JP6157972B2 - Aerosol sunscreen - Google Patents

Description

  The present invention relates to an aerosol type sunscreen agent. More specifically, the present invention relates to a stable aerosol type sunscreen agent that does not precipitate an ultraviolet absorber despite containing a high concentration of the ultraviolet absorber.

  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.

  The UVA protection index of a sunscreen agent is represented by a PA value (PA + to PA ++++), and the UVB protection index is represented by an SPF value (SPF2 to SPF50 +). The highest PA value so far has been PA ++, but since it has been raised to PA ++++ since 2013, it can be seen that an even higher sun protection effect is required.

  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, if an aerosol type sun protection agent containing a large amount of an ultraviolet absorber is used, the ultraviolet absorber is precipitated because of its low solubility in liquefied gas, and the introduction of aerosol valves and jets There is a problem that the injection state becomes worse due to clogging with the injection holes of the member, and further, injection cannot be performed.

  Patent Document 1 discloses a sunscreen cosmetic containing a specific modified polymer silicone, a volatile silicone and / or a volatile hydrocarbon oil, and an ultraviolet absorber and / or an ultraviolet scattering agent. Example 7 discloses a non-aqueous stock formulation aerosol composition. However, since the nonaqueous stock solution contains only an oil and an ultraviolet absorber, the modified polymer silicone tends to be sticky on the spray surface, has poor drying properties, and has a problem in usability.

  Comparative Example 4 of Patent Document 2 discloses an aerosol composition for sunscreen comprising a non-aqueous stock solution and a liquefied gas containing oil, alcohol, an ultraviolet absorber, and a powder having an ultraviolet scattering effect. However, there is a problem that the sun protection effect is insufficient because the ultraviolet absorbent is as small as 10% by weight in the stock solution.

  Patent Document 3 discloses an oil-in-water sunscreen cosmetic containing (a) a specific ultraviolet absorber, (b) a specific polyether-modified silicone, (c) a low-viscosity silicone oil, and (d) water. In particular, sunscreen cosmetics are disclosed in which bisethylhexyloxyphenol methoxyphenyl triazine, which is a triazine derivative capable of protecting against UVA and UVB, is essential to provide a high UV protection effect. Since this cosmetic contains 20% by mass or more of an ultraviolet absorber, the sun protection effect is very high. However, when an aerosol product containing a high concentration of an ultraviolet absorber and using a liquefied gas is used, the ultraviolet absorber is likely to precipitate, and particularly when a triazine derivative is contained as the ultraviolet absorber, it is gradually increased when stored for a long period of time. It has been found that there is a problem of precipitation.

Japanese Patent No. 3370687 JP 2010-270060 A JP 2012-162481 A

  The present invention has been made in view of the above problems, and contains a large amount of an ultraviolet absorber, has an excellent sun protection effect, can be sprayed thinly and uniformly over a wide range, and the spray surface is not sticky and has excellent usability. Another object of the present invention is to provide a stable aerosol type sunscreen agent in which no ultraviolet absorber is deposited.

  The aerosol-type sunscreen agent of the present invention is a UV absorber excluding the triazine derivative, in which a pressure-resistant container is filled with an aerosol composition composed of a non-aqueous stock solution containing a UV absorber excluding a triazine derivative, an oil component, and an alcohol and a liquefied gas. The content of the absorbent is 20 to 50% by mass in the nonaqueous stock solution, and the content of the liquefied gas is 50 to 80% by mass in the aerosol composition.

  The ultraviolet absorber excluding the triazine derivative is preferably at least one selected from the group consisting of aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, diphenyl acrylate derivatives, and benzophenone derivatives.

  It is preferable that content of the said alcohol is 30-70 mass% in a non-aqueous stock solution.

  It is preferable that the nonaqueous stock solution contains an inorganic oxide powder, and the content of the inorganic oxide powder is 0.1 to 15% by mass in the nonaqueous stock solution.

