JP6796007B2 - Powder cosmetics - Google Patents

Description

The present invention relates to powdered cosmetics, and more particularly to powdered cosmetics having excellent finish feeling and makeup durability.

Powdered cosmetics such as powder eyebrow, powder foundation, and face powder are cosmetics containing powder as a main component and appropriately mixed with water-based components, oils, and the like, and are widely used because they are simple to use. In addition to the usage method, powdered cosmetics have a wide range of usability such as spreading and spreading, and a feeling of use such as no burden, but make-up cosmetics can impart a fluffy texture. Conventionally, it has been known that powder has an optical effect and spherical powder imparts a soft soft focus effect, but in order to further improve the optical effect, a feeling of transparency is obtained. Surface-treated spherical powder technology in which two types of surface treatment agents are sequentially treated in the order of refraction on spherical powder having a soft focus effect (Patent Document 1), which has the effect of making unevenness inconspicuous and gives a natural finish. Spherical powder (Patent Document 2) coated in a multi-layered manner so that the refractive index of the outer layer obtained is smaller than the refractive index of the inner layer has been studied. By containing such spherical powder, it is possible to improve the spread and spread of the cosmetic, the ease of blurring for the make-up effect, the soft focus effect, and the natural finish effect, but the adhesion to the skin is impaired, so the makeup lasts. It was not at a satisfactory level in terms of sex.
On the other hand, as a technique for improving the longevity of powdered cosmetics, a technique using a water-repellent oil-repellent treated powder and a solid and / or semi-solid oil agent (Patent Document 3), an oily component and a swelling organically modified clay mineral The technique to be used (Patent Document 4) has been proposed. However, the technique using a water- and oil-repellent treated powder and a solid and / or semi-solid oil agent improves the makeup retention, but the adhesiveness is not sufficient, and the solid and / or semi-solid oils are used to improve the adhesiveness to the skin and eyebrows. / Or When the content of the semi-solid oil agent is increased, the spread and spread are impaired, it becomes difficult to blur, and the soft focus effect may be impaired. In addition, in the technique of using a swellable organically modified clay mineral as a gelling agent, it is necessary to uniformly disperse the swellable organically modified clay mineral in the preparation in order to obtain a product having good adhesion to the skin and moldability. If the dispersion is insufficient, a graininess may be felt during use, and a satisfactory result cannot be obtained in terms of smooth spread and spread and ease of blurring.

As described above, it has been difficult for powdered cosmetics to have both adhesiveness and makeup retention and a soft focus effect. However, powder cosmetics in make-up cosmetics, for example, eyebrow cosmetics for eyebrows, are used in powder form applied with fingers or props, liquid or oily solid type applied with a brush, etc., directly on the skin. There are a wide variety of dosage forms on the market, such as pencil-shaped ones, but among them, the powder shape is often selected when the soft focus effect is required. Eyebrows have a great influence on the impression given to humans, and the soft focus effect on the eyebrows that gives a soft impression and the makeup effect that it is easy to blur to obtain it are important functions required for eyebrows. In addition, eyebrow applies makeup not only to the skin but also to fibers called eyebrows to which powder does not easily adhere, and there is a strong demand for adhesiveness and makeup retention.

Japanese Unexamined Patent Publication No. 2005-154279 JP-A-2002-187810 Japanese Unexamined Patent Publication No. 2010-37213 JP-A-2010-235513

INDUSTRIAL APPLICABILITY The present invention provides a powdered cosmetic that has a ease of use that is easily blurred when applied and a cosmetic effect that has a soft soft focus effect, and is excellent in adhesiveness and makeup durability.

In such a situation, as a result of diligent research by the present inventors, the powder cosmetic contains a (meth) acrylic silicone-based graft copolymer having a cationic group and a spherical powder, so that it is easy to blur at the time of application. It was found that a powdered cosmetic having a fluffy soft focus effect and excellent adhesiveness and long-lasting makeup can be obtained. Spherical powder has an ease of blurring and a soft focus effect, but when combined with a (meth) acrylic silicone-based graft copolymer having a cationic group, the adhesion to the skin and keratin fibers is remarkably improved and the soft focus effect is enhanced. It has been found that the keratin fiber such as eyebrows also has a volume-increasing effect, and the present invention has been completed.

That is, the present invention provides a powder cosmetic containing the component (A) specific (meth) acrylic silicone-based graft copolymer and the component (B) spherical powder.

The present invention relates to a powdered cosmetic that has a ease of use that is easily blurred when applied and a cosmetic effect that has a soft soft focus effect, and is excellent in adhesiveness and makeup durability.

