JP6157969B2 - Aerosol-type foamy sunscreen - Google Patents

Description

  The present invention relates to an aerosol foam sunscreen. More specifically, the present invention relates to an aerosol foam sunscreen agent that is excellent in powder dispersibility and stability and can discharge a foam-like discharge product in which the powder is uniformly dispersed.

  Conventionally, sunscreen agents intended to protect the skin from ultraviolet rays have been widely used. In particular, in recent years, awareness of protecting the skin from ultraviolet rays has increased, and there has been a demand for sunscreen agents that are excellent in sunscreen prevention effects. The sunscreen agent contains an ultraviolet absorber, an ultraviolet scattering agent, and the like, thereby blocking the arrival of ultraviolet A wave (UVA) and ultraviolet B wave (UVB) to the skin and protecting the skin from the harm of ultraviolet rays.

  Common sunscreen agents include gels, creams, emulsions, and aerosols. Aerosol-type sunscreen agents are excellent in that they can be sprayed and applied uniformly and easily, and when used on the skin, they give a feeling of cooling and are easy to use on the hair. Excellent aerosol sunscreens have not been obtained.

  In order to enhance the sun protection effect, an aerosol type sun protection agent containing a large amount of UV scattering agent is used. Even if the container is shaken before use and the powder is evenly dispersed in the aerosol composition, Since the liquid starts to settle, there is a problem that the foam in which the powder is uniformly dispersed cannot be discharged, and the effect of preventing sunburn on the coated surface becomes uneven.

  Patent Document 1 discloses a foamable aerosol composition comprising an aqueous stock solution containing a specific amount of associative thickener and a liquefied gas. However, there is no disclosure about the effect of using the powder and the associative thickener in combination.

  Patent Document 2 includes an aqueous base containing an associative thickener and an oily base containing a lipophilic powder whose surface has been subjected to water repellency. The content of the oily base and the liquefied gas is 10 in the aerosol. A foamable aerosol composition for sun protection that is ˜50% by weight is disclosed. However, it is only described that the lipophilic powder subjected to the water repellent treatment is dispersed in the oil base, and it is not disclosed to disperse the powder in the aqueous base.

Japanese Patent No. 4722434 JP 2010-6738 A

  The present invention has been made in view of the above problems, and is excellent in the dispersibility and stability of the powder in the aerosol composition, and is discharged as a foam-like discharge product in which the powder is uniformly dispersed. The purpose of the present invention is to provide an aerosol-type foamy sunscreen agent that can be spread evenly and has an excellent sunscreen effect.

  The aerosol-type foam sunscreen of the present invention comprises a pressure-resistant container filled with an aerosol composition comprising a powder dispersion aqueous solution, an acrylate polymer, an aqueous stock solution containing a surfactant and a liquid oil, and a liquefied gas. Features.

  It is preferable that content of the powder contained in the said powder dispersion aqueous solution is 5-50 mass% in aqueous | water-based stock solution.

  It is preferable that content of the said liquefied gas is 3-40 mass% in an aerosol composition.

  The present invention is an aerosol foam sunscreen agent in which a pressure-resistant container is filled with an aerosol composition comprising an aqueous powder dispersion, an acrylic ester polymer, an aqueous stock solution containing a surfactant and a liquid oil, and a liquefied gas. , Excellent in dispersibility and stability of the powder in the aerosol composition, can discharge a foam-like discharge in which the powder is uniformly dispersed, and can be spread evenly on the coated surface; It is possible to provide an aerosol foamy sunscreen agent having an excellent sunscreen effect.

  The aerosol foamed sunscreen agent of the present invention is filled in a pressure resistant container with an aerosol composition comprising an aqueous stock solution and a liquefied gas.

  The aqueous stock solution contains an aqueous powder dispersion, an acrylate polymer, a surfactant, and a liquid oil.

  The powder-dispersed aqueous solution is used for the purpose of preventing sunburn and damage by scattering ultraviolet rays when the powder dispersed in the aqueous solution adheres to the skin and hair.

  The powder-dispersed aqueous solution is a powder in which a part of the surface of a powder having an ultraviolet scattering effect such as titanium oxide or zinc oxide having a primary particle diameter of 1 to 100 nm is coated with hydrous or anhydrous silicic acid, silica Are dispersed in water or an aqueous alcohol solution. By making the powder-dispersed aqueous solution an aerosol composition containing a specific acrylic ester polymer described later, the dispersibility and stability of the powder in the aerosol composition can be improved.