  The present invention comprises an ultraviolet absorber excluding a triazine derivative, a nonaqueous stock solution containing oil and alcohol, and an aerosol composition comprising a liquefied gas filled in a pressure resistant container, and the content of the ultraviolet absorber excluding the triazine derivative is non-existent. Because it is an aerosol type sunscreen agent that is 20-50% by mass in the water stock solution and the content of the liquefied gas is 50-80% by mass in the aerosol composition, it is excellent in sunscreen effect, easily thin and uniformly wide Therefore, it is possible to provide a stable aerosol type sunscreen agent that can be sprayed onto the surface, has a non-sticky spray surface, is excellent in feeling of use, and does not deposit an ultraviolet absorber.

2 is a photograph of a coated plate showing the evaluation results of the ultraviolet blocking effect of Example 1. It is a photograph of the coating plate which shows the evaluation result of the ultraviolet-blocking effect of Example 2. 6 is a photograph of a coated plate showing an evaluation result of an ultraviolet blocking effect of Comparative Example 1. It is a photograph of the coating plate which shows the evaluation result of the ultraviolet-blocking effect of the comparative example 2. It is a photograph of the coating plate which shows the evaluation result of the ultraviolet-blocking effect of the comparative example 3. It is a photograph of the coating plate which shows the evaluation result of the ultraviolet-blocking effect of the comparative example 4.

  The aerosol-type sunscreen agent of the present invention has a pressure-resistant container filled with an aerosol composition comprising a non-aqueous stock solution and a liquefied gas.

  The non-aqueous stock solution contains an ultraviolet absorber excluding the triazine derivative, an oil component, and alcohol.

  The ultraviolet absorber excluding the triazine derivative is used for the purpose of adhering to the skin and absorbing the ultraviolet rays to prevent the ultraviolet rays from reaching the skin.

  Examples of the ultraviolet absorber excluding the triazine derivative include hexyl diethylaminohydroxybenzoylbenzoate, ethylhexyl dimethylaminobenzoate, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, paradimethylaminobenzoate. Aminobenzoic acid derivatives such as octyl acid; ethyl hexyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, octyl salicylate, phenyl salicylate, homomenthyl salicylate, myristyl salicylate, etc .; ethylhexyl methoxycinnamate, methyl diisopropylcinnamate, dimethoxy Ethylhexyl glyceryl cinnamate, isopropyl paramethoxycinnamate, trimethoxyke Cinnamic acids such as methylbis (trimethylsiloxy) silylisopentyl cinnamate, octyl paramethoxycinnamate, sodium paramethoxycinnamate, potassium paramethoxycinnamate, glyceryl para-2-methoxyhexamate mono-2-ethylhexanoate Derivatives; Diphenyl acrylate derivatives such as octocrylene and ethocrylene; benzophenone derivatives such as oxybenzone-1, oxybenzone-2, oxybenzone-3, oxybenzone-4, oxybenzone-5, oxybenzone-6, oxybenzone-9; dimethoxybenzylidene dioxoimidazolidine propion Benzylidene camphor derivatives such as ethyl hexyl acid, dimethoxybenzylidene dioxoimidazolidine propionate; phenylbenzimidazolesulfonic acid Phenylbenzimidazole derivatives such as phenylbenzimidazolesulfonic acid Na and phenyldibenzimidazoletetrasulfonic acid 2Na; benzalmalolate derivatives such as polysilicon-15; dibenzoylmethane derivatives such as t-butylmethoxydibenzoylmethane; It is done. Among these, at least one selected from the group consisting of aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, diphenyl acrylate derivatives and benzophenone derivatives is contained in a high concentration, and also as an aerosol composition together with a liquefied gas Precipitation is unlikely to occur, which is preferable because the sun protection effect is enhanced.

  The content of the ultraviolet absorber excluding the triazine derivative is 20 to 50% by mass in the nonaqueous stock solution, and preferably 25 to 45% by mass. When the content of the UV absorber is less than 20% by mass, the amount adhering to the skin is small (concentration in the discharged product is low) and the effect of blocking UV rays tends to be low, and it is necessary to repeatedly spray and apply. There is. Moreover, when it exceeds 50 mass%, there exists a tendency for it to become difficult to spray and apply | coat uniformly, to become sticky on a spray surface, and to tend to precipitate when it stores for a long period of time.