Hereinafter, the present invention will be described in detail.
The (meth) acrylic silicone-based graft copolymer of the component (A) of the present invention is a weight obtained by reacting at least the following radical polymerizable monomers (a), (b), (c) and (d). It is a coalescence and includes a polymer obtained by further adding a copolymerizable monomer other than (a) to (d) and reacting.
In the present invention, (meth) acrylic means to include acrylic and methacrylic.
The (meth) acrylic silicone-based graft copolymer of the present invention is preferably dissolved in 99.5% ethanol at 25 ° C. in an amount of 50% by mass or more.
The ratio of each monomer is not limited as long as the effect of the present invention is obtained, but (a) = 20 to 50% by mass and (b) = 0.5 with respect to the total of the monomers of (a) to (d). ~ 4% by mass, (c) and (d) = 46 to 79.5% by mass, and (c) / (d) = 0.5 to 1.5.
When copolymerizable monomers other than (a) to (d) are used, the total of the monomers of (a) to (d) is preferably 66.5% by mass or more of the total.
In the present invention, the charging ratio of the monomers is substantially synonymous with the composition ratio thereof in the copolymer.
The (meth) acrylic silicone-based graft copolymer of the present invention is a B-type rotational viscometer at 25 ° C. of an ethanol solution obtained by dissolving the copolymer in 99.5% ethanol so as to have a content of 20% by mass. The viscosity measured in use (unit: mPa · s = CS) is 50 to 250, preferably 70 to 150.
The Tg of the (meth) acrylic silicone-based graft copolymer of the present invention is preferably −10 to 40 ° C., more preferably 0 to 30 ° C.
Here, Tg indicates the value of Tg calculated by the following Fox formula.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
In the above formula, W1 to Wn indicate each weight fraction of n kinds of monomers used in the synthesis, and Tg1 to Tgn indicate the glass transition temperature of the homopolymer obtained by polymerizing only each monomer.
Furthermore, the (meth) acrylic silicone-based graft copolymer of the present invention includes various forms such as a random copolymer and a block copolymer.

The monomer that is the raw material of the copolymer will be described below.
(A) Radical polymerizable monomer represented by the general formula (I)

In the formula, Me represents a methyl group and R1 represents a hydrogen atom or a methyl group.
R2 represents a linear or branched chain divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and may contain 1 or 2 ether bonds. Specifically, -CH2-,-(CH2) 2,-(CH2) 5-,-(CH2) 10-, -CH2-CH (CH3) -CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2OCH2 (CH3) CH2 -, -CH2CH2OCH2CH2CH2OCH2CH2CH2- and the like are exemplified.
R3 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, and an i-butyl group. , T-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group and other alkyl groups having 1 to 10 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo Cycloalkyl groups having 1 to 10 carbon atoms such as hexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group; cyclopropylmethyl group, 2-cyclopropylethyl group, cyclobutylmethyl group, cyclopentylmethyl group, 3- Cycloalkylalkyl groups having 1 to 10 carbon atoms such as cyclopentylpropyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, cycloheptylmethyl group and cyclooctylmethyl group can be mentioned.
m represents an integer of 5 to 100.

The monomer represented by the formula (I) is, for example, the formula (Ia).

The (meth) acrylate-substituted chlorosilane compound represented by the formula (Ib).

It can be obtained by subjecting a single-terminal hydroxyl group-substituted polysiloxane represented by (1) to a dehydrochloric acid reaction according to a conventional method, but the synthesis method is not limited to this.

Specific examples of the monomer represented by the formula (I) include the following. In the following formula, Me represents a methyl group and n-Bu represents an n-butyl group.

The radically polymerizable monomer (b) component represented by the formula (II) or the formula (III) is at least one selected from the cationic compounds represented by the following formula (II) or the formula (III). is there.

In formula (II), R4 represents a hydrogen atom or a methyl group.
R5, R6, and R7 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. Examples thereof include i-propyl group, n-butyl group, s-butyl group, i-butyl group and t-butyl group.
X represents -O-, -NH-, -O-CH2- or -O-CH2CH (OH)-.
Y represents a linear or branched chain divalent saturated hydrocarbon group having 1 to 4 carbon atoms, −CH2-, − (CH2) 2, − (CH2) 3-, − (CH2) 4-, -CH2-CH (CH3) -CH2- and the like are exemplified.
Z- is a counter anion, and examples thereof include chlorine ion, bromine ion, hydrogen sulfate ion, nitrate ion, perchlorate ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

In formula (III), R8 and R9 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, and n−. Examples thereof include propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group and t-butyl group.
R10 and R11 may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group and i-. Propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-nonyl group, isononyl group, n-decyl group, lauryl group, tridecyl Examples thereof include a group, a myristyl group, an n-pentadecyl group, a palmityl group, a heptadecyl group, and a stearyl group.

Radical polymerizable monomer represented by formula (IV) (c)

In the formula, R12 represents a hydrogen atom or a methyl group.
R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and the linear or branched alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group and n. -Propyl group and i-propyl group are exemplified.

(D) Radical polymerizable monomer represented by the formula (V)

In the formula, R14 represents a hydrogen atom or a methyl group.
R15 represents a hydroxyalkyl group having 1 to 4 carbon atoms, and examples thereof include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group.

Other copolymerizable monomers Examples of other copolymerizable monomers include the following.
((Meta) acrylic monomer)
N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic N-octyl acid, cyclohexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, ( Pentadecyl acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate, (Meta) acrylic acid ester having a linear, branched or alicyclic hydrocarbon group; acrylonitrile; acrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-octylacrylamide (Meta) acrylamide such as Nt-octylacrylamide; sulfonic acid group-containing (meth) acrylamide such as 2- (meth) acrylamide-2-methylpropanesulfonic acid; aminoethyl (meth) acrylate, t-butylaminoethyl Alkylaminoalkyl (meth) acrylates such as methacrylate and methylaminoethyl (meth) acrylate; Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide , Dialkylaminoalkyl (meth) metaacrylamide such as diethylaminoethyl (meth) acrylamide; cyclic compounds such as tetrahydrofurfurfryl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate and (meth) acrylic Acid esters; (meth) acrylic acid alkoxyalkyl esters such as (meth) ethoxyethyl acrylate, (meth) methoxyethyl acrylate; polyalkylenes such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monoesters of glycol and (meth) acrylic acid; (meth) acrylic ester containing sulfonic acid group; metaacryloyloxyalkyl phosphate monoester such as (meth) acryloyloxyethyl phosphate; glyceryl (meth) acrylic acid, 2 -Metaacryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxy Ethylhexahydrophthalic acid; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene (n = 2-50) glycol di (meth) ) Acrylate, propylene glycol di (meth) acrylate, polypropylene (n = 2 to 50) glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dipentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Trimethylolpropane di (meth) acrylate, methylenebisacrylamide, bisphenol F EO modified (n = 2 to 50) di (meth) acrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, bisphenol S EO modified (n = 2 to 50) n = 2-50) Di (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolhexanetri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, Ditrimethylolethanetetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dimethylolhexanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa ( Examples thereof include (meth) acrylates having two or more ethylenically unsaturated double bonds such as meth) acrylate, trimethylolpropane hepta (meth) acrylate, and trypentaerythritol octa (meth) acrylate.