  Specific powder-dispersed aqueous solutions include, for example, WT-01, WT-PF01, PXWT-1, MICRO TITANIUM DIOXIDE SMT-100WR manufactured by Teika Co., Ltd., which is a hydrous silicic acid coating type, manufactured by Catalyst Chemical Industries, Ltd. CONCELIGHT WP-10S, SOLAVEIL CT-30W, TIOVEIL AQN, etc., manufactured by Croda Japan Co., Ltd., Neosilveil PW-6010A-20, Neosunvale PW-6030A-20, manufactured by JGC Catalysts & Chemicals Co., Ltd. E made by Merck Co., Ltd., which is an uncoated type, such as Neosantale ZPW-6010 (S-25), Neosambert ZPW-6030 (S-25), etc. solex T, such as Eusolex T-AQUA, and the like. Of these, those coated with hydrous silicic acid or anhydrous silicic acid are preferred, and those coated with hydrous silicic acid are more preferred because of excellent dispersibility and uniform application. In order to enhance the sun protection effect, a powder dispersion aqueous solution in which an ultraviolet scattering agent such as titanium oxide or zinc oxide is further added and dispersed in the powder dispersion aqueous solution may be used.

  The primary particle diameter of the powder is preferably 1 to 100 nm, more preferably 5 to 70 nm. When the primary particle diameter is less than 1 nm, the particles tend to aggregate and become difficult to disperse. On the other hand, when the thickness exceeds 100 nm, the effect of scattering ultraviolet rays tends to be weak, and the sedimentation in the aerosol composition tends to be fast and difficult to discharge with a uniform composition.

  The content of the powder is preferably 7 to 80% by mass and more preferably 10 to 75% by mass in the aqueous powder dispersion. When the content of the powder is less than 7% by mass, the concentration of the powder in the aqueous stock solution tends to be low and the ultraviolet scattering effect tends to be insufficient. Moreover, when it exceeds 80 mass%, there exists a tendency for a dispersibility to be bad and to become difficult to handle.

  Moreover, 5-50 mass% is preferable in aqueous | water-based stock solution, and, as for content of powder, 7-45 mass% is more preferable. When the content of the powder is less than 5% by mass, the ultraviolet scattering effect tends to be insufficient. Moreover, when it exceeds 50 mass%, it becomes difficult to disperse | distribute powder uniformly in a discharge material, and there exists a tendency for it to become white easily on an injection surface.

  The water is a solvent of the powder dispersion aqueous solution, and examples thereof include purified water and ion exchange water.

  Examples of the alcohol include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, pentylene glycol, and glycerin, and monohydric alcohols such as ethanol and isopropanol.

  The powder-dispersed aqueous solution can contain a viscosity modifier, a surfactant and the like in addition to the powder (ultraviolet scattering agent), water and alcohol.

  The acrylic acid ester polymer associates with an alkaline agent to adjust the viscosity of the aqueous stock solution, facilitates dispersion of the powder in the aqueous stock solution and aerosol composition, improves foamability, eliminates stickiness, and provides a feeling of use. It is used for the purpose of improving. In addition, the acrylic ester polymer of this application adjusts to specific pH by using together with the alkali agent mentioned later, and is thickened by making it polymerize.

  Examples of the acrylate polymer include (acrylates / itaconic acid steareth-20) copolymer, (acrylates / itaconic acid ceteth-20) copolymer, and the like.

  The content of the acrylic ester polymer is preferably 0.1 to 10% by mass, and more preferably 0.3 to 5% by mass in the aqueous stock solution. When the content of the acrylate polymer is less than 0.1% by mass, the dispersibility of the powder tends to decrease, the foamability tends to decrease, and the usability tends to deteriorate. On the other hand, when the amount exceeds 10% by mass, the viscosity of the aqueous stock solution becomes too high and it is difficult to mix with a liquefied gas having a low viscosity, and the foam tends to be sticky.

  The alkaline agent is used for the purpose of adjusting the pH of the aqueous stock solution and adjusting the viscosity by polymerizing the acrylate polymer. Examples of the alkaline agent include organic alkalis such as triethanolamine, diisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, sodium hydroxide, hydroxylation Examples include inorganic alkalis such as potassium and ammonium hydroxide, and the pH of the aqueous stock solution can be adjusted to 6 to 9 using these alkali agents to increase the viscosity.

  In the above-mentioned surfactant, the aqueous stock solution and the liquefied gas form an oil-in-water emulsion in the container, and when discharged, the aqueous stock solution is foamed to form a fine foam, and the powder is applied to the skin and hair. It is used for the purpose of making it easier.