  The oil component acts as a solvent for dissolving the ultraviolet absorbent, and is used for the purpose of easily spraying and applying the ultraviolet absorbent and making the ultraviolet absorbent easily adhere to the skin. Moreover, when it contains the ultraviolet-ray scattering agent mentioned later, it acts also as a solvent which disperse | distributes an ultraviolet-ray scattering agent, and can spray and apply | coat an ultraviolet absorber and an ultraviolet-scattering agent equally.

  Examples of the oil include ester oil, silicone oil, fats and oils, and hydrocarbons.

  Examples of the ester oil include methylpentanediol dineopentanoate, diethylpentanediol dineopentanoate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, propylene glycol dilaurate, ethylene glycol distearate, and dilauric acid. Diesters of fatty acids and dihydric alcohols such as diethylene glycol, diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, triethylene glycol distearate, triethylene glycol diisostearate, triethylene glycol dioleate; monostearin Propylene glycol acid, propylene monooleate Monoesters of fatty acids such as recall and ethylene glycol monostearate and dihydric alcohols; Triesters of fatty acids such as glyceryl tri-2-ethylhexanoate and tri (caprylic / capric acid) glycerin and trihydric alcohols; isononanoic acid Esters of branched fatty acids and branched alcohols such as isononyl and isotridecyl isononanoate; esters of carboxylic acids and alcohols such as diethoxyethyl succinate and diisostearyl malate; isopropyl myristate, isopropyl palmitate, cetyl isooctanoate, hydroxy And esters of fatty acids and alcohols such as octyl stearate and ethylhexyl hydroxystearate. In particular, a diester of a fatty acid and a dihydric alcohol is preferable from the viewpoint that an ultraviolet absorber is blended with alcohol and can be stably dissolved in a liquefied gas.

  Examples of the silicone oil include methylpolysiloxane, cyclopentasiloxane, cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, tetrahydrotetramethylcyclotetrasiloxane, Examples include octamethyltrisiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane.

  Examples of the fats and oils include camellia oil, corn oil, olive oil, castor oil, safflower oil, jojoba oil, coconut oil, and rice salad oil.

  Examples of the hydrocarbon include liquid paraffin, normal pentane, and isopentane.

  The oil content is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass in the nonaqueous stock solution. When the oil content is less than 1% by mass, the ultraviolet absorber tends to precipitate and the adhesion of the ultraviolet absorber tends to deteriorate. Moreover, when it exceeds 30 mass%, there exists a tendency for it to become sticky on an injection surface.

  The alcohol is used as a solvent for dissolving the ultraviolet absorber for the purpose of suppressing stickiness due to oil, ultraviolet absorber, or the like, and improving the drying property on the ejection surface.

  Examples of the alcohol include monohydric alcohols having 2 to 3 carbon atoms such as ethanol and isopropanol.

  The content of the alcohol is preferably 30 to 70% by mass in the nonaqueous stock solution, and more preferably 35 to 65% by mass. When the alcohol content is less than 30% by mass, the ultraviolet absorber tends to precipitate, tends to be sticky on the ejection surface, and tends to deteriorate the drying property. Moreover, when it exceeds 70 mass%, it will become difficult to contain a ultraviolet absorber at high concentration, the effect which interrupts | blocks an ultraviolet-ray will tend to worsen, and there exists a tendency for the adhesiveness on a jet surface to worsen.

  The non-aqueous stock solution contains, in addition to the ultraviolet absorbent excluding the triazone derivative, oil and alcohol, an inorganic oxide powder, a powder other than the inorganic oxide powder, and an active ingredient other than the ultraviolet absorbent (hereinafter, other active ingredients). And a surfactant and the like can be appropriately contained.

  The inorganic oxide powder is used as an ultraviolet scattering agent that adheres to the skin and scatters ultraviolet rays to prevent sunburn of the skin. Examples of the inorganic oxide powder include zinc oxide, titanium oxide, and silica. In addition, it is preferable to use the surface treated with silicone such as hydrogen dimethicone, aluminum hydroxide, hydrous silica or the like. The inorganic oxide powder may be dispersed in an oil such as ester oil.