(Monomers other than (meth) acrylic)
Unsaturated monocarboxylic acids such as crotonic acid; aromatic vinyl compounds such as styrene; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic acid; monoalkyl maleic acid ester, monoalkyl fumarate Monoalkyl esters of unsaturated dicarboxylic acids such as esters and monoalkyl esters of itaconic acid; sulfonic acid group-containing monomers include, for example, vinyl sulfonic acid, alkene sulfonic acid such as (meth) allyl sulfonic acid; α-methylstyrene sulfone. Aromatic vinyl group-containing sulfonic acid such as acid; 1-3-amino group-containing unsaturated compound such as (meth) allylamine; amino group-containing aromatic vinyl compound such as N, N-dimethylaminostyrene; divinylbenzene, di Compounds having two or more ethylenically unsaturated double bonds such as isopropenylbenzene and trivinylbenzene; urethane oligomers having two or more ethylenically unsaturated double bonds; having two or more ethylenically unsaturated double bonds Silicone compounds; vinyl acetate, vinylpyrrolidone and the like are exemplified.

The content of the component (A) in the present invention is preferably 0.01 to 1% by mass (hereinafter, simply abbreviated as "%"), more preferably 0.05 to 0.5%. This range is more preferable in terms of excellent adhesiveness and long-lasting makeup.

The spherical powder of the component (B) used in the present invention is not particularly limited as long as it is usually used for cosmetics, and has an elliptical shape or a part or the whole of a spherical surface having irregularities in addition to a true spherical shape. A substantially spherical one can also be used. In addition, if it is spherical, the whole is composed of a single component, the inner core and the outer shell are composed of different components such as the core-shell type, and the different components are dispersed inside. Hollow powder having a cavity inside, and those containing or impregnating a beneficial component inside can be used without particular limitation. Specific examples thereof include organic powders such as nylon powder, polymethylmethacrylate powder, polyethylene powder and silicone powder, and inorganic powders such as silica powder and aluminosilicate powder. The average particle size of the spherical powder is preferably 3 to 40 μm, more preferably 5 to 30 μm. This range is preferable because it is easy to blur at the time of application and the soft focus effect is excellent. In the present invention, the average particle size is the average value of the width and length of the powder measured in the dispersed state in water using a laser diffraction / scattering type particle size distribution measuring device (average particle having an integrated volume of 50%). Diameter value) is measured. These commercially available products include Olgasol 2002D (average particle size 20 μm, manufactured by Atofina Japan), Matsumoto Microsphere M100 (average particle size 8 μm, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), TOSPERL 145 (average particle size 4.5 μm,). Momentive Performance Materials Japan Co., Ltd.), CHIFFONSIL P-3R (average particle size 5 μm, manufactured by Nikki Catalyst Kasei Co., Ltd.) and hollow SILICA MICRO BEAD BA-1 (average particle size 18 μm, manufactured by Nikki Catalyst Kasei Co., Ltd.) , TOSPERL 150KA (average particle diameter 5 μm, manufactured by Momentive Performance Materials Japan Co., Ltd.) having irregularities on the surface and the like. These may be treated with one or more of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants and the like. ..

The content of the component (B) in the present invention is preferably 3 to 40%, more preferably 5 to 30%. This range is more preferable because it is easy to blur at the time of application and the soft focus effect is excellent.

In the present invention, a silicone resin powder having a silicone powder surface is preferably used because it is easy to blur during coating and has a high soft focus effect. Examples of commercially available products include KSP-100, 101, 105, 300 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), TOSPERL145, 2000B * (above, manufactured by Momentive Performance Materials Japan) and the like. These silicone resin powders are preferably 30% or more, more preferably 60% or more in the component (B), and all of them may be silicone resin powders.

It is preferable that the powdered cosmetic of the present invention further contains the amino-modified silicone-treated powder of the component (C) in terms of cosmetic durability. For the component (C), either the amino-modified silicone is solvent-dispersed and the powder surface is coated, or the powder and the amino-modified silicone are brought into contact with each other and a solvent or the like is used as necessary to coat the powder surface using mechanical force. The method for treating the surface of these powders is not particularly limited, and a known treatment method is usually used. Specific examples thereof include a method of directly mixing with powder, a method of using a solvent such as water, ethanol, isopropyl alcohol, n-hexane, light isoparaffin, benzene and toluene, and a vapor phase method and a mechanochemical method. And so on. Among the mechanochemical methods, a method using a kneader having a mechanism for applying shear shearing force in a shear shearing state such as a lightning crusher, a pressurized kneader, a mix muller, a roller mill, a Banbury mixer, and a stone mill is preferable. ..

