JP7091059B2 - Powder cosmetics - Google Patents

Description

The present invention relates to powdered cosmetics, and more particularly to improving the feeling of use on the skin and improving the moldability and drop stability of powdered cosmetics by using an elastomer-coated inorganic powder and silicone powder.

Various powder treatments are performed to obtain the functions required for makeup cosmetics such as foundations and makeup bases.
For example, in order to have excellent hydrophobicity and improve washability, a hydrophobic treatment agent and an acrylic monomer having a specific structure (11-methacrylamide undecanoic acid, etc.) are contained as constituent monomers on the surface of the base powder. A powder coated with a polymer has been known (Patent Document 1).

In addition, in order to provide powdered cosmetics that have excellent makeup retention (prevention of makeup disintegration), in particular, powder makeup cosmetics such as foundations or makeup bases, by blending a specific treated powder, makeup retention (prevention of makeup disintegration) ) Was known to provide excellent powdered cosmetics (Patent Document 2).

Special table 2007-277167 Japanese Patent Application Laid-Open No. 2008-184399

However, when the treated inorganic powder taught in Patent Documents 1 and 2 is blended in cosmetics and applied to the skin, it gives the skin a squeaky feel and gives a powdery feel to the skin. There was a problem that there was a case.
Further, it has been known that a silicone powder is blended in order to improve the feeling of use, but the improvement of the moldability and the drop stability of the powdered cosmetic is insufficient.
The present invention has been made in view of the above circumstances, and by using an inorganic powder whose surface is coated with a specific elastomer and a silicone powder in combination, the feel of powdered cosmetics on the skin is improved and the powder is moist and powdery. The purpose is to give you a feeling that you don't have. Another object of the present invention is to provide a powdered cosmetic having excellent drop stability.

（一般式（１）中、Ｘは炭素数１～１８のアルキル基、Ｒ，Ｒ’はアルキレン基である（ただし、Ｒがメチレン基の時を除く）。ｍは２０～２０００、ｎは１～１００である。）

（式中Ｒ¹及びＲ²は、メチル基若しくは下記の（４）で表される基を示し、該基を１分子中に１～１００含有し、ｙは１～５０，０００の整数を表す。）

As a result of diligent studies to solve the above problems, the present inventors have a composition having an elastomeric property in which a silicone polymer having an amino group and a silicone polymer having a carboxyl group or an acrylic polymer having a carboxyl group are combined. The inorganic powder was coated with. Then, it was found that by using the inorganic powder coated with the elastomer and the silicone powder in the powder cosmetic, the powder cosmetic improves the feel to the skin and gives a moist and non-powdered sensation. Furthermore, they have found that a cosmetic having excellent drop stability can be obtained, and have completed the present invention.
The powdered cosmetic according to the present invention contains (A) 5 to 70% by mass of an inorganic powder having an elastomer coating layer containing the following (a1) and (a2), and (B) 1 to 20% by mass of a silicone powder. It is characterized by that.
Further, it is an elastomer composed of (a1) a silicone polymer having an amino group and (a2) a silicone polymer having a carboxyl group or an acrylic polymer having a carboxyl group, and the molar ratio of the amino group to the carboxyl group is Y /. It is characterized in that X = 0.1 to 1.2 (Y is the molar amount of the carboxyl group contained in the component (a2), and X is the molar amount of the amino group contained in the component (a1)). do.
Further, in the powder cosmetics, the amount of the elastomer is preferably 0.5 to 20% by mass with respect to the amount of the inorganic powder.
Further, in the powder cosmetic, the component (a1) is a silicone polymer having an amino group represented by the following general formula (1), and a silicone polymer.
(A2) A silicone polymer having a carboxyl group having the following general formula (2) or an acrylic polymer having a carboxyl group having the following general formula (3) is preferable.
( A1 ) A silicone polymer having an amino group having the following general formula (1) and
( A2 ) A silicone polymer having a carboxyl group having the following general formula (2) or an acrylic polymer having a carboxyl group having the following general formula (3),
It is an elastomer composed of, and the molar ratio of amino group to carboxyl group is Y / X = 0.1 to 1.2 (Y is the molar amount of carboxyl group contained in the component (B), and X is (A). ) The molar amount of amino groups contained in the component) is preferably in the range.

