JP6725575B2 - Aerosol type cosmetics - Google Patents

Description

The present invention relates to an undiluted solution containing a specific surface-coated powder and a volatile oil agent, and an aerosol-type cosmetic composition using a liquefied gas as a propellant, more specifically, excellent redispersibility of the powder, The present invention relates to an aerosol-type cosmetic composition that can be sprayed uniformly on the skin and hair, has a smooth feeling of use, and has no uneven color of the coating film even when colored.

In recent years, the number of hot summer days has been increasing in summer, so the demand for cosmetics that can feel cool is increasing, and for example, aerosol type cosmetics that can feel cool due to the heat of vaporization of liquefied gas, which is a propellant, are available. It is preferred and there are many products on the market. However, aerosol type cosmetics have a special environment in which undiluted liquid and liquefied gas or compressed gas that is a propellant coexist and are pressurized, so when powder is contained, the agglomeration of the powder in the aerosol container As a result, there is a problem in that the valve is clogged, resulting in poor ejection properties and non-uniform ejection. Therefore, in aerosol type cosmetics containing powder, it is important to maintain the redispersibility of the powder, and various studies have been made (for example, refer to Patent Documents 1 to 3).

JP, 2010-120871, A JP2012-106949A JP, 2005-101545, A

The object of the present invention, in the coexistence with a liquefied gas, by stably blending the powder in an aerosol container, with a smooth feeling of use, it is possible to uniformly spray, even in the case of coloring It is an object of the present invention to provide an aerosol-type cosmetic material in which the coating film has no color unevenness.

In view of such circumstances, as a result of intensive studies by the present inventors, the powder was subjected to a specific surface coating treatment, and by combining with a volatile oil agent, caking of the powder in the aerosol container was suppressed, and at the time of use. The present invention has been completed by finding that the improved redispersibility provides an aerosol-type cosmetic composition in which the coating film has no color unevenness even when colored.

That is, the present invention provides an aerosol type cosmetic composition containing a stock solution containing the following components (A) and (B) and a liquefied gas as a propellant.
(A) Powders surface-coated with the following surface-coating treatment agents (a) and (b) (a) Both-end-reactive diorganopolysiloxane R ¹ R ² ₂ SiO— represented by the following general formula (1) (R ² ₂ SiO) _L -SiR ¹ R ² ₂ (1)
(In the formula, each R ¹ represents a hydroxyl group, each R ² independently represents a hydrocarbon group having 1 to 20 carbon atoms, and L represents an integer of 3 to 10,000).
(B) Amino group-containing silane compound represented by the following general formula (2) R ³ R ⁴ _m SiX _(3-m) (2)
(In the formula, R ³ represents a hydrocarbon group having at least one amino group and having 1 to 20 carbon atoms, R ⁴ represents an alkyl group having 1 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms. Represents, and m is 0 or 1.)
(B) Volatile oil agent

The aerosol-type cosmetic composition of the present invention has good redispersibility even when it contains a powder, and a uniform cosmetic film can be easily applied while feeling a cool sensation. Further, it is useful as a makeup cosmetic, because even when applied by using a hand or a small tool, it can be smoothly spread and spread, and a uniform makeup film having no color unevenness can be obtained even if it is colored.

Hereinafter, the present invention will be described in detail.
The aerosol type cosmetic of the present invention is one in which a stock solution containing components (A) and (B) and a liquefied gas as a propellant are filled in a container having a pressure resistant valve. Depending on the purpose of use, the aerosol can be adjusted to a spray (fog) or foam (foam) form. It can be sprayed on the skin and stretched by hand, or sprayed on a puff or sponge. , Apply using those props and use. In the present invention, a spray form is preferred from the viewpoint that it can be uniformly sprayed on the skin and hair. Therefore, the filling ratio of the stock solution and the liquefied gas in the aerosol is preferably 10 to 90% by mass of the stock solution (hereinafter simply abbreviated as “%”) and 10 to 90% of the liquefied gas.

(Undiluted solution)
The surface-coated powder of the component (A) used in the present invention means a surface-coating treatment agent (a) a diorganopolysiloxane having both ends reactive with a specific structure, and a surface-coating treatment agent (b) a specific structure. It is obtained by simultaneously coating the amino group-containing silane compound of.

Among the surface coating treatment agents used in the present invention, (a) is a diorganopolysiloxane reactive at both ends, and is a hydroxysilyl group-modified silicone at both ends represented by the following general formula (1).
R ¹ R ² ₂ SiO-(R ² ₂ SiO) _L -SiR ¹ R ² ₂ (1)
(In the formula, each R ¹ represents a hydroxyl group, each R ² independently represents a hydrocarbon group having 1 to 20 carbon atoms, and L represents an integer of 3 to 10,000).

Although the above (a) is a liquid oil-like compound, it is preferably used in the present invention in the form of an aqueous suspension or an aqueous emulsion from the viewpoint of improving the feel of the component (A). The method for preparing the aqueous emulsion of (a) may be a generally known method, for example, a method of emulsion polymerizing a low molecular cyclic siloxane as a starting material, or a method of emulsifying an oily both-end-reactive diorganopolysiloxane. Etc. are illustrated.