A particularly preferable embodiment is a method using a shear shear type low-speed kneader. For example, amino-modified silicone, powder, and a solvent are mixed using a lightning crusher or the like and heated to 70 ° C. to 120 ° C. After that, a method of crushing can be mentioned. Further, as another preferable embodiment, the amino-modified silicone is dissolved in a volatile solvent and then mixed with a powder, and the solvent is dried and removed, or heated to 70 ° C. to 120 ° C. when the solvent is dried and removed, and then dissolved. There is a method of crushing. Of these, an amino-modified silicone-coated powder obtained by mixing the amino-modified silicone and the powder using a shear-shearing low-speed kneader, heating the powder to 70 ° C. to 120 ° C., and then crushing the powder is particularly preferable.

When the powder coated with the amino-modified silicone as described above is heated to about 70 ° C. to 120 ° C., the amino group and the oxygen atom of the siloxane bond in the amino-modified silicone interact more strongly with the powder surface. However, it is preferable because the treatment on the powder surface becomes more uniform, and the moist feeling and the long-lasting makeup are further enhanced. In addition, by kneading with a solvent, the surface of the base material is scratched by strong friction during kneading, and electrostatically adsorbed to the newly exposed active sites, improving the coating on the powder surface. It is preferable because it improves the moist feeling and the durability of makeup.

The amount of the amino-modified silicone of the component (C) to be treated is not particularly limited, but the one treated with 0.1 to 10 parts by mass of the amino-modified silicone with respect to 100 parts by mass of the powder has a light spread and a moist feeling. It is preferable from the viewpoint of adhesiveness to the skin, and more preferably, one treated with 0.5 to 7 parts by mass of amino-modified silicone with respect to 100 parts by mass of the powder is particularly remarkable in their effects.

The powder treated with the component (C) of the present invention is not particularly limited as long as it is usually used for cosmetics, except for the spherical powder of the component (A), and is an inorganic powder or a glittering powder. Examples thereof include body types, organic powders, pigment powders, and composite powders. Specific examples thereof include titanium oxide, zinc oxide, cerium oxide, mica, sericite, talc, kaolin, silicon carbide, barium sulfate, boron nitride and the like, but in the present invention, those treated with mica and talc are preferably used. Be done. Examples of these commercially available products include "Mica Y-2300WA3" (manufactured by Yamaguchi Mica) as treated with mica and "EX-15WA3" (manufactured by Yamaguchi Mica) as treated with talc. .. The component (C) may be treated at the same time as a treatment agent other than the amino-modified silicone of the present application, such as a fatty acid, a metal soap, or a fluorine compound, as long as it does not interfere with the present invention.

The content of the component (C) in the present invention is not particularly limited, but is preferably 1 to 30%, more preferably 3 to 25%. This range is preferable in that it is more excellent in lightness of spreading and spreading and maintenance of moisturizing feeling.

In addition to the above components, the powdered cosmetics of the present invention include oils such as solid oils, semi-solid oils and liquid oils, surfactants, polymers, colorants, powders and ultraviolet absorbers, which are usually used in cosmetics. Preservatives, antibacterial agents, antioxidants, fragrances, beauty ingredients and the like can be appropriately contained within a range that does not interfere with the effects of the present invention.

Examples of the oil agent include liquid paraffin, liquid oil such as squalane, solid oil such as paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax and Fishertropus wax, olive oil, castor oil, jojoba oil, mink oil, macadamian nut oil and the like. Fats and oils, cetyl isooctanate, isopropyl myristate, isopropyl myristate, octyldodecyl myristate, isotridecyl isononanoate, pentaerythlit ester of loginate, cholesterol fatty acid ester, di-lauroyl-L-glutamate (cholesteryl behenyl) Examples thereof include esters such as octyldodecyl), silicone oils such as dimethylpolysiloxane, cyclic silicone, phenyl-modified polysiloxane, fluorine-modified polysiloxane, amino-modified polysiloxane, and alkyl-modified polysiloxane.

Surfactants include stearic acid, lauric acid, myristic acid, bechenic acid, isostearic acid, oleic acid, 12-hydroxystearic acid, poly12-hydroxystearic acid, fatty acid soaps, acylglutamates, alkyl phosphates, Anionic surfactants such as polyoxyalkylene-added alkyl phosphates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, glycerin fatty acid esters and their alkylene glycol adducts, propylene glycol fatty acid esters And alkylene glycol adducts thereof, sorbitan fatty acid esters and alkylene glycol adducts thereof, sugar fatty acid esters, polyoxyalkylene-modified organopolysiloxanes, glycerin-modified organopolysiloxanes and other nonionic surfactants.

Gelling agents include dextrin fatty acid esters, inulin fatty acid esters, organically modified bentonite, fumigant anhydrous silicic acid, aluminum stearate, aluminum isostearate, zinc stearate, magnesium stearate, etc., and polymers include carrageenan and xanthan gum. Methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Examples of ultraviolet absorbers include silicic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, and phenylbenzoimidazole. Derivatives, phenylbenzotriazole derivatives and the like include paraoxybenzoic acid derivatives, preservatives such as phenoxyethanol and alcandiol, and beauty ingredients such as rosemary extract, chamomile extract, collagen, hyaluronic acid and ceramide.