The specific surface area of the inorganic oxide powder is preferably 1 to 1,000 m ² / g, more preferably 5~800m ² / g, more preferably 10 to 200 m ² / g. When the specific surface area is less than 1 m ² / g, the powder surface tends to be smooth and the effect of scattering ultraviolet rays tends to be weak, and the spray surface tends to become white. On the other hand, when it exceeds 1000 m ² / g, the specific gravity tends to be too light and the dispersibility in the aerosol composition tends to be poor, it tends to scatter when sprayed, and it tends to be difficult to adhere to the skin. In addition, the specific surface area in this invention is a specific surface area measured by BET method using nitrogen.

  The primary particle diameter of the inorganic oxide powder is preferably 1 to 100 nm, and more preferably 5 to 50 nm. When the primary particle size is less than 1 nm, it tends to agglomerate hard, and even if the aerosol composition is stirred before use, it is difficult to disperse and tends to be unable to be injected with a uniform composition. On the other hand, when it exceeds 100 nm, the ultraviolet scattering effect tends to be weakened, and tends to become white when dried on the skin or hair.

  When the inorganic oxide powder is contained, the content in the nonaqueous stock solution is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass. When the content of the inorganic oxide powder is less than 0.1% by mass, the effect of containing the inorganic oxide powder tends to be difficult to obtain. Moreover, when it exceeds 15 mass%, it tends to become white on the ejection surface.

  Powders other than the inorganic oxide powder are used for the purpose of improving the feeling of use by improving the stickiness caused by the ultraviolet absorber. Examples of the powder include corn starch aluminum octenyl succinate, nylon powder, talc, and bentonite. In particular, it is preferable to use a spherical nylon powder because the jetting surface is further non-sticky.

  The content of the powder other than the inorganic oxide powder is preferably 0.1 to 15% by mass, and more preferably 0.3 to 10% by mass in the nonaqueous stock solution. When content of the said powder is less than 0.1 mass%, there exists a tendency for the effect containing powder other than inorganic oxide powder to become difficult to be acquired. Moreover, when it exceeds 15 mass%, it tends to be easily clogged with an aerosol valve or an injection member.

  The other active ingredient is used for the purpose of imparting effects such as moisturizing the skin, suppressing itching and inflammation, imparting a refreshing feeling, and masking the odor of the ultraviolet absorber. 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, diglycerin, dipropylene glycol, xylitol, sorbitol, maltitol, mannitol, collagen, hyaluronic acid, caronic acid, sodium lactate, dl-pyrrolidone carboxylate, keratin, casein, lecithin, urea; Antioxidants such as ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole; retinol, retinol acetate, retinol palmitate, calcium pantothenate, ascorbic acid Vitamins such as magnesium acid, sodium ascorbate, dl-α-tocopherol, tocopherol acetate, tocopherol, tocopherol nicotinate, dibenzoylthiamine, riboflavin and mixtures thereof; allantoin hydroxyaluminum, tannic acid, citric acid, lactic acid, alum, etc. Astringents; local anesthetics such as dibucaine hydrochloride, tetracaine hydrochloride, lidocaine hydrochloride, lidocaine; anti-inflammatory agents such as diphenhydramine, tocopherol acetate, glycyrrhetinic acid, dipotassium glycyrrhizinate; aluminum chloride, aluminum oxychloride, basic aluminum bromide Antiperspirant components such as aluminum sulfate, chlorohydroxyaluminum, zinc sulfate, zinc phenolsulfonate, basic zinc aluminum lactate; Bactericides such as rumethylphenol and benzalkonium chloride; deodorants such as lauric acid methacrylate, methyl benzoate, methyl phenylacetate, geranyl crotolate, acetophenone myristate, benzyl acetate, benzyl propionate, and green tea extract; Can be mentioned. In addition, what is necessary is just to dissolve these active ingredients in oil or alcohol according to solubility.

  The content in the case of containing other active ingredients is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass in the nonaqueous stock solution. When the content of the other active ingredient is less than 0.1% by mass, the amount adhering to the skin is small and the effect of the active ingredient tends to be insufficient. Moreover, when it exceeds 10 mass%, it becomes difficult to spray and apply | coat uniformly, and there exists a tendency for an effect to be insufficient with respect to content.