  Examples of the surfactant include polyoxyethylene polyoxypropylene alkyl ethers such as POE · POP cetyl ether and POE · POP decyl tetradecyl ether; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate; POE lanolin alcohol and the like Polyoxyethylene lanolin alcohol; polyoxyethylene hydrogenated castor oil such as POE hydrogenated castor oil; POE cetyl ether, POE stearyl ether, POE oleyl ether, POE lauryl ether, POE behenyl ether, POE octyldodecyl ether, POE isocetyl ether, POE Polyoxyethylene alkyl ethers such as isostearyl ether; polyethylene such as polyethylene glycol monostearate Recall fatty acid ester, hexaglyceryl monolaurate, hexaglyceryl monomyristate, pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglyceryl monooleate, pentaglyceryl monostearate, decaglyceryl monolaurate, decaglyceryl monomyristate, monostearin Polyglycerin fatty acid ester such as decaglyceryl acid, decaglyceryl monoisostearate, decaglyceryl monooleate; polyoxyethylene glycerin fatty acid ester such as POE glyceryl monooleate; monococonut oil fatty acid POE sorbitan, monopalmitic acid POE sorbitan, monostearin Acid POE sorbitan, monoisostearic acid POE sorbitan, monooleic acid POE sorbitan Polyoxyethylene sorbitan fatty acid esters and the like; monolaurate POE sorbit, tetrastearate POE sorbit, polyoxyethylene sorbit fatty acid esters such as tetraoleate POE sorbitol; nonionic surfactants, and the like. Further, imidazoline-based amphoteric surfactants such as betaine acetate, imidazolium betaine, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, lauryldimethylaminoacetic acid betaine, alkylbetaine, Amphoteric surfactants such as betaine amphoteric surfactants such as amidobetaine and sulfobetaine, fatty acid soaps, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, Silicones such as anionic surfactants such as polyoxyethylene / methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer, poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer Surfactants, natural surfactants such as surfactin sodium, cyclodextrin, hydrogenated enzyme soybean lecithin, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid Potassium, N-coconut oil fatty acid acyl-L-glutamate sodium, N-lauroyl-L-glutamate triethanolamine, N-lauroyl-L-glutamate potassium, N-lauroyl-L-glutamate sodium, N-myristoyl-L-glutamate N-acyl glutamate such as potassium, sodium N-myristoyl-L-glutamate and sodium N-stearoyl-L-glutamate, N-coconut oil fatty acid acyl-L-glutamic acid, N-lauroyl-L-glutamic acid, N-stear N-acylglutamic acid such as yl-L-glutamic acid, N-acylglycine salt such as N-coconut oil fatty acid acylglycine potassium, N-coconut oil fatty acid acylglycine sodium, N-coconut oil fatty acid acyl-DL-alanine triethanolamine Amino acid surfactants such as N-acylalanine salts, and mixtures thereof.

  0.5-10 mass% is preferable in aqueous | water-based stock solution, and, as for content of surfactant, 1-8 mass% is more preferable. When the content of the surfactant is less than 0.5% by mass, the foaming property is weak and tends to be difficult to apply uniformly. Moreover, when it exceeds 10 mass%, surfactant tends to remain on the adhesion surface and the feeling of use tends to decrease.

  The liquid oil is used for the purpose of eliminating a squeak due to powder when applying a foam, and acting as a solvent for an ultraviolet absorber.

  The liquid oil is liquid at 25 ° C., for example, methylpentanediol dineopentanoate, diethylpentanediol dineopentanoate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, propylene dilaurate Glycol, ethylene glycol distearate, diethylene glycol dilaurate, diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, triethylene glycol distearate, triethylene glycol diisostearate, triethylene glycol dioleate, isopropyl myristate , Isopropyl palmitate, cetyl isooctanoate, hydro Octyl xystearate, ethylhexylxyl hydroxystearate, propylene glycol monostearate, propylene glycol monooleate, ethylene glycol monostearate, glyceryl tri-2-ethylhexanoate, tri (caprylic / capric acid) glycerin, isononane Ester oils such as isononyl acid, isotridecyl isononanoate, diethoxyethyl succinate, diisostearyl malate, jojoba ester; methyl polysiloxane, cyclopentasiloxane, cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, tetrahydrotetramethylcyclotetrasiloxane, octamethyltrisi Hexane, decamethyltetrasiloxane, methyl hydrogen polysiloxane, silicone oils such as methyl phenyl polysiloxane; liquid paraffin, normal pentane, and the like hydrocarbon oils, such as isopentane.