(In the general formula (1), X is an alkyl group having 1 to 18 carbon atoms, R and R'are alkylene groups (except when R is a methylene group). M is 20 to 2000 and n is 1. ~ 100. )

(In the formula, R ¹ and R ² indicate a methyl group or a group represented by (4) below, and 1 to 100 of the group is contained in one molecule, and y represents an integer of 1 to 50,000. .)

According to the present invention, when an inorganic powder having the elastomer coating layer and a silicone powder are used for powder cosmetics, the feel on the skin is improved and the powder has a moist and non-powder sensation. Then, it is possible to provide a cosmetic having excellent drop stability.

Hereinafter, the present invention will be described in detail.
(A) Inorganic powder having an elastomer coating layer The inorganic powder having an elastomer coating layer used in the present invention is obtained by mixing (a1) a silicone polymer having an amino group and (a2) a silicone polymer having a carboxyl group and heating the mixture. This is an elastomer produced by coating the surface of an inorganic powder. First, the constituent components (a1) and (a2) of the elastomer used in the present invention will be described.

(A1) Silicone Polymer Having an Amino Group The (a1) silicone polymer having an amino group used in the present invention is a side chain type amino-modified silicone represented by the following general formula (1).

（一般式（１）中、Ｘは炭素数１～１８のアルキル基、Ｒ，Ｒ’はアルキル基である。）

(In the general formula (1), X is an alkyl group having 1 to 18 carbon atoms, and R and R'are alkyl groups.)

In the general formula (1), m is preferably 20 to 2000 because the hardness of the obtained elastomer is preferable. If it is less than 20, it is not preferable in that it may not form an elastomer. Further, if it exceeds 2000, it may cause difficulty in handling and manufacturing, which is not preferable.

In the general formula (1), n is preferably 1 to 100 because the hardness of the obtained elastomer is preferable. If it is less than 1, it may not be preferable in that it may not form an elastomer. Further, if it exceeds 100, it may not be preferable in that the elastomer may be too hard.

In the general formula (1), an alkyl chain is preferably used for R, and a propyl group is preferable because of mass productivity.
In the general formula (1), an alkyl chain is preferably used for R', and an ethyl group is preferable because of mass productivity.

(A1) The amino group equivalent of the silicone polymer having an amino group is preferably 500 g / mol to 20000 g / mol because the hardness of the obtained elastomer is preferable. If the amino group equivalent is less than 500, the elastomer may be too hard, which is not preferable. Further, if the amino group equivalent exceeds 20000, an elastomer may not be formed, which is not preferable.

(A1) Commercially available products of silicone polymers having an amino group include, for example, KF-8004, KF-8005S, KF-867S (manufactured by Shin-Etsu Chemical Co., Ltd.), XF42-B1989 (manufactured by MOMENTIVE), ADM1650, ADM1370 (Asahi Kasei). Wacker Silicone Co., Ltd.), SF8452C, SS3551 (Toray Dow Corning Co., Ltd.) and the like.

The amino group equivalent represents a numerical value representing the weight of the substance per mol of the amino group with respect to the substance containing the amino group.

(A2) Silicone polymer having a carboxyl group or acrylic polymer having a carboxyl group As the (a2) silicone polymer having a carboxyl group used in the present invention, the carboxyl group equivalent represented by the following general formula (2) is 1000 g / mol. It is a side chain type carboxyl-modified silicone having a weight of about 40,000 g / mol.
The (a2) carboxyl group-containing acrylic polymer used in the present invention is a side-chain type carboxyl-modified acrylic polymer having a carboxyl group equivalent of 200 g / mol to 1000 g / mol represented by the following general formula (3).

The above-mentioned carboxyl group equivalent represents a numerical value representing the weight of the substance per mol of the carboxyl group with respect to the substance containing the carboxyl group.

The general formula (2) is composed of the following chemical formula 2 and chemical formula 3.

