ceresin wax 6.0 10. Silicone resin (* 10) 6.0 11. Decamethylcyclopentasiloxane remaining amount12. Glycerin 1.5 13. Butylene glycol 5.0 14. Purified water 20.0 * 14: Sugar wax S-10E (Daiichi Kogyo Seiyaku Co., Ltd.) (Production method) Kneading 1-9 with a hot roll mill,
Is added. To this, a homogeneous mixture of 12 to 14 is gradually added with stirring. The container is again heated and melt-filled into a container to obtain a W / O emulsified solid base. W / of Example 8
The O-emulsion type base had a smooth feeling of use and contributed to the continuation of the cosmetic effect as the base of the foundation. In addition, since it contained an aqueous component, it had a refreshing feeling and at the same time had a high emollient effect.

Example 9: Powder foundation (prescription) (%) Treated titanium oxide (Production Example 1) 12.0 2. Treated Bengala (Production Example 3) 0.16 3. Treated yellow iron oxide (Production Example 4) 4.6 4. 4. Treated black iron oxide (Production Example 5) 0.05 Treated talc (Production Example 6) 20.0 6. Processed mica (Production Example 7) Remaining amount 7. 7. Treated nylon powder (Production Example 10) 3.0 8. Treated organopolysiloxane elastomer powder (Production Example 12) 2.0 Silicone resin (* 7) 2.5 10. Dipentaerythritol fatty acid ester (* 15) 1.0 11. Perfluoropolyether (* 16) 4.0 12. 12. Polyoxyethylene-modified organosipolyloxane (* 17) 2.0 13. Glycerin trioctanoate 2.0 Appropriate amount of fragrance 15. Ultraviolet absorber (* 8) 1.0 * 15: Cosmole 168AR (manufactured by Nisshin Oil Co., Ltd.) * 16: Fomblin HC / 04 (manufactured by Asimont) * 17: Silicone KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.) ( Production method) 1 to 8 are mixed and pulverized, and the mixture of 9 to 15 is gradually added and kneaded sufficiently. This is crushed and pressed into a plate to form a powder foundation. Example 9
Powder foundation has a smooth feeling of use, and is excellent in water resistance and makeup persistence.

[0057]

The cosmetic of the present invention has a smooth feeling of use, is excellent in uniformity of a cosmetic film, and is excellent in water resistance and cosmetic durability.

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[Procedure amendment]

[Submission date] January 12, 2000 (2000.1.1)
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

A dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain, an acrylate and / or
Alternatively, the copolymerization with a radical copolymerizable monomer mainly composed of methacrylate can be carried out in a polymerization ratio of 1/19 to 2/1 by a usual radical such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, or the like. The polymerization is performed in the presence of a polymerization initiator, and any of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be applied. Commercially available acrylic-modified silicone resins include KP561, KP571, and KP541, KP543, KP545 (all manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in a solvent.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

Examples 1 to 5 and Comparative Examples 1 to 3 Oily foundation An oily foundation having the formulation shown in Table 1 was prepared, and the following methods were used to determine smoothness during use, uniformity of a decorative film, water resistance, and cosmetic durability. Was evaluated. Table 1 also shows the results.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

Example 6: Oily solid foundation (formulation) (%) Treated titanium oxide (Production Example 1) 11.0 2. 2. Treated zinc oxide (Production Example 2) 2.0 Treated Bengala (Production Example 3) Appropriate amount 4. 4. Treated yellow iron oxide (Production Example 4) Appropriate amount 5. Treated black iron oxide (Production Example 5) Appropriate amount 6. Treated mica (Production Example 7) 20.0 Treated iron oxide-treated fine particle titanium oxide (Production Example 11) 5.0 8. Montan wax 3.0 9. 9. Candelilla wax 2.0 Silicone resin (* 7) 5.0 11. Silicone resin (* 10) 5.0 12. 12. Glycerin trioctanoate remaining amount 13. Ethylene glycol distearate 1.0 Diglycerin triisostearate 3.0 15. Appropriate amount of fragrance * 10: Silicon KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Production method) 8 to 14 are mixed and dissolved by heating, and 1 to 7 and 15 are added and kneaded with a cold roll mill. After heating and dissolving again, filling the dish, it is left to cool to obtain an oily solid foundation. The oily solid foundation of Example 6 had a uniform decorative film and was excellent in the durability of the cosmetic.

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Claims (3)

[Claims] 1. The following components (a) and (b): (a) perfluoropolyetheralkylphosphoric acid and its salt, perfluoropolyetheralkylsulfuric acid and its salt, perfluoropolyetheralkylcarboxylic acid and its salt A cosmetic, comprising (b) a silicone resin, which is treated with a compound having a perfluoropolyether group having a molecular weight of 300 or more selected from the group consisting of: 2. The cosmetic according to claim 1, further comprising the following component (c): (c) an amphiphilic silicone compound containing a hydrophilic segment and an organopolysiloxane segment in the molecule. Fees. 3. The cosmetic according to claim 1, wherein the cosmetic is an emulsion type.