Further, among the surface coating agents used in the present invention, (b) is an amino group-containing silane compound, which is represented by the following general formula (2).
R ³ R ⁴ _m SiX _(3-m) (2)
(In the formula, R ³ represents a hydrocarbon group having at least one amino group and having 1 to 20 carbon atoms, R ⁴ represents an alkyl group having 1 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms. Represents, and m is 0 or 1.)

Preferred examples of the above (b) include N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane.

Further, as a preferable mode of the component (A) used in the present invention, a polymer having a fine three-dimensional crosslinked structure of silicone (condensation reaction of the above surface coating agents (a) and (b)) ( Hereinafter, it is a powder whose surface is coated with a "silicone micro-crosslinked product". The finely crosslinked silicone may be a compound having no rubber elasticity, and the mass ratio of the surface coating treatment agents (a) and (b) is generally within the range of 100:0.1 to 100:35. be able to. If the content of (b) is less than 0.1% by mass, it will be in the form of viscous silicone oil or gum, and if it is more than 35% by mass, it will be in the form of elastic silicone elastomer, and the water repellency of the surface-coated powder will be reduced. Tend.

Further, the silicone finely crosslinked product is a polymer having no rubber elasticity, that is, rubber hardness, and the measured value by the durometer type AO measurement method (soft rubber hardness measurement) defined in ISO7619-1 is less than 10, It is more preferably less than 5, and even more preferably 0.

Furthermore, regarding the rheological properties of the above silicone microcrosslinked product, the complex elastic modulus in dynamic viscoelasticity measurement (25° C., strain rate 17%, shear frequency 4 Hz) is 3,000 to 100,000 Pa, loss coefficient tan δ (loss elastic modulus). G″/storage modulus G′) is preferably 1.0 to 2.5. More preferably, the complex modulus is 10,000 to 100,000 Pa and the loss coefficient tan δ is 1.0 to 2 When the complex elastic modulus is less than 3,000 Pa, the silicone rubber exhibits properties as a silicone oil, and the feeling of use of the surface-coated powder tends to deteriorate. When the loss coefficient tan δ is less than 1.0, the elastic body exhibits the properties of an elastic body and exhibits the water repellency and the adhesion to the skin. When the loss coefficient tan δ is larger than 2.5, the silicone rubber exhibits properties as a silicone oil, and the usability of the surface-coated powder tends to deteriorate.

The rheological properties of the silicone microcrosslinked product can be measured as follows.
Dynamic viscoelasticity measuring device: Rheosol-G3000 (manufactured by UBM)
Measuring jig: 20 mm diameter parallel plate Measuring frequency: 4 Hz
Measurement temperature: 25±1.0℃
Measurement strain setting: The strain rate is set to 17%, and measurement is performed in the automatic measurement mode.
Measurement sample thickness (gap): 1.0 mm
The reason why the shear frequency is set to 4 Hz here is that it is within the range of physical motion speeds that are common to humans, and is close to the speed when applying cosmetics to the skin.

In the component (A) used in the present invention, the powder which can be surface-coated is not particularly limited as long as it is a powder used in ordinary cosmetics, and it is an inorganic powder, an organic powder, a metal soap powder. , Glitter powders, pigment powders, composite powders of these, and the like, and their particle shape (spherical, needle-shaped, plate-shaped, etc.), particle diameter (fume-shaped, fine particles, pigment grade, etc.), particle structure ( Any of them can be used regardless of whether they are porous or non-porous.

Specifically, white inorganic pigments such as titanium oxide, zinc oxide and barium sulfate, carbon black, chromium hydroxide, colored inorganic pigments such as ultramarine, talc, muscovite, phlogopite, phlogopite, biotite, synthetic Mica, sericite, synthetic sericite, kaolin, silicon carbide, bentonite, smectite, diatomaceous earth, aluminum silicate, aluminum magnesium metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, White powder such as magnesium carbonate, hydroxyapatite, boron nitride, bismuth oxychloride, fish scale foil, polyethylene terephthalate/aluminum/epoxy laminated powder, polyethylene terephthalate/polyolefin laminated film powder, polyethylene terephthalate/polymethylmethacrylate laminated film powder, etc. Glittering powder, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, styrene-acryl copolymer resin, etc., synthetic resin powder, polypropylene resin , Organic polymer resin powder such as urethane resin, organic low molecular weight powder such as zinc stearate and N-acyl lysine, natural organic powder such as silk powder and cellulose powder, Red No. 201, Red No. 202, Red 205 No., red 226, red 228, orange 203, orange 204, blue 404, yellow 401, and other organic pigment powders, red 3, red 104, red 106, orange 205, yellow 4 No. 5, Yellow No. 5, Green No. 3, Blue No. 1, etc., powders of organic pigments such as zirconium, barium or aluminum lake, and metal powders such as aluminum powder, gold powder, silver powder, etc. One or more species may be used, and if necessary, a surface coating treatment may be performed or a composite may be used.