  The content of the liquid oil is preferably 1 to 30% by mass and more preferably 3 to 20% by mass in the aqueous stock solution. When the content of the liquid oil is less than 1% by mass, the effect of suppressing squeaking due to powder tends to be difficult to obtain. Moreover, when it exceeds 30 mass%, it tends to be sticky on the coated surface, and the feeling of use tends to decrease.

  In the aqueous stock solution, in addition to the powder dispersion aqueous solution, the acrylate polymer, the surfactant and the liquid oil, other active ingredients other than the ultraviolet absorber, the ultraviolet scattering agent and the ultraviolet absorber (hereinafter referred to as other active ingredients) In addition, alcohols, powders other than the powder contained in the aqueous powder dispersion (hereinafter also referred to as other powders), and the like can be appropriately contained.

  By containing the ultraviolet absorber, the effect of blocking ultraviolet rays can be enhanced, and sunburn and damage can be further prevented. However, it tends to be sticky on the coated surface, tends to reduce the feeling of use, and tends to decrease foamability, and it is preferable not to contain an ultraviolet absorber.

  Examples of the ultraviolet absorber include hexyl diethylaminohydroxybenzoylbenzoate, ethylhexyl dimethylaminobenzoate, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, and paradimethylaminobenzoic acid. Aminobenzoic acid derivatives such as octyl; ethyl hexyl salicylate, homosalate, dipropylene glycol salicylate, ethylene glycol salicylate, octyl salicylate, phenyl salicylate, homomenthyl salicylate, myristyl salicylate, methyl salicylate, etc .; ethylhexyl methoxycinnamate, diisopropione Methyl cinnamate, ethyl hexyl glyceryl dimethoxycinnamate, isomethoxyparamethoxycinnamate Pill, 2-ethylhexyl paramethoxycinnamate, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, octyl paramethoxycinnamate, sodium paramethoxycinnamate, potassium paramethoxycinnamate, paramethoxycinnamate Cinnamic acid derivatives such as mono-2-ethylhexanoic acid glyceryl; diphenyl acrylate derivatives such as octocrylene and ethocrylene; oxybenzone-1, oxybenzone-2, oxybenzone-3, oxybenzone-4, oxybenzone-5, oxybenzone-6, oxybenzone Benzophenone derivatives such as -9; ben such as ethyl hexyl dimethoxybenzylidene dioxoimidazolidine propionate, octyl dimethoxybenzylidene dioxoimidazolidine propionate Reden camphor derivatives; phenylbenzimidazole derivatives such as phenylbenzimidazolesulfonic acid, phenylbenzimidazolesulfonic acid Na, phenyldibenzimidazoletetrasulfonic acid 2Na; benzalmalonate derivatives such as polysilicon-15; t-butylmethoxydibenzoyl Dibenzoylmethane derivatives such as methane; and the like.

  Content in the case of containing a ultraviolet absorber is 1-20 mass% in aqueous | water-based stock solution, and 5-15 mass% is more preferable. When the content of the ultraviolet absorber is less than 1% by mass, the effect of the ultraviolet absorber tends to be difficult to obtain. On the other hand, when it exceeds 20% by mass, it tends to be sticky and the feeling of use tends to be lowered, and the dispersibility of the powder tends to be lowered, and the powder tends to be difficult to apply uniformly.

  The other active ingredients are used for the purpose of imparting effects such as moisturizing the skin, suppressing itching and inflammation, and imparting a refreshing feeling.

  Other active ingredients include, for example, various fragrances such as natural fragrance and synthetic fragrance; refreshing agents such as l-menthol, camphor and mint oil; ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene Moisturizers such as glycol, glycerin, xylitol, sorbitol, maltitol, mannitol, collagen, hyaluronic acid, caronic acid, sodium lactate, dl-pyrrolidone carboxylate, keratin, casein, lecithin, urea, jojoba ester; ascorbic acid, α -Antioxidants such as tocopherol, dibutylhydroxytoluene; retinol, retinol acetate, retinol palmitate, calcium pantothenate, magnesium ascorbate phosphate, sodium ascorbate, dl-α -Vitamins such as tocopherol, tocopherol acetate, tocopherol, tocopherol nicotinate; astringents such as allantoin hydroxyaluminum, tannic acid, citric acid, lactic acid, alum; local anesthetics such as dibucaine hydrochloride, tetracaine hydrochloride, lidocaine hydrochloride, lidocaine Anti-inflammatory agents such as diphenhydramine, glycyrrhetinic acid, dipotassium glycyrrhizinate; antiperspirant ingredients such as chlorohydroxyaluminum and zinc paraphenolsulfonate; lauric acid methacrylate, methyl benzoate, methyl phenylacetate, geranyl crotolate, acetophenone myristate, Deodorizers such as benzyl acetate, benzyl propionate, and green tea extract; In addition, what is necessary is just to dissolve these active ingredients in liquid oil, alcohol, and water according to solubility.