  The surfactant is used for the purpose of improving the dispersibility of inorganic oxide powders and powders other than inorganic oxide powders. Examples of the surfactant include silicone surfactants such as polyoxyethylene / methylpolysiloxane copolymer, polyoxyethylene / polyoxypropylene / methylpolysiloxane copolymer, monoglycerin fatty acid ester, poly (di- Non-ionic surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, etc. . Among these, a nonionic surfactant having an HLB of 1 to 10 is preferable, and a nonionic surfactant having an HLB of 2 to 9 is more preferable.

  When the surfactant is contained, the content in the nonaqueous stock solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass. When the content of the surfactant is less than 0.1% by mass, the effect of containing the surfactant tends to be difficult to obtain. Moreover, when it exceeds 10 mass%, it tends to become sticky on the ejection surface.

  The non-aqueous stock solution can be prepared by dissolving an ultraviolet absorber in oil and adding alcohol thereto. Moreover, what is necessary is just to add each component to the prepared non-aqueous stock solution, when making an inorganic oxide powder and another active ingredient contain in a non-aqueous stock solution. The content of inorganic oxide powder or the like may be adjusted to form a slurry. Other active ingredients can also be added after dissolving in oil or alcohol. You may add inorganic oxide powder and powders other than inorganic oxide powder as a mixture.

  20-50 mass% is preferable in an aerosol composition, and, as for content of a nonaqueous undiluted | stock solution, 25-45 mass% is more preferable. When the content of the nonaqueous stock solution is less than 20% by mass, the concentration of the ultraviolet absorber in the projectile tends to be low, and a sufficient sun protection effect tends not to be obtained. Moreover, when it exceeds 50 mass%, it becomes easy to stick and there exists a tendency for a usability | use_condition to deteriorate.

  The liquefied gas is a liquid having a pressure in the pressure vessel and acts as a main solvent for dissolving the nonaqueous stock solution. In particular, even when the viscosity of the nonaqueous stock solution increases due to the inclusion of the ultraviolet absorber or the inorganic oxide powder, the liquefied gas acts as a solvent, so that the viscosity as the aerosol composition can be lowered. Moreover, it can spray with the spray particle of a moderate magnitude | size, and can make it adhere uniformly to an injection surface.

  Examples of the liquefied gas include liquefied petroleum gas, dimethyl ether, hydrofluoroolefin, and a mixture thereof. Among these, liquefied petroleum gas is preferable because it can be injected softly by adjusting the pressure. Moreover, it is preferable to contain a dimethyl ether and hydrofluoro olefin from the reason that the combustibility can be suppressed and the cooling effect with respect to an injection surface is improved.

  Content of liquefied gas is 50-80 mass% in an aerosol composition, and 55-75 mass% is preferable. When the content of the liquefied gas is less than 50% by mass, the sprayed product tends to become a rough mist, which makes it difficult to adhere uniformly, and tends to be sticky and deteriorate the usability. Moreover, when it exceeds 80 mass%, the ultraviolet absorber tends to precipitate in the aerosol composition, the concentration of the ultraviolet absorber in the injection becomes low, and it adheres unevenly on the injection surface and is sufficient to prevent sunburn. There is a tendency that the effect cannot be obtained.

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

  The aerosol-type sunscreen agent of the present invention can be produced by filling a pressure-resistant container with a nonaqueous 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 a metal such as aluminum or tinplate, is made of a synthetic resin such as polyethylene terephthalate, or is made of a pressure-resistant glass, 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 that closes the stem hole of the stem, and a tube that supplies the aerosol composition in the container into the housing.

It is preferable to use a housing having a vapor tap hole for introducing the gas phase of the aerosol composition from the viewpoint that the injected particles can be made fine and the combustibility can be suppressed. Incidentally, it is preferable that the cross-sectional area of the vapor tap hole is 0.005~1mm ^2, 0.01~0.5mm ² is more preferable.

  The spray form by the aerosol type sunscreen agent of the present invention is preferably mist-like spray, and the average particle diameter of spray particles is preferably 10 to 50 μm, more preferably 15 to 45 μm. When the average particle diameter is smaller than 10 μm, the spray particles are likely to be scattered on the injection target such as the skin and the hair, so that the amount of adhesion tends to decrease or the suction tends to be facilitated. Moreover, when an average particle diameter is larger than 50 micrometers, there exists a tendency for it to become difficult to adhere uniformly to an injection surface.