In the component (A) used in the present invention, the method of surface-coating these powders with the above-mentioned surface coating treatment agents (a) and (b) is not particularly limited. And powder are directly mixed (heated) for coating, and the surface coating agent is dissolved or dispersed in a solvent such as ethanol, isopropyl alcohol, n-hexane, and the powder is added to this solution or dispersion. A wet coating method, a mechanochemical method, and the like, in which the solvent is added and mixed, and then the solvent is removed by drying or the like, heating, and pulverization are performed.

Further, the component (A) can be obtained based on the method described in International Publication 2014/102863 pamphlet. For example, it is also possible to simply mix the powder and the above-mentioned silicone finely crosslinked product with a mixer or the like for coating. Further, more preferably, a method of fixing the silicone finely crosslinked product to the particle surface by heating after depositing the silicone finely crosslinked product on the powder particle surface in the presence of the powder by the in-situ method Can be used. By this method, the uniformity of the coating on the surface of the powder particles is enhanced, and a surface-coated powder having a better and lighter feeling of use and more excellent adhesion to the skin can be obtained.

The component (A) thus obtained has a powder surface coated with the surface coating treatment agents (a) and (b), and the coating amount is not particularly limited, but the powder and the surface coating are not limited. The mass ratio with the treating agent is preferably 99.99:0.01 to 70:30, and particularly preferably 99.9:0.1 to 90:10. Within this range, a surface-coated powder having a smoother, lighter feel, a moist feel, and excellent adhesion to the skin can be obtained.

The content of the component (A) in the present invention is not particularly limited, but it is preferably 0.1 to 40% in the stock solution, and more preferably 0.5 to 30%. Within this range, there is no unevenness when the aerosol type cosmetic composition of the present invention is sprayed and applied, and the elongation at the time of application is good, which is more preferable.

The volatile oil agent of the component (B) used in the present invention is not particularly limited as long as it is liquid and volatile at 20° C. and normal pressure, and its viscosity and origin are not limited. Any of silicone-based oils, hydrocarbon-based oils, ester-based oils and the like can be used, and one or more of these can be used. Among these, silicone oil is preferable from the viewpoint of elongation and spread, and specific examples thereof include dimethylpolysiloxane having a kinematic viscosity of about 2CS at 25°C, decamethylcyclopentasiloxane, methyltrimethicone, and the like, and particularly decamethylcyclo Pentasiloxane and methyltrimethicone are also preferable in terms of spreading and spreading, proper adhesion to the skin and stability of the cosmetic with time.

The content of the component (B) in the present invention is not particularly limited, but it is preferably 10 to 90%, more preferably 10 to 60% in the stock solution. Within this range, the aerosol-type cosmetic composition of the present invention is more preferable because it has a better spread and spread, an appropriate feeling of adhesion to the skin and excellent stability over time of the cosmetic composition.

In addition to the above-mentioned essential components, the stock solution of the aerosol-type cosmetic composition of the present invention contains an oil component other than the component (B), an oil gelling agent, and a powder other than the component (A), as long as the effects of the present invention are not impaired. It may contain components usually contained in cosmetics such as a body, a surfactant, an aqueous component, an ultraviolet absorber, a moisturizer, an antioxidant, a cosmetic component, an antiseptic, a dye and a fragrance.

The oily component is not particularly limited as long as it is a component other than the component (B) and is usually used for cosmetics, and is in the form of liquid, paste, solid, etc., and origin of animal oil, vegetable oil, synthetic oil, etc. Any oil agent such as hydrocarbons, oils and fats, ester oils including ultraviolet absorbers, higher alcohols, silicone oils, fluorinated oils, and lanolin derivatives can be used. Specifically, liquid ones are liquid paraffin, heavy liquid isoparaffin, α-olefin oligomer, squalane, polyisobutylene, hydrocarbons such as polybutene, olive oil, castor oil, macadamian nut oil and other oils, jojoba oil. , Diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, 2 -Cetyl ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl 2-ethylhexanoate, oleyl oleate, olein Octyldodecyl acid, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, Isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, dipentaerythritol fatty acid ester, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, myristic acid 2 -Octyldodecyl, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, 2-ethylhexyl methoxycinnamate, diisostearyl malate, glyceryl triisooctanoate, triisostearin. Glyceryl acid, diglyceryl diisostearate, diglyceryl triisostearate, diglyceryl tetraisostearate, decaglyceryl decaisostearate, glyceryl triisopalmitate, glyceryl trimyristate, diglyceryl isostearate myristate, tritridecyl trimellitate etc. Amino acid oils such as esters, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, N-lauroyl-L-glutamic acid di(phytostearyl-2-octyldodecyl), fatty acids such as isostearic acid and oleic acid, Oleyl alcohol , Higher alcohols such as isostearyl alcohol, dimethylpolysiloxane, methylphenylpolysiloxane, alkoxy-modified organopolysiloxane, silicone oils such as fluorine-modified silicone, fluorine-based oils such as perfluoropolyether, lanolin, lanolin acetate, Examples thereof include lanolin derivatives such as lanolin fatty acid isopropyl and lanolin alcohol. Pastes and solids are petrolatum, ceresin wax, polyethylene wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, ozokerite wax, hydrocarbons such as ethylene propylene copolymer, fats and oils such as owl, beeswax, carna. Uva wax, candelilla wax, gay wax, montan wax and other waxes, cholesterol fatty acid ester, amino acid oils such as N-lauroyl-L-glutamic acid di (cholesteryl behenyl octyldodecyl), stearic acid, lauric acid, myristic acid , Fatty acids such as behenic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, behenyl alcohol, pentaerythritol rosin acid, oil gelling agents such as 12-hydroxystearic acid, dextrin palmitate, palmitic acid/ Dextrin fatty acid ester of 2-ethylhexanoate dextrin, stearate dextrin, sucrose stearate, sucrose palmitate, octanoate dextrin, palmitate/stearate dextrin, oleate dextrin, isopalmitate dextrin, isostearate dextrin. Examples thereof include sucrose stearate, sucrose acetate stearate, sucrose fatty acid ester, aluminum isostearate, calcium stearate, and the like, and one or more of these may be used.