（式中Ｒ1及びＲ2は、メチル基若しくは下記の［化３］で表される基を示し、該基を１分子中に１～１００含有し、ｙは１～５０，０００の整数を表す。）

(In the formula, R1 and R2 represent a methyl group or a group represented by the following [Chemical formula 3], and 1 to 100 of the group is contained in one molecule, and y represents an integer of 1 to 50,000. )

The general formula (3) is composed of the following chemical formula 4.

（一般式（３）中、m/(m+n) = 0～0.5である。）

(In the general formula (3), m / (m + n) = 0 to 0.5.)

Examples of commercially available products of the silicone polymer having a carboxyl group represented by the general formula (2) include Sensorcil PCA (manufactured by Croda International).

The acrylic polymer having a carboxyl group represented by the general formula (3) can be synthesized by a known method.
Specific examples include 12-methacrylamide dodecanoic acid (MAD) / 2-acrylamide-2-methylpropanesulfonic acid (AMPS) copolymer (90/10), 12-methacrylamide dodecanoic acid (MAD) 18.50 g (65). .37 mmol), 2-acrylamide-2-methylpropanesulfonic acid (AMPS: manufactured by Sigma-Aldrich Japan) 1.50 g (7.24 mmol), sodium hydroxide 0.29 g (7.25 mmol), azobisisobuty 0.30 g (1.83 mmol) of ronitrile (manufactured by Nakaraitesk) was dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol according to a conventional method. Argon was bubbled for 60 minutes to degas, the container was covered with septum, and the mixture was heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. After drying under reduced pressure, 15.2 g of a random MAD / AMPS copolymer (90/10) was obtained (yield: 75.1%). The weight average molecular weight was 50,000.

The carboxyl group equivalent of the component (a2) is preferably 200 to 40,000 because the hardness of the obtained elastomer is preferable. If it is less than 200, the elastomer may be too hard, which is not preferable. Further, if it exceeds 40,000, it may not form an elastomer, which is not preferable.

The molar ratio of the amino group in the silicone polymer having (a1) amino group to the carboxyl group of (a2) the silicone polymer having a carboxyl group or the acrylic polymer having a carboxyl group is Y / X = 0.1 to 1.2. (Y is the molar amount of the carboxyl group contained in the component (a2), and X is the molar amount of the amino group contained in the component (a1)). More preferably, it is 0.1 to 0.8. If it is less than 0.1, it may not form an elastomer, which is not preferable. Further, if it is larger than 1.2, it may not form an elastomer, which is not preferable.

The above elastomer is coated on the surface of the inorganic powder. When an inorganic powder coated with an elastomer is used for cosmetics, it improves the feel on the skin and has a moist and non-powdered sensation. In addition, it is possible to obtain a cosmetic having excellent drop stability.

The amount of the elastomer is 0.5 to 20% by mass, more preferably 1 to 15% by mass with respect to the inorganic powder. If it is blended in an amount of more than 20% by mass, it is not preferable because it may cause fusion of inorganic powder and deterioration of moldability of powdered cosmetics. Further, if the blending amount is less than 0.5% by mass, the effect of improving the feel may not be obtained, which is not preferable.

The blending amount of the inorganic powder having the elastomer coating layer is 5 to 70% by mass, more preferably 20 to 50% by mass, based on the powder cosmetic. If it is blended in an amount of more than 70% by mass, other ingredients normally required for powder cosmetics cannot be blended and the function may be inferior, which is not preferable. Further, if the blending amount is less than 5% by mass, the effect of improving the feeling of use may not be obtained, which is not preferable.

As the inorganic powder coated with the elastomer, a powder material that can be used in cosmetics is selected. Of these, talc, mica, sericite, kaolin, titanium oxide, iron oxide, zinc oxide and the like are preferably used.

Examples of commercially available talc include JET-R series (manufactured by Asada Flour Milling Co., Ltd.), Micro Ace series (manufactured by Nippon Talc Co., Ltd.), FL108, FG106, MG115, RL217 manufactured by Fuji Talc Co., Ltd. and the like. Examples of mica include PDM series, PDM-L series, and PDM-FE manufactured by Topy Industries, Ltd.