  The content in the case of containing other active ingredients is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass in the aqueous stock solution. When the content of the active ingredient is less than 0.1% by mass, the effect of containing the active ingredient tends to be difficult to obtain. Moreover, when it exceeds 10 mass%, there exists a tendency for the dispersibility and foaming property of a powder to fall easily, and to become easy to inhibit the effect which interrupts | blocks an ultraviolet-ray.

  The alcohols are used for the purpose of suppressing stickiness due to the solvent of the active ingredient, liquid oil, active ingredient, etc., and improving the drying property on the ejection surface.

  Examples of alcohols include monohydric alcohols having 2 to 3 carbon atoms such as ethanol and isopropanol, and polyhydric alcohols having 3 to 5 carbon atoms such as propylene glycol, 1,3-butylene glycol, and glycerin. Can be mentioned.

  In the case of containing alcohols, the content in the aqueous stock solution is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass. When content of alcohol is less than 1 mass%, there exists a tendency for the effect of alcohol to become difficult to be acquired. Moreover, when it exceeds 30 mass%, there exists a tendency for the dispersibility and foamability of a powder to fall easily.

  The other powders are used for the purpose of further improving the sun protection effect, improving stickiness and improving the feeling of use.

  Examples of other powders include corn starch aluminum octenyl succinate, talc, silica, nylon powder, bentonite and the like. Moreover, the said ultraviolet scattering agent can also be contained further.

  The average particle size of other powders is preferably 1 to 40 μm, more preferably 3 to 30 μm. When the average particle size is less than 1 μm, the particles tend to aggregate and the redispersibility after sedimentation tends to deteriorate. On the other hand, when it exceeds 40 μm, sedimentation in the aerosol composition is fast and tends to be difficult to discharge with a uniform composition, and tends to be clogged with the introduction hole of the aerosol valve and the discharge hole of the discharge member.

  In the case of containing other powders, the content in the aqueous stock solution is preferably 0.1 to 10% by mass, and more preferably 0.3 to 5% by mass. When the content of the other powder is less than 0.1% by mass, the effect of the powder tends to be difficult to obtain. Moreover, when it exceeds 10 mass%, even if it mixes before use, it tends to settle and tends to become difficult to discharge with a uniform composition.

  Aqueous stock solutions are, for example, powder-dispersed aqueous solutions, aqueous bases in which acrylic acid ester polymers and surfactants are added to water or aqueous alcohol solutions, alkaline aqueous solutions in which alkaline agents are added to water, and UV absorbers as necessary Prepare an oily base with each of the oil-soluble active ingredients added to a liquid oil or alcohol, add a powder-dispersed aqueous solution to the aqueous base to disperse the powder, and add an aqueous alkaline solution to this to adjust the viscosity. Further, it can be prepared by adding an oily base to form an emulsion. In addition, the viscosity is adjusted by adding an alkaline aqueous solution in which an alkaline agent is dissolved in water to an aqueous solution in which the surfactant and the acrylate polymer are dissolved in water, and then a part of the liquid oil, alcohol, and the surfactant. It may be prepared by adding an oily base in which is dissolved to form an emulsion and finally adding an aqueous powder dispersion. Further, as the powder dispersion aqueous solution, a commercially available powder dispersion aqueous solution added with an ultraviolet scattering agent may be used in order to enhance the sun protection effect.

  The content of the aqueous stock solution is preferably 60 to 97% by mass and more preferably 70 to 95% by mass in the aerosol composition. When the content of the aqueous stock solution is less than 60% by mass, the foam tends to be rough and difficult to apply uniformly. Moreover, when it exceeds 97 mass%, there exists a tendency for foamability to be bad and to become difficult to spread.

  The liquefied gas is a liquid having a vapor pressure in the pressure-resistant container, and is emulsified with an aqueous stock solution to form an aerosol composition. When discharged to the outside, it vaporizes to foam the stock solution to form a foam (foam) To.

  Examples of the liquefied gas include liquefied petroleum gas, dimethyl ether, hydrofluoroolefin, and a mixture thereof. Among these, liquefied petroleum gas and hydrofluoroolefin are preferably used from the viewpoint of easily forming an aqueous stock solution and an emulsion, and liquefied petroleum gas is particularly preferable from the viewpoint of excellent foamability.