The powder is a powder other than the component (A), and if it is a powder generally used in cosmetics, it may have a spherical, plate-like or needle-like shape, or may have a particle size such as smoke, fine particles or pigment grade. It is not particularly limited by the particle structure such as porous and non-porous, and inorganic powders, glitter powders, organic powders, pigment powders, metal powders, composite powders, etc. Can be mentioned. These powders may be used alone or in combination of two or more, and if necessary, other than the surface coating treatment agent used as the component (A), a fluorine compound, a silicone compound, a metal soap, collagen, carbonization, etc. Surface coating treatment may be performed by a known method using hydrogen, higher fatty acid, higher alcohol, ester, wax, wax, surfactant or the like, or a composite material may be used.

As the surfactant, any one can be used as long as it is a surfactant commonly used in cosmetics, such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and the like. Are listed. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl such as PEG-10 dimethicone. Polyether-modified organopolysiloxane such as co-modified organopolysiloxane, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl 3-polydimethylsiloxy Examples thereof include polyglycerin-modified organopolysiloxane such as ethyl dimethicone. Of these, polyoxyalkylene alkyl co-modified organopolysiloxane, polyether-modified organopolysiloxane, and polyglycerin-modified organopolysiloxane are preferable from the viewpoint of stability over time.

Examples of the aqueous component include alcohols such as ethyl alcohol, propylene glycol, 1,3-butylene glycol, 1,2-pentanediol, dipropylene glycol, tripropylene glycol, glycols such as polyethylene glycol, glycerin and diglycerin. And glycerols such as polyglycerin.

The method for producing the undiluted solution of the aerosol-type cosmetic composition of the present invention is not particularly limited and may be prepared by a conventional method. For example, component (A) and part of component (B), and further, if necessary, a surfactant are kneaded using a three-roller, and the rest of component (B) is added to this and mixed to obtain a uniform mixture. In addition to obtaining such a dispersion, purified water or a water-soluble component may be added to the oil phase and emulsified to obtain a uniformly stirred emulsion.

(Propellant)
Examples of the liquefied gas used in the present invention include liquefied petroleum gas (LPG), ethers such as dimethyl ether (DME) and diethyl ether, and fluorinated hydrocarbons. Liquefied petroleum gas is a hydrocarbon having 2 to 5 carbon atoms, and examples thereof include ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, and a mixture thereof. Among these, liquefied petroleum gas and dimethyl ether are preferably used from the viewpoint of improving long-term stability in the aerosol container, and liquid at 25° C. and 0.3 MPa is more preferable. Furthermore, from the viewpoint of safety at high temperatures, liquefied petroleum gas (LPG 0.15) whose pressure at 20° C. is adjusted to 0.15 MPa is preferable.

The components of the propellant may be used alone or as a mixture of two or more, but it is preferable to use DME and LPG in combination in terms of cool feeling at the time of injection and a spray state. The content ratio is a mass ratio, preferably DME:LPG=1:1 to 1:10, and more preferably 1:5 to 1:8.

The mass ratio of the undiluted solution of the aerosol cosmetic of the present invention to the propellant is not particularly limited, but is preferably 10:90 to 90:10, more preferably 20:80 to 40:60. Is. Within this range, a cool sensation is obtained during use, and the stock solution does not penetrate too much into the sponge when sprayed onto the sponge, which is preferable.

The method for filling the aerosol type cosmetic composition of the present invention is not particularly limited, but a stock solution prepared by a conventional method is filled in a pressure resistant container, an aerosol valve is fixed to the container, and then a propellant is injected through the valve. Furthermore, an aerosol type cosmetic can be obtained by attaching a spraying member according to the purpose to the aerosol valve. Further, when the stock solution forms an oil phase and an aqueous phase, in the filling process, in order to reduce the number of times and homogenize, it may be filled after forming a water-in-oil emulsion or the like. The body or the like may be filled separately before injecting the propellant.