  The aerosol type sunscreen agent of the present invention contains an ultraviolet absorber at a high concentration, is excellent in sunscreen prevention effect, can be sprayed thinly and uniformly over a wide area, the jetting surface is not sticky and excellent in feeling of use, It is a stable aerosol type sunscreen agent that does not deposit UV absorbers. Furthermore, since the filled aerosol composition is composed of a non-aqueous stock solution and a liquefied gas, the dryness is good and the dripping is difficult, and a cooling effect is obtained by vaporizing the liquefied gas immediately after injection.

  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: Uvinul A plus B (trade name), manufactured by BASF Japan Ltd. * 2: Uvinul A plus Granular (trade name), manufactured by BASF Japan Ltd. * 3: Eusolex OCR (trade name), manufactured by Merck & Co., Ltd. * 4 : Eusolex OS (trade name), manufactured by Merck & Co., Ltd. * 5: PARSOL MCX (trade name), manufactured by DSM Nutrition Japan Co., Ltd. * 6: Tinosorb S (trade name), manufactured by BASF Japan Ltd. * 7: Neosolute MP (product) Name), manufactured by Nippon Seika Co., Ltd. * 8: DC345 (trade name), manufactured by Toray Dow Corning Co., Ltd. * 9: TTO-S-2 (trade name), specific surface area: 70 m ² / g, primary particle size: 50nm, manufactured by Ishihara Sangyo Kaisha, Ltd. * 10: MZ-500HP (trade name), specific surface area: 40m ² g, primary particle diameter: 25nm, manufactured by Tayca Corporation

Examples 1-7 and Comparative Examples 1-7
According to the formulations shown in Tables 2-3, each stock solution (see Table 1) and liquefied gas (* 11) were filled in a pressure-resistant glass container, 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.
* 11: Mixture of normal butane and isobutane (vapor pressure at 25 ° C is 0.2 MPa)

(1) Stability of aerosol composition Each test aerosol product was visually inspected for 1 month after standing at low temperature (-20 ° C) and high temperature (45 ° C) for the following criteria. Based on the evaluation.
○: No precipitate was generated.
Δ: A thin haze occurred, but disappeared when the aerosol product was shaken up and down.
X: A precipitate was generated.

(2) Usability The aerosol product for test was immersed in a constant temperature water bath at 25 ° C. for 30 minutes, and 1 g was sprayed onto the arm, and the state of the spray surface was evaluated based on the following criteria.
A: Dried immediately, the jetting surface was not sticky, was smooth and smooth, and did not turn white.
○: Dryed immediately, the spray surface was not sticky, and did not become white.
Δ1: There was no stickiness, but the spray surface became white.
Δ2: Slightly sticky, but the spray surface did not become white.
X1: It was difficult to dry and was sticky.
X2: There were many dances and it hardly adhered to the arm.
−: Not evaluated because precipitation occurred.

(3) Ultraviolet ray blocking effect Each spray aerosol product is coated with a coating plate that changes from white to purple when exposed to ultraviolet rays (photocrosic plate, manufactured by Yoshida Cosme Works Co., Ltd.) so that the injection amount of the non-aqueous stock solution is 1 g. Spraying, irradiating the coating plate with an ultraviolet lamp, and spraying each other aerosol product for testing with reference to Example 1 (UVAPF measured according to ISO 24442 is 19.2) corresponding to the UVA protection index PA ++++ Compared with the discolored state of the board, the evaluation was made based on the following criteria.
○: As in the case of the reference product, the color did not change even after irradiation for 10 minutes.
X: Discolored within 30 seconds.
-: Not evaluated because precipitation occurred.

  Moreover, the evaluation result (photograph of the coating plate after irradiating an ultraviolet lamp for 10 minutes) of Examples 1 and 2 and Comparative Examples 1 to 4 is shown in FIGS.