  3-40 mass% is preferable in aerosol composition, and, as for content of liquefied gas, 5-30 mass% is more preferable. When the content of the liquefied gas is less than 3% by mass, the foaming property is poor and it tends to be difficult to spread. Moreover, when it exceeds 40 mass%, there exists a tendency for a stock solution and liquefied gas to become difficult to emulsify, and for a bubble to become coarse and to become difficult to apply | coat uniformly.

  In addition to the liquefied gas, a compressed gas can be contained for the purpose of adjusting the pressure in the pressure vessel, adjusting the discharge state, and the like. As compressed gas, carbon dioxide gas, nitrous oxide gas, nitrogen gas, compressed air, etc. can be contained, for example.

  The aerosol foamed sun protection agent of the present invention can be produced by filling a pressure resistant container with an aqueous stock solution, fixing and sealing an aerosol valve, and filling a liquefied gas from the aerosol valve. Note that the liquefied gas may be filled by undercup filling before the aerosol valve is fixed.

  The pressure vessel is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include an aerosol vessel used for ordinary aerosol products. For example, it is made of pressure glass, made of metal such as aluminum or tinplate, or made of synthetic resin such as polyethylene terephthalate, and has a pressure resistance and is formed into a bottomed cylindrical shape having an opening at the upper end. Things can be used.

  As the aerosol valve, for example, a mounting cup fixed to the opening of the pressure vessel, a housing held by the mounting cup, a stem accommodated in the housing so as to be movable up and down, and the stem is always biased upward. And a stem rubber for closing the stem hole of the stem, and a tube for supplying the aerosol composition in the container into the housing.

  The aerosol foam sunscreen agent of the present invention is excellent in the dispersibility and stability of the powder in the aerosol composition, and a fine foam-like discharge in which the powder is uniformly dispersed is discharged, and the coated surface It is an aerosol-type foamy sunscreen that can be spread evenly and has an excellent sunscreen effect. Moreover, since it can contain a large amount of powder which is an ultraviolet scattering agent, it can be a sunscreen agent having a sufficient sun protection effect without containing an ultraviolet absorber. Furthermore, although it contains a large amount of powder, there is no creaking due to the powder and no stickiness due to the liquid oil, resulting in excellent usability.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these.

Preparation of Stock Solution Each stock solution used in the test aerosol products of Examples and Comparative Examples was prepared according to the formulation shown in Table 1.

＊１：ＷＴ−ＰＦ０１（商品名）、粉体：４０質量％含有、テイカ株式会社製
＊２：Ｓｏｌａｖｅｉｌ ＣＴ−３０Ｗ（商品名）、粉体：４０質量％含有、クローダジャパン株式会社製
＊３：ＴＴＯ−Ｓ−２（商品名）、一次粒子径：５０ｎｍ、石原産業株式会社製
＊４：ＳＩＬＩＣＡ ＰＥＡＲＬ ２０ＣＧ（商品名）、日揮触媒化成株式会社製
＊５：Ｓｔｒｕｃｔｕｒｅ２００１（商品名）、アクゾノーベル株式会社製
＊６：カーボポール９４０（商品名）、日光ケミカルズ株式会社製
＊７：ペミュレンＴＲ−１（商品名）、日光ケミカルズ株式会社製
＊８：ＮＩＫＫＯＬ ＴＬ−１０（商品名）、日光ケミカルズ株式会社製
＊９：ＳＨ３７７１Ｍ（商品名）、東レ・ダウコーニング株式会社製
＊１０：Ｎｅｏｓｏｌｕｅ ＭＰ（商品名）、日本精化株式会社製
＊１１：ＦＬＯＲＡ ＥＳＴＥＲＳ Ｋ-２０Ｗ、ＪＯＪＯＢＡ（商品名）、池田物産株式会社製
＊１２：メッキンス Ｍ（商品名）、上野製薬株式会社製

* 1: WT-PF01 (trade name), powder: 40% by mass, manufactured by Teika Co., Ltd. * 2: Solaveil CT-30W (trade name), powder: 40% by mass, manufactured by Claude Japan Co., Ltd. * 3 : TTO-S-2 (trade name), primary particle size: 50 nm, manufactured by Ishihara Sangyo Co., Ltd. * 4: SILICA PEARL 20CG (trade name), manufactured by JGC Catalysts & Chemicals Co., Ltd. * 5: Structure 2001 (trade name), Akzo Nobel * 6: Carbopol 940 (trade name), Nikko Chemicals Co., Ltd. * 7: Pemulen TR-1 (trade name), Nikko Chemicals Co., Ltd. * 8: NIKKOL TL-10 (trade name), Nikko Chemicals * 9: SH3771M (trade name) manufactured by Toray Dow Corning Co., Ltd. * 10: Neosolute MP (trade name), Japan Mfg. Co., Ltd. * 11: FLORA ESTERS K-20W, JOJOBA (trade name), Ikedabussan Co., Ltd. * 12: Mekkinsu M (trade name), Ueno Fine Chemicals Industry Co., Ltd.