The aerosol type cosmetics of the present invention are not particularly limited, but are preferably used for sunscreen cosmetics and makeup cosmetics, and can be used for sunscreens, foundations, concealers, blushers, makeup bases, eye shadows and the like.

Examples will be shown below, but the present invention is not limited to these examples.
1. Preparation of Silicone Crosslinked Sample Sample 1:
In a PP 300 ml container, 0.1 g of sodium lauroylmethyltaurine was dissolved in 100 g of ion-exchanged water, and then (a) 10 g of diorganopolysiloxane with both ends reactive (viscosity 30 mPa·s) was gradually added under stirring at 6000 rpm with a homomixer. Accompany. The mixture was stirred at room temperature for 10 minutes and emulsified to obtain an aqueous emulsion (a). While stirring this with a stirrer, 4 g of a 25 wt% IPA solution of (b) aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) is added. Then, the pH was adjusted to 10.5 with a 1N-NaOH aqueous solution, the mixture was stirred for 15 minutes, transferred to an aluminum dish, and dried at 105° C. for 24 hours to obtain a silicone finely crosslinked product. The silicone finely crosslinked product obtained was measured by a durometer AO to have an NA (not more than the measurement limit), a complex elastic modulus of 23000 Pa and a tan δ of 1.091.

Sample 2:
(A) 500 g of both-end reactive diorganopolysiloxane (viscosity 30 mPa·s) was charged into a polyethylene beaker having a capacity of 2 liters, and 22.5 g of sodium lauroylmethyltaurine and 50 g of ion-exchanged water were gradually stirred with a homomixer at 5000 rpm. Was added dropwise to the solution to invert the phase. After thickening, the stirring speed was increased to 7,000 rpm and stirred for 15 minutes, and 450 g of ion-exchanged water was added for dilution. Then, it was emulsified and dispersed once with a tabletop pressure homogenizer (manufactured by APV Gorin) at 70 MPa to obtain a water emulsion (1) of (a). The water-emulsion (1) was dried at 105° C. for 3 hours to volatilize and remove water, and the solid content of the solid content was 6000 as determined by GPC. The solid content was 51.0%.

In a PP 300 ml container, ion-exchanged water (90.4 g) was added to the emulsion (1) (19.6 g), and the mixture was stirred at room temperature for 10 minutes using a homomixer at 6000 rpm. While stirring this with a stirrer, 4 g of a 25 wt% IPA solution of (b) aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) is added. Then, the pH was adjusted to 10.5 with a 1N-NaOH aqueous solution, the mixture was stirred for 15 minutes, transferred to an aluminum dish, and dried at 105° C. for 24 hours to obtain a silicone finely crosslinked product. The obtained silicone finely crosslinked product was measured by a durometer AO to have an NA (not more than the measurement limit), a complex elastic modulus of 39500 Pa and a tan δ of 1.187.

Sample 3:
A polyethylene beaker with a capacity of 2 liters was charged with 450 g of octamethylcyclotetrasiloxane, 500 g of deionized water and 6.75 g of sodium lauroylmethyltaurine, premixed with a homomixer agitation of 2000 rpm, and 4 g of citric acid was added to 70°C. The temperature was raised and emulsion polymerization was carried out for 24 hours with a homomixer of 5000 rpm. A high-molecular-weight (a) water emulsion was obtained by emulsifying and dispersing once with a tabletop pressure homogenizer (manufactured by APV Gorin) at 50 MPa. Then, 10% sodium carbonate was added to adjust the pH to 7 to obtain a water emulsion (2) of (a). The water-emulsion (2) was dried at 105° C. for 3 hours, and the solid content obtained by volatilizing and removing water was found to have a molecular weight in terms of PS by GPC of 10,000. The solid content was 46.5%.

In a PP 300 ml container, 88.5 g of ion-exchanged water was added to 21.5 g of the emulsion (2), and the mixture was stirred at room temperature for 10 minutes using a homomixer at 6000 rpm. While stirring this with a stirrer, 4 g of a 25 wt% IPA solution of (b) aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) is added. Then, the pH was adjusted to 10.5 with a 1N-NaOH aqueous solution, the mixture was stirred for 15 minutes, transferred to an aluminum dish, and dried at 105° C. for 24 hours to obtain a silicone finely crosslinked product. The obtained silicone finely crosslinked product was measured by a durometer AO to have an NA (not more than the measurement limit), a complex elastic modulus of 17500 Pa and a tan δ of 1.353.