Inorganic powder having (A) elastomer coating layer used in the present invention by a step of mixing the inorganic powder and (a1) a silicone polymer having an amino group and a step of mixing (a2) a silicone polymer having a carboxyl group and heating. Can be obtained.

(A) The inorganic powder having an elastomer coating layer can be obtained by a known method for producing a coating powder. To give a specific example, an inorganic powder and a silicone polymer having an amino group (a1) are added to a henshal mixer and mixed at a low speed for 10 minutes. Then, (a2) a silicone polymer having a carboxyl group is added thereto, mixed at a low speed for 10 minutes, and heated to obtain an elastomer-coated inorganic powder used in the present invention.
Further, even if the order of addition of the component (a1) and the component (a2) is reversed, an inorganic powder having an elastomer coating layer used in the present invention can be obtained.

(B) Silicone powder The blending amount of the (B) silicone powder is 1 to 20% by mass, more preferably 2 to 10% by mass, based on the powdered cosmetics. If it is blended in an amount of more than 20% by mass, the drop stability may be inferior, which is not preferable. Further, if the blending amount is less than 1% by mass, the effect of improving the feeling of use may not be obtained, which is not preferable.

Examples of the commercially available silicone powder (B) include KSP series (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil series (manufactured by Toray Dow Corning Co., Ltd.), and Tospearl series (manufactured by Momentive Co., Ltd.).

In addition to (A) the inorganic powder having an elastomer coating layer and (B) the silicone powder used in the present invention, an inorganic powder or an organic powder that can be used in cosmetics may be blended.

Inorganic powders include, for example, boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, kaolin, bentonite, smectite, calcium carbonate, magnesium carbonate, calcium phosphate, silicic acid anhydride, magnesium oxide, etc. Tin oxide, iron oxide, yttrium oxide, chromium oxide, titanium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, dark blue, ultramarine, calcium phosphate, aluminum hydroxide, barium sulfate, magnesium sulfate, silicic acid, Aluminum magnesium silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, magnesium aluminate, magnesium aluminometasilicate, chlorhydroxyaluminum , Clay, zeolite, hydroxyapatite, ceramic powder, spinel, mulite, cordierite, aluminum nitride, titanium nitride, silicon nitride, lantern, samarium, tantalum, terbium, europium, neodium, Mn-Zn ferrite, Ni-Zn ferrite, silicone Carbite, cobalt titanate, barium titanate, iron titanate, lithium cobalt titanate, cobalt aluminate, tin oxide containing antimon, indium oxide containing tin, magnetite, aluminum powder, gold powder, silver powder, platinum powder, copper powder, noble metal colloid , Iron powder, zinc powder, cobalt blue, cobalt violet, cobalt green, low-order titanium oxide, fine particle titanium oxide, butterfly-like barium sulfate, petal-like zinc oxide, tetrapod-like zinc oxide, fine particle zinc oxide, oxidation as a pearl pigment Titanium-coated mica, titanium oxide-coated mica, titanium oxide-coated synthetic mica, titanium oxide-coated silica, titanium oxide-coated synthetic mica, titanium oxide-coated talc, zinc oxide-coated silica, titanium oxide-coated colored mica, red iron oxide-coated mica, red iron oxide, black Examples thereof include iron oxide-coated mica titanium, carmine-coated mica titanium, and silica-coated mica titanium.
Of these, boron nitride, mica, sericite, kaolin, titanium oxide, iron oxide, zinc oxide and the like are preferably used.