Examples 1-7 and Comparative Examples 1-4
According to the formulations shown in Tables 2 and 3, each stock solution (see Table 1) and liquefied gas (* 13) were filled into a pressure-resistant container made of polyethylene terephthalate, and an aerosol valve was fixed to prepare a test aerosol product. The following evaluation was performed about the obtained aerosol product for a test. The results are shown in each table.
* 13: Mixture of normal butane, isobutane and propane (vapor pressure at 25 ° C is 0.35 MPa)

(1) Dispersibility of powder The aerosol product for test was allowed to stand in a state where the powder was uniformly dispersed, and the time when the dispersed powder started to settle was measured.
○: 10 seconds or more Δ: 5 to 10 seconds ×: within 5 seconds

(2) Redispersibility of powder The following criteria were used to determine the redispersibility of powder that had settled at the bottom of the container when the aerosol product for test was left at 25 ° C for 1 month and the container was shaken up and down repeatedly. Based on the evaluation.
A: Dispersed uniformly within 3 times.
○: Evenly dispersed 4 to 6 times.
Δ: Uniformly dispersed in 7 to 10 times.
X: Even if shaken 10 times, a part of the powder remained settled on the bottom and was not uniformly dispersed.

(3) Foam quality Each test aerosol product was immersed in a constant temperature water bath at 25 ° C. for 30 minutes, 0.5 g was discharged onto the palm, the foam quality of the formed foam was confirmed visually, and evaluated based on the following criteria: did.
○: The texture was finely and three-dimensionally foamed.
Δ1: Three-dimensional foaming but rough foam.
Δ2: Poor foaming property and part of the liquid dripped.
X: Poor foaming and dripping.

(4) Feeling of use Each test aerosol product was immersed in a constant temperature water bath at 25 ° C. for 30 minutes, 0.5 g was discharged onto the palm of the hand, and the condition when spread on the arm was evaluated.
○: Stickiness was not felt.
X1: There was stickiness like a feeling of adhesion.
X2: Although there was no stickiness, the applied part was squeezed.

Formulation Example 1 Aerosol-type sunscreen agent 45 g (90% by mass) of the following stock solution was filled in a pressure-resistant container made of polyethylene terephthalate (full volume 100 ml), and an aerosol valve was fixed. And the aerosol product for a test was manufactured by filling liquefied gas (* 13) 5g (10 mass%) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in each table.

<Undiluted solution>
Hydrous silicate-coated titanium oxide dispersed aqueous solution (* 1) 20.0
Silica (* 4) 1.0
(Acrylates / Stearless Itaconic Acid-20) Copolymer (* 5) 0.5
Polyoxyethylene hydrogenated castor oil (* 14) 1.5
Polyoxyethylene / methylpolysiloxane copolymer (* 9) 2.5
Dineopentanoic acid methylpentanediol (* 10) 5.0
Cyclopentasiloxane (* 15) 1.5
Triethanolamine 0.3
Methyl paraoxybenzoate (* 12) 0.1
Ethanol 10.0
Purified water 57.6
Total (parts by mass) 100.0
* 14: HCO-40 (trade name), manufactured by Nikko Chemicals Co., Ltd. * 15: DC345 (trade name), manufactured by Toray Dow Corning Co., Ltd.

Formulation Example 2 Aerosol-type sunscreen agent 45 g (90% by mass) of the following stock solution was filled in a pressure-resistant container made of polyethylene terephthalate (full amount 100 ml), and an aerosol valve was fixed. And the aerosol product for a test was manufactured by filling liquefied gas (* 13) 5g (10 mass%) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in each table.