(Measurement by Durometer AO)
A styrene square case (vertical 36×horizontal 36×height 14 mm) is charged so that the silicone micro-crosslinked product is slightly exposed from the surface, and the surface is flattened to be a test surface. The pressure plate of the durometer is placed at a position of 20 mm on the test surface, and the pressure plate is pressed against the test piece while the surface of the test surface and the pressure plate are maintained in parallel, and the scale of the needle is read. This operation was repeated 5 times and the average value was used as the measured value. In addition, when the needle did not move due to the measurement, it was set to NA (below the measurement limit).

(Dynamic viscoelasticity measurement)
G'(storage elastic modulus) and G" (loss elastic modulus) were obtained under the conditions shown below to obtain a complex elastic modulus and tan δ.
Viscoelasticity measuring device: Rheosol-G3000 (manufactured by UBM)
Measuring jig: 20 mm diameter parallel plate Measuring frequency: 4 Hz
Measurement temperature: 25±1.0℃
Measurement strain setting: The strain rate is set to 17%, and measurement is performed in the automatic measurement mode.
Measurement sample thickness (gap): 1.0 mm

2. Production of Surface-Coated Powder (Component (A)) Production Example 1: ((a)/(b)=100/10) 5% Surface-coated Mica In a PE container having a capacity of 20 liters, water 7L and Y- 1300 kg of 2300 (manufactured by Yamaguchi Mica Co., Ltd.) was charged and dispersed at 2000 rpm for 5 minutes with a disper mixer (Prime Mix Co.; AM-40). 103 g of the above water emulsion (2) was added and stirred at 2500 rpm for 5 minutes. Then, 96 g of a 5 mass% aqueous solution of aminopropyltriethoxysilane (KBE-903; manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a crosslinking agent. The pH was adjusted to 10.3 with a 1N-NaOH aqueous solution, and then the mixture was reacted with stirring at 3000 rpm for 30 minutes. After filtering with a centrifugal dehydrator and washing with 7 L of water, the dehydrated cake was dried in a dryer at 120° C. for 16 hours. At this time, when a temperature sensor was inserted into the cake and the temperature was recorded, it was heated at 115° C. or higher for 7 hours. The dried cake was pulverized with a pulverizer to obtain 5% surface-coated mica.

Production Example 2: ((a)/(b)=100/10) 0.1% surface-coated mica The water emulsion (2) of Production Example 1 and the charged amount of 5% by mass aminopropyltriethoxysilane aqueous solution were respectively charged. A 0.1% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 2.0 g and 1.8 g.

Production Example 3: ((a)/(b)=100/10) 10% surface-coated mica The water emulsion (2) of Production Example 1 and the amount of aminopropyltriethoxysilane 5% by weight aqueous solution charged were 196 g each. A 10% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 182 g.

Production Example 4: ((a)/(b)=100/10) 0.05% surface-coated mica The water emulsion (2) of Production Example 1 and the amount of aminopropyltriethoxysilane 5% by mass aqueous solution charged were respectively changed. A 0.05% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 1.0 g and 0.9 g.

Production Example 5: ((a)/(b)=100/10) 15% surface-coated mica Aqueous emulsion (2) of Production Example 1 and aminopropyltriethoxysilane 5% by mass aqueous solution were charged at 293 g, respectively. A 15% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 272 g.

Production Example 6: ((a)/(b)=100/0.1) 5% surface-coated mica The water emulsion (2) of Production Example 1 and the charged amount of 5% by mass aminopropyltriethoxysilane aqueous solution were respectively charged. A 5% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 108 g and 1.0 g.

Production Example 7: ((a)/(b)=100/35) 5% surface-coated mica The water emulsion (2) of Production Example 1 and the aminopropyltriethoxysilane 5 mass% aqueous solution were charged at 80 g each. A 5% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 259 g.

Production Example 8: ((a)/(b)=100/0.05) 5% Surface Coated Mica The water emulsion (2) of Production Example 1 and the amount of aminopropyltriethoxysilane 5% by weight aqueous solution charged were respectively changed. A 5% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 107 g and 0.5 g.

Production Example 9: ((a)/(b)=100/50) 5% surface-coated mica The water emulsion (2) of Production Example 1 and the amount of aminopropyltriethoxysilane 5% by weight aqueous solution charged were 72 g each. A 5% surface-coated mica was obtained in the same manner as in Production Example 1 except that the amount was changed to 333 g.

Production Example 10: ((a)/(b)=100/10) 5% surface-coated talc Production Example 1 except that JA-13R (manufactured by Asada Flour Milling Co., Ltd.) was used instead of the powder of Production Example 1. A 5% surface-coated talc was obtained according to

Production Example 11: ((a)/(b)=100/10) 5% surface-coated sericite Production example except that sericite FES (manufactured by Sanshin Mining Co., Ltd.) was used instead of the powder of Production Example 1. According to 1, a 5% surface-covered sericite was obtained.

3. Production of Aerosol-Type Cosmetics Examples 1 to 13 and Comparative Examples 1 to 5: Aerosol-Type Foundation An aerosol-type foundation was prepared by the composition shown in Table 1 and the following production method. The obtained samples were evaluated for (a) no caking, (b) smoothness during application, and (c) no uneven color by the following methods, and the results are also shown in Table 1.