The colorant and powder are not particularly limited by the shape of a plate, a spindle, a needle, etc., the particle size of a fumes, fine particles, pigment grade, etc., and the particle structure of porous, non-porous, etc., and are inorganic. Examples thereof include powders, glittering powders, organic powders, dye powders, and composite powders. Specifically, corn, ultramarine, carbon black, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, titanium oxide, zinc oxide, cerium oxide, mica, sericite, talc, kaolin, silicon carbide, barium sulfate, Inorganic powders such as boron nitride, bright powders such as bismuth oxychloride and aluminum powder, organic powders such as silicone powder and polyethylene powder, organic tar pigments, and dye powders such as rake pigments of organic pigments. , Titanium oxide coated mica, iron oxide treated mica, iron oxide coated mica titanium, organic pigment treated mica titanium dioxide / titanium oxide coated mica, titanium oxide coated glass powder, iron oxide titanium oxide coated glass powder, titanium oxide containing silicon dioxide , Composite powder such as barium sulfate-coated mica titanium, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, etc., and one or more of these can be used. May be treated with one or more of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants and the like.

The powdered cosmetic of the present invention contains powder as a main component, contains 60% or more of powder containing components (B) and (C) in the cosmetic, and has a solid shape and powder. It may be in any shape.

The powdered cosmetic of the present invention can be applied to make-up cosmetics such as foundation, white powder, eye color and eyebrow, and basic cosmetics such as body powder and whitening powder, and preferably the softness of the effect of the present application and the lasting effect of makeup. It is preferably used for make-up cosmetics, which are expected to have a fluffy makeup effect, and is preferably used for eyebrow cosmetics, which are easy to remove makeup in daily life. Examples of the usage include a method of using with a hand or a finger, a method of using with a brush, a puff, a sponge, or the like.

The powdered cosmetic of the present invention can be produced by a commonly known method. Although not particularly limited, the following methods can be mentioned.
A method in which a powder component containing the component (b) and other powders is mixed with an oil agent containing the component (a) and other oils and then crushed into a loose shape, a method in which the powder component is crushed and then dry-compressed. , A powder component containing the component (b) and other powders, an oil agent containing the component (a) and other oils, and a volatile solvent such as light liquid isoparaffin and isododecane are mixed to form a slurry. Examples thereof include a wet molding method in which the volatile solvent is removed after filling and molding.

Hereinafter, the present invention will be described in detail with reference to examples. It should be noted that these do not limit the present invention in any way.
Manufacture of (meth) acrylic silicone-based graft copolymer

[Manufacturing Example 1]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 31 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (4 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 31: 27: 40
(Note 1) IPA Kanto Chemical Co., Ltd. (Note 2) V-601 Wako Pure Chemical Industries, Ltd. (Note 3) X-24-8201 Shin-Etsu Chemical Co., Ltd.
(Note 4) EA Kanto Chemical Co., Ltd. (Note 5) HEMA Kanto Chemical Co., Ltd. (Note 6) MAPTAC Evonik Degussa Japan Co., Ltd., 50% aqueous solution

[Manufacturing example 2]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-22-174DX) (Note 7) 40 g, ethyl acrylate (Note 4) 31 g, 2-hydroxyethyl methacrylate (Note 5) 27 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , 170 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 90 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174DX = 2: 31: 27: 40
(Note 7) X-22-174DX manufactured by Shin-Etsu Chemical Co., Ltd.

[Manufacturing example 3]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-22-174ASX) (Note 8) 40 g, ethyl acrylate (Note 4) 31 g, 2-hydroxyethyl methacrylate (Note 5) 27 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , Isopropanol (Note 1) 50 g was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 83 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174ASX = 2: 31: 27: 40
(Note 8) X-22-174ASX manufactured by Shin-Etsu Chemical Co., Ltd.

[Manufacturing example 4]
In a three-necked flask, under a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40.4 g, ethyl acrylate (Note 4) 27.3 g, 2-hydroxyethyl methacrylate (Note 5) 31.3 g, 3-trimethylammoniumpropylmethacrylamide 2 g of chloride (Note 6) and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 27.3: 31.3: 40.4

[Manufacturing Example 5]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (Note 4) 26 g, 2-hydroxyethyl methacrylate (Note 5) 30 g, 3-trimethylammonium propylmethacrylamide chloride (Note 6) 8 g , 120 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 83 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 4:26:30:40

[Manufacturing example 6]
In a three-necked flask, in a nitrogen atmosphere, 100 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 20 g, ethyl acrylate (Note 4) 41.5 g, 2-hydroxyethyl methacrylate (Note 5) 36.5 g, 3-trimethylammonium propylmethacrylamide chloride (Note 5) Note 6) 4 g and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 41.5: 36.5: 20

[Manufacturing example 7]
In a three-necked flask, under a nitrogen atmosphere, 50 g of isopropanol (Note 1) was stirred, and at 70 to 80 ° C., 4 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2), one end. Methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 50 g, ethyl acrylate (Note 4) 23 g, 2-hydroxyethyl methacrylate (Note 5) 25 g, 3-trimethylammonium propyl methacrylamide chloride (Note 6) 4 g , 100 g of isopropanol (Note 1) was added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in IPA was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 96 g of a transparent rubber-like substance.
From the infrared absorption spectrum, it was confirmed that the obtained rubber-like material was the target (meth) acrylic silicone-based graft copolymer.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2: 23: 25: 50