<Undiluted solution>
Hydrous silicate-coated titanium oxide dispersed aqueous solution (* 1) 25.0
Silica (* 4) 1.0
(Acrylates / Stearless Itaconic Acid-20) Copolymer (* 5) 2.0
Palm oil fatty acid polyoxyethylene sorbitan (* 8) 1.0
Polyoxyethylene / methylpolysiloxane copolymer (* 9) 2.0
Dineopentanoic acid methylpentanediol (* 10) 8.0
Isononyl isononanoate (* 16) 2.0
Triethanolamine 0.3
Methyl paraoxybenzoate (* 12) 0.1
Diethylaminohydroxybenzoyl hexyl benzoate /
Ethylhexyl methoxycinnamate (* 17) 4.0
Octocrylene (* 18) 4.0
Ethanol 8.0
Purified water 42.6
Total (parts by mass) 100.0
* 16: Saracos 99 (trade name), manufactured by Nisshin Oillio Group, Inc. * 17: Uvinul A plus B (trade name), manufactured by BASF Japan Ltd. * 18: Eusolex OCR (trade name), manufactured by Merck & Co., Ltd.

Formulation Example 3 Aerosol-type sunscreen agent 45 g (90% by mass) of the following stock solution was filled in a pressure-resistant container made of polyethylene terephthalate (full volume 100 ml), and an aerosol valve was fixed. And the aerosol product for a test was manufactured by filling liquefied gas (* 13) 5g (10 mass%) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in each table.

<Undiluted solution>
Silica-coated titanium oxide dispersion aqueous solution (* 19) 20.0
Silica (* 4) 1.0
(Acrylates / Stearless Itaconic Acid-20) Copolymer (* 5) 1.0
Palm oil fatty acid polyoxyethylene sorbitan (* 8) 1.0
Polyoxyethylene / methylpolysiloxane copolymer (* 9) 2.0
Dineopentanoic acid methylpentanediol (* 10) 4.0
Jojoba ester (* 11) 1.0
Liquid paraffin (* 20) 1.0
Triethanolamine 0.3
Methyl paraoxybenzoate (* 12) 0.1
Ethanol 3.0
Propylene glycol 2.0
Purified water 63.6
Total (parts by mass) 100.0
* 19: Neo sun veil PW-6030A-20 (trade name), powder (anhydrous silicate-coated titanium oxide): 40% by mass, manufactured by JGC Catalysts & Chemicals Co., Ltd. * 20: High Coal K-230 (trade name), Kaneda Made by Co., Ltd.

Formulation Example 4 Aerosol-type sunscreen agent 45 g (90% by mass) of the following stock solution was filled in a pressure-resistant container made of polyethylene terephthalate (full volume 100 ml), and an aerosol valve was fixed. And the aerosol product for a test was manufactured by filling liquefied gas (* 13) 5g (10 mass%) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in each table. Titanium oxide (* 3) and zinc oxide (* 21) were added in advance and dispersed in a hydrous silicate-coated titanium oxide dispersion aqueous solution (* 1).

<Undiluted solution>
Hydrous silicate-coated titanium oxide dispersed aqueous solution (* 1) 35.0
Titanium oxide (* 3) 10.0
Zinc oxide (* 21) 15.0
(Acrylates / Stearless Itaconic Acid-20) Copolymer (* 5) 1.0
Palm oil fatty acid polyoxyethylene sorbitan (* 8) 1.0
Polyoxyethylene / methylpolysiloxane copolymer (* 9) 2.0
Dineopentanoic acid methylpentanediol (* 10) 5.0
Jojoba ester (* 11) 1.5
Triethanolamine 0.3
Methyl paraoxybenzoate (* 12) 0.1
Ethanol 5.0
Propylene glycol 2.0
Purified water 22.1
Total (parts by mass) 100.0
* 21: MZ-500HP (trade name), primary particle size: 25 nm, manufactured by Teika Co., Ltd.

  About each aerosol product for a test of the obtained prescription examples 1-4, said evaluation was performed similarly to an Example and a comparative example. The evaluation results are shown in Table 4.

Claims (2)

An aerosol composition comprising a powder dispersion aqueous solution containing powder and a solution for dispersing the powder in an aqueous stock solution, an aqueous stock solution containing an acrylate polymer, a surfactant and a liquid oil, and a liquefied gas is pressure resistant. Filled into containers ,
The powder is a powder coated with hydrous silicic acid or silicic anhydride, and is contained in an aqueous stock solution in an amount of 5 to 50% by mass,
The said acrylic ester polymer is an aerosol type foamy sunscreen agent containing the (acrylates / stearic itaconate-20) copolymer or the (acrylates / cetaconic acid ceteth-20) copolymer . The content of the liquefied gas, aerosol foam sunscreen agent according to claim 1 which is 3 to 40 mass% in the aerosol composition.