Examples of commercially available products of these inorganic powders include IRIODIN (registered trademark) series, TIMIRON (registered trademark) series, COLORONA series (registered trademark) series, DICHRONA (registered trademark) series, and XIRONA (registered trademark) series of MERCK. RONASTAR (registered trademark) series, BASF's DESERTREFLEECTIONS series, TIMICA series, FLAMENCO series, CLOIZENNE series, DUOCROME series, GEMTONE series, CELLINI series, MEARLMAID series, REFLECKS series, CHROMA-LITE series Registered Trademark) Series, VISIONAIRE (Registered Trademark) Series, MIRAGE Series, Metashine (Registered Trademark) of Nippon Ita Glass Co., Ltd., PROMINENCE (Registered Trademark) of Nippon Koken Co., Ltd. Examples include the Precioso White PeartesmarkPiments series and the like. Effect pigments such as aluminum flakes, silica flakes, alumina flakes, glass flakes, red iron oxide coated mica, carmine, titanium oxide coated borosilicate (sodium / calcium), titanium oxide coated borosilicate (calcium / aluminum), bismuth oxychloride, fish scale foil , Stainless powder, Tourmaline powder, Gem crushed powder such as sapphire and ruby, Mango violet, Glass fiber, Carbon fiber, Silicon carbide fiber, Alumina fiber, β-Wollastonite, Zonolite, Potassium titanate fiber, Aluminum borate fiber , Basic magnesium sulfate fiber, silicon nitride fiber and the like.

Organic powder (polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder (eg, methylmethacrylate crosspolymer), polystyrene powder, styrene and acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluorination Ethylene powder, cellulose powder, etc.); Organic pigments such as zirconium, barium or aluminum lake (eg, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red Examples thereof include organic pigments such as 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404.

<Drywall manufacturing method>
Inorganic powder components, oily components and other components are mixed in advance with a Henschel mixer and then crushed twice with a palperizer. Then, the obtained mixture is filled in a resin inner dish container, dry press-molded by a known method, and a solid powder obtained by blending an inorganic powder having an elastomer coating layer of the present invention and a silicone powder in a cosmetic. You can get cosmetics.

<Other manufacturing methods>
As a method for producing by blending an inorganic powder having an elastomer coating layer and a silicone powder of the present invention with a cosmetic, a known method can be used. For example, the production method for producing by drying a slurry using a volatile solvent according to Patent No. 542209, and the production method for producing by filling and removing the slurry using a volatile solvent according to Patent No. 5972437. It can be preferably obtained.

In this technology, all inorganic powders and organic powders contained in cosmetics can be coated with an elastomer at once, and other oils can be added to obtain cosmetics. That is, all the inorganic powders and organic powders in the cosmetics are mixed in advance, an elastomer-forming oil is added to the obtained mixed powder and heated to obtain an elastomer-coated mixed powder, and then other than (a1) and (a2) are obtained. By blending the oil content, a cosmetic having an excellent feel and drop resistance was obtained.

On the other hand, the elastomer-forming oils (a1) and (a2) used in the present technique are added together with other oils, and the function of the present invention cannot be obtained in the heating step.
That is, when inorganic powder and organic powder in cosmetics are mixed, (a1) and (a2) and other oils are mixed and added, and heated, the cosmetics are inferior in both feel and drop resistance. turn into.

The oils other than (a1) and (a2) can be contained in a qualitative and quantitative range that does not impair the effects of the present invention. Liquid fats and oils, solid fats and oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, silicones, moisturizers, water-soluble polymers, thickeners, film agents, UV absorbers, metal ion sealants, lower alcohols, multivalent Alcohol, sugar, amino acids, organic amines, high molecular weight emulsions, pH adjusters, skin nutrients, antioxidants, antioxidant aids, and fragrances are appropriately blended as needed, and a conventional method is used according to the desired dosage form. Can be manufactured by

Liquid fats and oils include, for example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, and flaxseed oil. , Saflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin and the like.
Examples of solid fats and oils include coconut oil, palm oil, horse fat, hardened palm oil, palm oil, beef fat, sheep fat, hardened beef fat, palm kernel oil, pork fat, beef bone fat, mokurou kernel oil, hardened oil, and beef. Examples include leg fat, mokurou, and hydrogenated castor oil.

Examples of waxes include honey wax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibotarou, whale wax, montan wax, nukarou, lanolin, capoc wax, lanolin acetate, liquid lanolin, sugar cane, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin. , Jojobaro, hard lanolin, serrac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether and the like.
Examples of the hydrocarbon oil include liquid paraffin, zokerite, squalane, pristane, paraffin, selecin, squalene, petrolatum, microcrystalline wax and the like.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tortic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid ( DHA) and the like.