[Manufacturing Example 8]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 31 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , DADMAC (Note 9) 3.34 g and Isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The charging ratio of the monomer is as follows.
DADMAC: EA: HEMA: X-24-8201 = 2: 31: 27: 40
(Note 9) DADMAC Tokyo Chemical Industry Co., Ltd., 60% aqueous solution

[Manufacturing example 9]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 30 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 27 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 6 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 89 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 3:30:27:40

[Manufacturing Example 10]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 35 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propyl methacrylamide chloride (MAPTAC) (Note 6) 6 g and isopropanol (Note 1) 50 g were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 3:35:32:30

[Manufacturing Example 11]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 36 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (4 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 2:36:32:30

[Manufacturing Example 12]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 30 g, ethyl acrylate (EA) (Note 4) 37 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (2 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 90 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 10 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1:37:32:30

[Manufacturing Example 13]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-22-174DX) (Note 7) 30 g, ethyl acrylate (EA) (Note 4) 36 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 32 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (4 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 86 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 11 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-22-174DX = 2: 36: 32: 30

[Manufacturing Example 14]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 16 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 42 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (2 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 91 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 30 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 16.2: 42.4: 40.4

[Manufacturing Example 15]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 40 g, ethyl acrylate (EA) (Note 4) 27 g, 2-hydroxyethyl methacrylate (HEMA) (Note 5) 31 g , 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6) (2 g) and isopropanol (Note 1) (50 g) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 88 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is 15 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 27.3: 31.3: 40.4

[Manufacturing Example 16]
Dimethyl 2,2-azobis (2-methylpropionate) (V-601) at 70-80 ° C. with stirring 100 g of isopropanol (IPA) (Note 1) in a three-necked flask in a nitrogen atmosphere. (Note 2) 4 g, one-ended methacrylate-substituted dimethylpolysiloxane (X-24-8201) (Note 3) 20.2 g, ethyl acrylate (EA) (Note 4) 65.7 g, 2-hydroxyethyl methacrylate (HEMA) ( Note 5) 13.1 g, 2 g of 3-trimethylammonium propylmethacrylamide chloride (MAPTAC) (Note 6), and 50 g of isopropanol (Note 1) were added over 3 to 4 hours. Next, 1 g of dimethyl 2,2-azobis (2-methylpropionate) (Note 2) dissolved in isopropanol was added and reacted in a temperature range of 70 to 80 ° C. for 5 hours to obtain a viscous solution. .. This solution was poured into purified water to precipitate a graft polymer, and then the precipitate was separated by filtration and dried under reduced pressure at 80 ° C. to obtain 87 g of a transparent rubber-like substance.
Infrared absorption spectrum confirmed that the obtained rubber-like product was the target (meth) acrylic silicone-based graft copolymer (this product was dimethylpolysiloxane, amide bond by infrared absorption spectrum). , It was confirmed that the polymer has an ester bond, an alkyl group, and a hydroxyl group).
The glass transition temperature (Tg) theoretically calculated from EA and HEMA is −10 ° C.
The charging ratio of the monomer is as follows.
MAPTAC: EA: HEMA: X-24-8201 = 1: 65.7: 13.1: 20.2

Examples 1-14 and Comparative Examples 1-4: Eyebrow (solid)
Eyebrow with the formulation shown in Table 1 below was prepared, and the ease of blurring, soft focus effect, adhesiveness, and makeup persistence were evaluated by the following methods. The results are also shown in Table 1.

* 1: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 2: TOSPEARL 2000B * (manufactured by Momentive Performance Materials Japan)
* 3: KSP-102 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 4: Silicon KF-96 (6CS) (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5: KP-561P (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 6: Silicon KP-545
(30% solid content decamethylcyclopentasiloxane solution, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. 1 to 13 are uniformly mixed with a super mixer.
B. Dissolve 14 to 23 uniformly.
C. B is added to A and uniformly dispersed.
D. C was crushed and press-molded into a gold plate to obtain an eyebrow.

(Evaluation methods)
The following evaluation items (a) to (d) were evaluated by the following methods.
(Evaluation item)
I. Ease of blurring b. Soft focus effect c. Adhesiveness 2. Makeup persistence

We asked 20 specialized panels to apply the sample, and each of them had the following criteria for each item of "easiness to blur", "adhesion", "soft focus effect" as a finish, and "makeup persistence". According to the above, the evaluation was made on a 5-point scale, a score was given to each sample, and the average score of the scores of all panels was judged according to the following criteria. The "soft focus effect" is whether or not a soft makeup effect is obtained while having a coloring effect on the eyebrows, and the "makeup lasting" is the state immediately after applying eyebrow and 6 hours after daily life. It was compared with the condition and evaluated.
<Absolute evaluation criteria>
(Score): (Evaluation)
4: Very good 3: Good 2: Normal 1: Bad 0: Very bad <Criteria>
(Judgment): (Average score)
◎: More than 3.5 points: Very good ○: More than 2.5 points and less than 3.5 points: Good △: More than 1 point and less than 2.5 points: Slightly bad ×: 1 point or less: Bad

As is clear from the results in Table 1, Examples 1 to 14, which are the products of the present invention, have "easiness of blurring", "adhesiveness" at the time of application, "soft focus effect" as a finish, and "makeup lasting". It was an excellent powder cosmetic for all items of "sex". In addition, the effect of increasing the volume of eyebrows was also obtained.
On the other hand, Comparative Example 1 containing no spherical powder of the component (b) was difficult to blur when applied, had poor adhesion, and was not satisfactory in the soft focus effect of the finish and the long-lasting makeup. Further, Comparative Example 2 containing the spherical powder of the component (b) but not containing the (meth) acrylic silicone-based graft copolymer having the cationic property of the component (a) and, instead, having no cationic property (Acrylates). In Comparative Example 3 and Comparative Example 4 in which the / stearyl acrylate / dimethicone methacrylate) copolymer and the (Acrylate / dimethicone) copolymer were replaced, the adhesiveness, the soft focus effect, and the long-lasting makeup were not satisfactory.