(Production method)
A: A part of components (1) to (13) (component (16) in Comparative Example 5) was kneaded with three rollers.
B: A and the remainder of component (13) (component (16) in Comparative Example 5) to component (15) were mixed and uniformly dispersed to obtain a stock solution.
: In Example 13, components (17) to (18) were mixed, added to A and emulsified at room temperature to obtain a stock solution.
C: Fill the stock solution obtained in B into an aluminum pressure-resistant container (diameter 35 mm, height 11 cm, cylinder) or glass pressure-resistant container (diameter 40 mm, height 12.5 cm, cylinder) and then fix the valve. Then, the propellant was filled through the valve to obtain an aerosol type foundation.
The stock solution and the propellant were filled in a ratio shown in the table so that the total amount was 32 g.

(Evaluation method 1: (b) Smoothness at application, (c) No uneven color)
The aerosol type foundations of Examples 1 to 13 and Comparative Examples 1 to 5 were sprayed onto 10 cosmetics evaluation specialist panels for 2 seconds while keeping the sponge and aerosol spray outlets at a distance of 2 cm, and then applied to all faces. Each of the samples was evaluated according to the following evaluation criteria, each sample was given a score, and the average score of all panels was evaluated according to the following criteria. With regard to (c), the time at which the volatile components were completely volatilized was 30 minutes after application, and the appearance of the applied film was visually evaluated.

[Evaluation criteria]
(Score): (Result)
5 points: Very good 4 points: Good 3 points: Normal 2 points: Slightly bad 1 point: Bad [Criteria]
(Judgment): (Average score)
◎: 4.5 points or more ○: 3.5 points or more and less than 4.5 points ×: Less than 3.5 points

(Evaluation method 2: (a) No caking)
The aerosol type foundations filled in the glass containers of Examples 1 to 13 and Comparative Examples 1 to 5 were allowed to stand for 1 month in a constant temperature bath at 40° C., and then left at room temperature for 1 day to return the temperature to room temperature. .. In all the samples, powder precipitated on the bottom and a clear liquid phase separated on the top. The container was shaken up and down 5 times and shaken and mixed, and then evaluated on a scale of 3 according to the following evaluation criteria, a rating was given to each sample, and evaluation was performed according to the following evaluation criteria.

[Criteria]
(Judgment): (criterion criteria)
◎: The powder is easily redispersed and becomes uniform ○: Part of the powder is solidified, but no clogging is observed even when sprayed ×: Part or all of the powder is solidified, Clogging occurs when jetting

As is clear from the results shown in Table 1, the aerosol type foundations of Examples 1 to 13 had no caking, had a smooth feel at the time of application, had no color unevenness, and had a beautiful finish. On the other hand, Comparative Example 1 in which untreated talc was used in place of the component (A) caused caking during storage, lacked uniformity even when applied, and had a high unevenness of color and a heavy burden on the skin. there were. In Comparative Example 2 using the powder coated with only the surface treatment agent (a) in place of the component (A), and Comparative Example 3 using the powder coated with only the surface treatment agent (b). However, color unevenness was generated, and the adhesion to the skin was insufficient. Further, in Comparative Example 4 in which the powder coated with the silicone crosslinked product other than the component (A) was used, the silicone crosslinked product swelled due to the liquefied gas, and the stability in the aerosol container was not excellent. In Comparative Example 5 containing a non-volatile polar oil in place of the component (B), a lot of foundation was absorbed in the sponge when used, and when applied, the skin was not smooth and the color was uneven. It happened and was not desirable.
From the above results, by combining the components of the present invention, an aerosol-type foundation having a smooth feeling during application, no caking, excellent storage stability, and no uneven color of the coating film was obtained.

Example 14: Aerosol type blusher (stock solution component) (%)
(1) Surface-coated mica 10 described in Production Example 4
(2) Triethoxycaprylylsilane (2%) treated titanium dioxide 5
(3) Red 226 0.8
(4) Mica titanium *6 3
(5) Triethoxycaprylylsilane (2%)-treated sericite Remainder (6) PEG-9 polydimethylsiloxyethyl dimethicone *51
(7) Methylparaben 0.2
(8) Polyethylene powder*7 0.2
(9) Dimethylpolysiloxane (25°C, kinematic viscosity 6CS) 10
(10) Decamethylcyclopentasiloxane 50
(11) Ethyl alcohol 4
*6: TIMIRON STARLUSTER MP-115 (Merck)
*7: Miperon PM-200 (manufactured by Mitsui Chemicals, Inc.)

(Production method)
A: Components (1) to (11) are dispersed uniformly.
B: 9 g of the stock solution obtained in A was charged into an aluminum pressure-resistant container (cylindrical shape with a diameter of 35 mm and a height of 11 cm), then a valve was fixed, LPG 0.15 10 g and carbon dioxide gas 1 g were charged through the valve, and an aerosol type I got a blusher.