Higher alcohols include, for example, linear alcohols (eg, lauryl alcohols, cetyl alcohols, stearyl alcohols, behenyl alcohols, myristyl alcohols, oleyl alcohols, cetostearyl alcohols, etc.); branched chain alcohols (eg, monostearyl glycerin ethers (batyl alcohols). ), 2-Deciltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.) and the like.
Synthetic ester oils include isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate. , Lanolin acetate, Isocetyl stearate, Isocetyl isostearate, Cholesteryl 12-hydroxystearate, Di-2-ethylhexanoate ethylene glycol, Dipentaerythritol fatty acid ester, Monoisostearate N-alkylglycol, Dicaprate neopentylglycol, Apple Diisostearyl Acid, Di-2-Heptylundecanoate Glycerin, Tri-2-ethylhexanoate Trimethylol Propane, Triisostearate Trimethylol Propane, Tetra-2-ethylhexanoate Pentaerythritol, Tri-2-ethylhexanoate Glycerin , Trioctanoate glycerin, triisopalmitate glycerin, triisostearate trimethylolpropane, cetyl 2-ethylhexanoate, 2-ethylhexylpalmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl Ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitic acid, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyllaurate, sebacine Examples thereof include di-2-ethylhexyl acid acid, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

Examples of the silicone oil include chain polysiloxane (eg, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxane (eg, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane). (Sasiloxane, etc.)) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) forming a three-dimensional network structure, etc. Be done.

Moisturizing agents include, for example, polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, martitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate. , Sodium lactate, bile acid salt, dl-pyrrolidone carboxylate, alkylene oxide derivative, short chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, sardine extract, melilot extract and the like.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester. , N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); Salicylic acid-based UV absorbers (eg, amil salicylate, menthyl salicylate, homomentyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); -4-Isopropyl cinnamate, Methyl-2,5-diisopropyl cinnamate, Ethyl-2,4-diisopropyl cinnamate, Methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy Synnamate, Isoamyl-p-methoxysynamate, Octyl-p-methoxysinamate (2-ethylhexyl-p-methoxysinamate), 2-ethoxyethyl-p-methoxysinamate, cyclohexyl-p-methoxysinamate, ethyl -α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone-based ultraviolet absorbers (eg, 2,4-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl- Benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- (4'-methylbenzylidene) -d, l-kanfu Ah, 3-benziliden-d, l-Phenyl; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t -Octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoilmethane; 4-methoxy-4'-t-butyldibenzoylmethane; 5- (3,3-,3-) Dimethyl-2-norbornylidene) -3-pentan-2-one, dimorpholinopyridadino; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 2,4-bis-{[4- (2-ethylhexyl) Oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl)-(1,3,5) -triazine and the like.

The cosmetics containing the inorganic powder having the elastomer coating layer and the silicone powder of the present invention can be prepared with water, powders other than the above, surfactants, lower alcohols, polyhydric alcohols, moisturizers, preservatives, and high molecular weight powders, if necessary. It is possible to contain molecules (including coating agents), antioxidants, fragrances, various other agents, etc. in a qualitative and quantitative range that does not impair the effects of the present invention.

The powdered cosmetic of the present invention can be a foundation, a cheek, a sunscreen, or any product form, and is particularly suitable for use as a foundation.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is shown in mass% with respect to the system in which the component is blended.
First, the evaluation methods and evaluation criteria used in the following tests will be described.

<Elastomer coating test>
As for the test method, it was confirmed by visual observation and tactile sensation that the original powder and the elastomer were not separated. In addition, it was confirmed by elemental analysis that an appropriate amount of elastomer was coated with respect to the charged amount and that it floated on water and showed water repellency, and that the coating was appropriate.
◯: Powder is coated with elastomer ×: Powder is not coated with elastomer

First, the blending amount of the composition used in the present invention to become an elastomer when (a1) a silicone polymer having an amino group and (a2) a silicone polymer having a carboxyl group is mixed was examined.