Example 15: Foundation A foundation was produced by the following formulation and manufacturing method.
(Ingredient) (%)
1. 1. (Dimethicone / Meticone silsesquioxane) Crosspolymer * 1 10.0
2. 2. Spherical silica (average particle size 5 μm) 1.5
3. 3. Spherical nylon (average particle diameter 7 μm) 1.0
4. Spherical polymethylmethylmethacrylate crosspolymer (average particle size 6 μm) 2.5
5. Lecithin 0.1% treated titanium oxide 8.0
6. Hydrogen Dimethicone 0.75% Treated Zinc Oxide * 7 2.5
7. Triethoxycaprylylsilane 2% treated red iron oxide 1.1
8. Triethoxycaprylylsilane 2% treated yellow iron oxide 1.4
9. Triethoxycaprylylsilane 2% treated black iron oxide 0.2
10. Talc remaining amount 11. Mica 25.0
12. Amino-modified silicone 1% treated mica 2.5
13. Synthetic phlogopite 3.0
14. Boron Nitride 2.0
15. Methyl paraoxybenzoate 0.2
16. Dimethylpolysiloxane * 4 1.5
17.2-Cetyl ethylhexanoate 3.0
18. Ethylhexyl methoxycinnamate 5.5
19. Ethanol 0.5
20. (Meta) Acrylic Silicone Graft Copolymer of Production Example 2 0.2

* 7: XZ-300F-LP (manufactured by Sakai Chemical Industry Co., Ltd.)

(Production method)
A. 1 to 15 are uniformly mixed with a super mixer.
B. 16 to 20 are uniformly mixed and dissolved.
C. Add B to A and mix uniformly.
D. C was crushed and press-molded into a gold plate to obtain a foundation.

The obtained foundation was a foundation excellent in "spreading and spreading" at the time of application, "adhesiveness", "soft focus effect" as a finish, and "makeup durability".

Example 16: Loose white powder A loose white powder was produced by the following formulation and manufacturing method.
(Ingredient) (%)
1. 1. (Dimethicone / Meticone silsesquioxane) Crosspolymer * 1 25.0
2. 2. Spherical polymethylmethyl methacrylate crosspolymer (average particle size 6 μm) 10.0
3. 3. Lecithin 0.1% treated titanium oxide 1.0
4. Red No. 226 0.04
5. Talc remaining amount 6. Mica 15.0
7. Synthetic phlogopite 10.0
8. Boron Nitride 5.0
9. N-lauroyl-L-lysine 5.0
10. Phenoxyethanol 0.2
11. Dimethylpolysiloxane * 4 0.2
12. 2-Ethyl hexane hydroxystearate 0.2
13. Ethanol 0.5
14. (Meta) Acrylic Silicone Graft Copolymer of Production Example 2 0.2

(Production method)
A. 1 to 9 are uniformly mixed with a super mixer.
B. 10 to 14 are uniformly mixed and dissolved.
C. Add B to A and mix uniformly.
D. C was crushed and filled in a container to obtain a loose white powder.

The obtained loose white powder was a white powder having excellent "spreading and spreading", "adhesiveness", "soft focus effect" as a finish, and "makeup durability" at the time of application.

Example 17: Body powder A body powder was produced by the following formulation and manufacturing method.
(Ingredient) (%)
1. 1. Spherical silica (average particle diameter 5 μm) 8.5
2. 2. Spherical nylon (average particle diameter 7 μm) 1.0
3. 3. Hydrogen dimethicone 5% treated Zinc oxide (particle size 300 nm) 10.0
4. Red iron oxide 0.2
5. Yellow iron oxide 0.4
6. Black iron oxide 0.05
7. Triethoxycaprylylsilane 2% treated talc Remaining amount 8. Mica 25.0
9. 6% Zinc Laurate Treatment Sericite 5.0
10. Amino-modified silicone 3% treated mica 3.0
11. Synthetic phlogopite 11.0
12. Boron Nitride 2.0
13. Methyl paraoxybenzoate 0.2
14. Isotridecyl isononanoate 3.5
15. Ethylhexyl methoxycinnamate 2.0
16. Ethanol 0.5
17. (Meta) Acrylic Silicone Graft Copolymer of Production Example 2 0.2
18. Fragrance 1.0

(Production method)
A. 1 to 13 are uniformly mixed with a super mixer.
B. 14 to 18 are uniformly mixed and dissolved.
C. Add B to A and mix uniformly.
D. C was crushed and press-molded into a gold plate to obtain a body powder.

The obtained body powder was a body powder having excellent "spreading and spreading", "adhesiveness", "soft focus effect" as a finish, and "makeup durability" at the time of application.