(result)
The aerosol type blusher of Example 14 had no caking, was excellent in storage stability, had a smooth spread at the time of application, had no color unevenness, and had an excellent finish.

Example 15: Aerosol-type white powder (undiluted solution component) (%)
(1) Surface-coated mica 10 described in Production Example 2
(2) Talc Remaining amount (3) Red No. 202 0.1
(4) Blue 404 0.1
(5) Black iron oxide 0.1
(6) PEG-10 Dimethicone *81
(7) Zinc oxide 10
(9) Decamethylcyclopentasiloxane 50
(10) Titanium oxide coated synthetic phlogopite 5
(11) Squalane 5
(12) Dimethylpolysiloxane (25°C, kinematic viscosity 20CS) 10
(13) Methyl methacrylate crosspolymer powder *910
*8: KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
*9: Matsumoto Microsphere M-305 (Matsumoto Yushi-Seiyaku Co., Ltd.)

(Production method)
A: Components (1) to (13) are uniformly dispersed.
B: 9 g of the stock solution obtained in A was charged into an aluminum pressure-resistant container (cylindrical shape with a diameter of 35 mm and a height of 11 cm), then a valve was fixed, LPG 0.15 10 g and carbon dioxide gas 1 g were charged through the valve, and an aerosol type I got a blusher.

(result)
The aerosol-type white powder of Example 15 had no caking, was excellent in storage stability, had no color unevenness even when directly sprayed on the skin, and had a beautiful finish.

Example 16: Aerosol type sunscreen (undiluted solution component) (%)
(1) Surface-coated mica 10 described in Production Example 7
(1) Triethoxycaprylylsilane (2%) treated fine particle zinc oxide *10 5
(2) Fine particles of titanium dioxide treated with sodium lauroyl aspartate *11 10
(3) 2-Ethylhexyl methoxycinnamate 5
(4) Mixture of partially crosslinked organopolysiloxane polymer *125
(5) Behenoxydimethicone *13 0.5
(6) PEG-9 polydimethylsiloxyethyl dimethicone *51
(7) Dimethylpolysiloxane (25°C, kinematic viscosity 2CS) 12
(8) Carrageenan 0.2
(9) Purified water Remaining amount*10: MZX-508OTS (manufactured by Teika)
*11: ASI Titanium CR-50 (manufactured by Daito Kasei Co., Ltd.)
*12: KSG-850Z (manufactured by Shin-Etsu Chemical Co., Ltd.)
*13: ABIL Wax 2440 (melting point 40°C) (manufactured by EVONIK)

(Production method)
A: The components (1) to (7) are heated and mixed at 50° C. and uniformly dispersed.
B: Components (8) and (9) were added to B and emulsified at room temperature to obtain a stock solution.
C: After filling 6 g of the stock solution obtained in B into an aluminum pressure resistant container, a valve was fixed, and LPG 0.15 6 g was charged into the pressure resistant container through the valve to obtain an aerosol type sunscreen.

(result)
The aerosol-type sunscreen of Example 16 has no caking, is excellent in storage stability, has a uniform spray state, and has a cool feeling, and has little color unevenness when directly applied to the skin and is smooth when spread by hand. It was a touch.

Claims (5)

Aerosol-type makeup containing a stock solution containing the following components (A) and (B) and a liquefied gas as a propellant, and the content of the component (A) is 0.5 to 40% by mass in the stock solution. Fee.
(A) Powder which is surface-coated with a polymer having a fine three-dimensional crosslinked structure of silicone, which is obtained by condensation reaction of the following surface coating treatment agents (a) and (b) (a) with the following general formula (1) Shown at both ends reactive diorganopolysiloxane R ¹ R ² ₂ SiO-(R ² ₂ SiO) _L -SiR ¹ R ² ₂ (1)
(In the formula, each R ¹ represents a hydroxyl group, each R ² independently represents a hydrocarbon group having 1 to 20 carbon atoms, and L represents an integer of 3 to 10,000).
(B) Amino group-containing silane compound represented by the following general formula (2) R ³ R ⁴ _m SiX _(3-m) (2)
(In the formula, R ³ represents a hydrocarbon group having at least one amino group and having 1 to 20 carbon atoms,
R ⁴ represents an alkyl group having 1 to 4 carbon atoms, X represents an alkoxy group having 1 to 4 carbon atoms, and m is 0 or 1.)
(B) Volatile oil agent The aerosol cosmetics according to claim 1, wherein the mass ratio of the stock solution and the liquefied gas is 90:10 to 10:90. The aerosol cosmetics according to claim 1 or 2 , wherein the content of the component (B) is 5 to 90% by mass in the undiluted solution. Wherein in component (A), containing a mass ratio of the powder and the surface coating treatment agent (a) and (b), 99.9: 0.1 to 90: in a which claim 1-3 10 Aerosol cosmetics described. Wherein in component (A), the mass ratio of the surface coating treatment agent and (a) (b) is 100: 0.1 to 100: 35 aerosol cosmetic composition according to any one of claims 1 to 4.