The elastomers used in the present invention of the formulations listed in the following tables were prepared according to the following production methods.
<Manufacturing method>
A silicone polymer having a carboxyl group and a silicone polymer having an amino group were added, stirred, and heated at 105 ° C. for 12 hours to obtain an elastomer used in the present invention.

First, the present inventor has a molar ratio of amino group to carboxyl group Y / X (Y) in which the composite of (a1) a silicone polymer having an amino group and (a2) a silicone polymer having a carboxyl group exhibits elastomeric properties. (A2) is the molar amount of the carboxyl group contained in the component, and X is the molar amount of the amino group contained in the (a1) component). Y / X is a carboxyl group equivalent (mmol) / amino group amount (mmol) calculated from a carboxyl group equivalent obtained from NMR and a diamino group equivalent.
The prescriptions of the test examples listed in Tables 1 and 2 below are as follows.

(* 1) KF-8004 (Shin-Etsu Chemical Co., Ltd.)
When ¹ H NMR of KF-8004 was measured and the diamine equivalent was calculated from the integrated values of the signal derived from CH ₃ and the signal derived from -CH _2- , it was 3090.4 g / mol.
(* 2) Sensorcil PCA (Croda)
When ¹ H NMR of the sensor sill PCA was measured and the carboxyl equivalent was calculated from the integrated values of the signal derived from CH ₃ and the signal derived from −CH _2- , it was 5631 g / mol.

In the range of Test Examples 1-4 to 1-9, it was found that the composite of (a1) a silicone polymer having an amino group and (a2) a silicone polymer having a carboxyl group becomes an elastomer.
Therefore, it was found that the molar ratio of amino group to carboxyl group was excellent at Y / X = 0.1 to 1.2.

Next, the present inventor examined whether it is possible to replace it with an acrylic polymer having a carboxyl group as another component (a2).

(* 3) The COOH-containing acrylic polymer was obtained by the following method.
12-Methylamide dodecanoic acid (MAD) /2-acrylamide-2-methylpropanesulfonic acid (AMPS) copolymer (90/10), 12-methacrylamidedodecanoic acid (MAD) 18.50 g (65.37 mmol), 2- Acrylamide-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan) 1.50 g (7.24 mmol), sodium hydroxide 0.29 g (7.25 mmol), azobisisobutyronitrile (Nakalitesque) Maker) 0.30 g (1.83 mmol) was dissolved in 60.0 g of methanol. Azobisisobutyronitrile was recrystallized from methanol according to a conventional method.
Argon was bubbled for 60 minutes to degas, the container was covered with septum, and the mixture was heated at 60 ° C. for 20 hours for polymerization. After completion of the polymerization reaction, the reaction solution was dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration.
After drying under reduced pressure, 15.2 g of a random COOH-containing acrylic polymer was obtained (yield: 75.1%). The obtained COOH-containing acrylic polymer had a weight average molecular weight of 50,000.

From this, it was found that the elastomer used in the present invention can be obtained even with an acrylic polymer having a carboxyl group.

<Elastomer-coated inorganic powder>
Furthermore, the present inventor has examined in the following whether the elastomer used in the present invention can be coated with various inorganic powders.

<Manufacturing method>
(C) Various inorganic powders and a silicone polymer having a carboxyl group are added to a henshal mixer, and the mixture is mixed at a low speed for 10 minutes. Then, a silicone polymer having an amino group was added thereto, mixed at a low speed for 10 minutes, and heated to obtain an inorganic powder having an elastomer coating layer used in the present invention.

Various inorganic powder talc in Table 4: Talc JA-68R (manufactured by Asada Flour Milling Co., Ltd.)
Mica: PDM-9WA (manufactured by Topy Industries, Ltd.)
Synthetic phlogopite iron: PDM-FE (manufactured by Topy Industries, Ltd.)

From Test Examples 3-1 to 3-4, it was found that the elastomer according to the present invention can be coated with various (C) inorganic powders.

(A) An inorganic powder having an elastomer coating layer was obtained.

<Powdered cosmetics>
The present inventor has studied the blending of talc having an elastomer coating layer and silicone powder into the powdered cosmetics according to the present invention based on the following evaluation criteria.