Example 18: Cheek Cheek was produced by the following formulation and manufacturing method.
(Ingredient) (%)
1. 1. (Dimethicone / Meticone silsesquioxane) Crosspolymer * 1 2.0
2. 2. Spherical silica (average particle size 5μ) 2.0
3. 3. Red No. 226 0.04
4. Red No. 202 0.25
5. Dimethicone 2% treated talc Remaining amount 6. Mica 5.0
7. Sericite 10.0
8. Amino-modified silicone 1% treated mica 3.0
9. Dimethicone 2% treated synthetic phlogopite 11.0
10. Boron Nitride 5.0
11. Mica Titanium * 8 14.0
12. Barium sulphate 3.0
13. Methyl paraoxybenzoate 0.3
14. Sorbitan sesquiisostearate * 9 0.15
15. Liquid paraffin * 10 10.0
16. Vaseline 5.5
17. Diethylhexyl succinate 1.5
18. Dimethyl distearyl ammonium hecto 1.0
19. Ethanol 1.0
20. (PEG-15 / Lauryl Dimethicone) Cross Polymer 1.5
21. (Meta) Acrylic Silicone Graft Copolymer of Production Example 2 0.2
22. Fragrance 1.0

* 8: FLAMENCO SPARKLE RED 420J (manufactured by BASF)
* 9: Cosmall 182 (manufactured by Nisshin Oillio)
* 10: KLEAROL WHITE MINERAL OIL (manufactured by SONNEBORN)

(Production method)
A. 1 to 13 are uniformly mixed with a super mixer.
B. 14 to 22 are mixed uniformly.
C. Add B to A and mix uniformly.
D. 30 parts by mass of isododecane as a solvent is added to 100 parts by mass of C and mixed to form a slurry.
E. After filling and molding D, isododecane was removed to obtain teak.

The obtained cheeks were excellent in "easiness to blur", "adhesiveness", "soft focus effect" as a finish, and "makeup durability" at the time of application.

Example 19: Eye color An eye color was produced by the following formulation and manufacturing method.
(Ingredient) (%)
1. 1. Spherical polymethylmethyl methacrylate crosspolymer (average particle size 6 μm) 4.0
2. 2. Yellow iron oxide 2.0
3. 3. Black iron oxide 0.5
4. Boron Nitride 5.0
5. Dimethicone 2% treated talc 15.0
6. Mica remaining amount 7. Amino-modified silicone 1% treated mica 3.0
8. Mica Titanium * 11 15.0
9. Titanium oxide coated synthetic phlogopite * 12 5.0
10. Titanium oxide coated glass powder * 13 3.0
11. Dimethylpolysiloxane 2% treated synthetic phlogopite 11.0
12. Boron Nitride 5.0
13. Methyl paraoxybenzoate 0.3
14. Barium sulphate 3.0
15. Dimethylpolysiloxane (10CS) 5.0
16. Sorbitan sesquiisostearate * 9 1.0
17. Diisostearyl malate 7.0
18. Ethanol 0.5
19. (Meta) Acrylic Silicone Graft Copolymer of Production Example 2 0.2

* 11: FLAMENCO GOLD 220C (manufactured by BASF)
* 12: HELIOS R300S (manufactured by Topy Industries, Ltd.)
* 13: Microglass Metashine MBE025RB (manufactured by Nippon Sheet Glass)

(Production method)
A. Ingredients 1-14 are uniformly mixed with a super mixer.
B. 15 to 19 are mixed uniformly.
C. Add B to A and mix uniformly.
D. C was crushed and press-molded into a gold plate to obtain an eye color.

The obtained eye color was excellent in "spreading and spreading" at the time of application, "adhesiveness", "soft focus effect" as a finish, and "makeup durability".

Claims (5)

The following components (A) and (B);
(A) A (meth) acrylic silicone-based graft copolymer which is a reaction product of the following radically polymerizable monomers (a), (b), (c) and (d);
(A) The following general formula (I)
(In the formula, Me is a methyl group, R1 is a hydrogen atom or a methyl group, R2 may contain one or two ether bonds, and is a linear or branched chain having 1 to 10 carbon atoms. Saturated hydrocarbon group, R3 is a saturated hydrocarbon group having 1 to 10 carbon atoms, m represents an integer of 5 to 100.) Compound (b) The following general formula (II)
(In the formula, R4 may be a hydrogen atom or a methyl group, R5, R6, R7 may be the same or different, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is -O-, -NH-, -O. -CH2- or -O-CH2CH (OH)-, Y is a linear or branched divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and Z- is a counter anion). Compounds and formula (III)
(In the formula, R8 and R9 may be the same or different, hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R10 and R11 may be the same or different, and hydrogen atoms or alkyls having 1 to 18 carbon atoms. The group, Z-represents a counter anion.) At least one selected from the compounds represented by (c) the following general formula (IV).
(In the formula, R12 represents a hydrogen atom or a methyl group, and R13 represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.) Compound (d) The following general formula (V) )
(In the formula, R14 represents a hydrogen atom or a methyl group, and R15 represents a hydroxyalkyl group having 1 to 4 carbon atoms.) A powder cosmetic containing a compound (B) spherical powder represented by the compound (B). The powder cosmetic according to claim 1, wherein the component (A) is a (meth) acrylic silicone-based graft copolymer further having a repeating unit derived from a (meth) acrylic acid derivative other than (a) to (d). Fee. The powder cosmetic according to any one of claims 1 or 2, wherein the component (B) contains a silicone resin powder. The powder cosmetic according to any one of claims 1 to 3, further comprising the component (C) amino-modified silicone-treated powder. The powdered cosmetic according to any one of claims 1 to 4, wherein the powdered cosmetic is eyebrow.