<Drop test>
The breakage of the pharmaceutical product when the composition of each test example was dropped 5 times from a height of 30 cm was evaluated according to the following criteria.
○: Not damaged ×: Damaged

<Usage feel>
The compositions of each Test Example were evaluated relative to each other based on Test Example 4-1. When placed on the palm and applied to the skin, the overall feel of use, including non-powderiness, lightness, smoothness, fit, and familiarity with the skin, was evaluated by the following criteria by a panel of 10 experts.
⊚: More than 9 out of 10 respondents answered that the test examples were more comfortable to use than the standard.
◯: 6 or more and less than 9 out of 10 responded that the feeling of use of the test example was better than the standard.
Δ: 3 or more and less than 6 out of 10 responded that the feeling of use of the test example was better than the standard.
X: Less than 3 out of 10 responded that the feeling of use of the test example was better than the standard.

<Manufacturing method of dry powder cosmetics>
The powder component, oil component and other components shown in the following formulation were mixed in advance with a Henschel mixer and then crushed twice with a palperizer. The obtained mixture was filled in a resin inner plate container and dry-press molded by a known method to obtain a solid powder cosmetic.

Next, by blending talc coated with the elastomer used in the present invention as the component (A) and silicone powder as the component (B), it was examined whether or not the drop resistance could be improved in addition to the improvement of the feeling of use. rice field.

(* 1) Elastomer-treated talc (talc JA-68R (A: 2%, B: 3%))
(* 2) Talc JA-68R (manufactured by Asada Flour Milling Co., Ltd.)
(* 3) PDM-9WA (manufactured by Topy Industries, Ltd.)
(* 5) Microsphere M-306 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)
(* 6) KSP100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(* 7) Sunsphere L-51S (manufactured by AGC SI Tech)
(* 8) EP1-CR-50P (manufactured by Daito Kasei Kogyo Co., Ltd.)
(* 10) EP1-Bengala # 216P (manufactured by Daito Kasei Kogyo Co., Ltd.)
(* 11) EP1-Ocher # 1P (manufactured by Daito Kasei Kogyo Co., Ltd.)
(* 12) EP1-BL-100P (manufactured by Daito Kasei Kogyo Co., Ltd.)
(* 14) RA-G-308 (manufactured by Nippon Fine Chemical Co., Ltd.)
(* 17) Este Mall 182V (manufactured by Nisshin Oillio Group)

As can be seen from Test Examples 4-4 to 4-5, the combination of (A) talc having an elastomer coating layer and (B) silicone powder is very excellent in terms of drop stability in addition to usability. It turned out.

Next, the present inventors examined whether or not the feeling of use was improved even when an inorganic powder having an elastomer coating layer other than talc was used.

From Test Examples 5-1 to 5-2, it was found that the feeling of use was improved even when an inorganic powder having an elastomer coating layer other than talc was used.

Claims (2)

(A) 5 to 70% by mass of an inorganic powder having an elastomer coating layer containing the following (a1) and (a2).
(B) Silicone powder 1 to 20% by mass,
A powdered cosmetic characterized by containing.
(A1) A silicone polymer having an amino group having the following general formula (1) ,
(A2) A silicone polymer having a carboxyl group having the following general formula (2) or an acrylic polymer having a carboxyl group having the following general formula (3) .
It is an elastomer consisting of
The molar ratio of amino group to carboxyl group is Y / X = 0.1 to 1.2 (Y is the molar amount of carboxyl group contained in the component (a2), and X is the amino group contained in the component (a1). An elastomer characterized by being in the range of (molar amount).

(In the general formula (1), X is an alkyl group having 1 to 18 carbon atoms, R and R'are alkylene groups (except when R is a methylene group). M is 20 to 2000 and n is 1. ~ 100. )

(In the formula, R ¹ and R ² indicate a methyl group or a group represented by (4) below, and 1 to 100 of the group is contained in one molecule, and y represents an integer of 1 to 50,000. .)

The powder cosmetic according to claim 1, wherein the inorganic powder is talc and the amount of elastomer is 0.5 to 20% by mass with respect to the amount of (A) talc.