  As shown in FIGS. 1 and 2, it can be seen that in Examples 1 and 2, the aerosol composition was uniformly applied and remained white without discoloration. However, as shown in FIG. 3, in Comparative Example 1, since the content of the liquefied gas was too much, the sprayed material was scattered more, the adhesion amount was reduced, and the color was totally changed. Further, it can be seen that since the sprayed material could not be uniformly adhered to the coating plate, it was partially darkly discolored. Moreover, as shown in FIG. 5, since the comparative example 3 has little ultraviolet absorber content, the ultraviolet-blocking effect is weak and it turns out that the injected location has changed into light purple as a whole. In addition, Example 3-7 was the same result as Example 1 and 2. Moreover, since the aerosol product for a test was not injected on the upper part of all the application boards shown to FIGS. 1-6, it changed to deep purple.

Formulation Example 1 Aerosol-type sunscreen agent 16 g (40% 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 24g (60 mass%) of liquefied gas (* 11) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in Table 4.

<Undiluted solution>
Diethylaminohydroxybenzoyl hexyl benzoate /
Ethyl hexyl methoxycinnamate (* 1) 16.0
Diethylaminohydroxybenzoyl hexyl benzoate (* 2) 3.4
Octocrylene (* 3) 3.0
Ethyl hexyl salicylate (* 4) 3.6
Ethanol 53.0
Dineopentanoic acid methylpentanediol (* 7) 10.0
Cyclohexasiloxane (* 8) 10.0
Octenyl succinate corn starch aluminum (* 12) 1.0
Total (parts by mass) 100.0
* 12: DRY FLO PURE (trade name), manufactured by Axon Nobel Co., Ltd.

Formulation example 2 Aerosol-type sunscreen agent The following undiluted | stock solution 12g (30 mass%) was filled into the pressure | voltage resistant container made from a polyethylene terephthalate (100 ml of full injection amount), and the aerosol valve was fixed. And the liquefied gas (* 11) 24g (60 mass%) was filled from the aerosol valve | bulb, and then the liquefied gas (* 13) 4g (10 mass%) was filled, and the aerosol product for a test was manufactured. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in Table 4.
* 13: Dimethyl ether

<Undiluted solution>
Diethylaminohydroxybenzoyl hexyl benzoate /
Ethylhexyl methoxycinnamate (* 1) 15.0
Diethylaminohydroxybenzoyl hexyl benzoate (* 2) 2.0
Octocrylene (* 3) 2.0
Ethyl hexyl salicylate (* 4) 2.0
Oxybenzone-3 (* 14) 2.0
Ethanol 62.0
Isotridecyl isononanoate (* 15) 7.0
Liquid paraffin (* 16) 7.0
Octenyl succinate corn starch aluminum (* 12) 1.0
Total (parts by mass) 100.0
* 14: Uvinul MC40 (trade name), manufactured by BASF Japan Ltd. * 15: Saracos 913 (trade name), manufactured by Nisshin Oillio Group Co., Ltd. * 16: High call K-230 (trade name), manufactured by Kaneda Corporation

Formulation Example 3 Aerosol-type sunscreen agent 16 g (40% 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 24g (60 mass%) of liquefied gas (* 11) from the aerosol valve | bulb. Said evaluation was performed about the obtained aerosol product for a test. The results are shown in Table 4.

<Undiluted solution>
Diethylaminohydroxybenzoyl hexyl benzoate /
Ethyl hexyl methoxycinnamate (* 1) 16.0
Diethylaminohydroxybenzoyl hexyl benzoate (* 2) 3.0
Octocrylene (* 3) 3.0
Ethylhexyl salicylate (* 4) 3.0
Ethanol 53.0
Di-2-ethylhexanoic acid neopentyl glycol (* 17) 10.0
Cyclohexasiloxane (* 8) 5.0
Titanium oxide (* 9) 1.0
Zinc oxide (* 10) 1.0
Nylon powder (* 18) 5.0
Total (parts by mass) 100.0
* 17: Cosmall 525 (trade name), manufactured by Nisshin Oillio Group Co., Ltd. * 18: DAIAMID MSP-100 (trade name), manufactured by Daicel Evonik Co., Ltd.

  Moreover, the evaluation result (the photograph of the coating plate after irradiating a UV lamp for 10 minutes) of the prescription examples 1 to 3 is the same as in Examples 1 and 2, and the portion where the propellant is applied is not discolored. It remained white.

1 dark purple 2 white 3 light purple

Claims (3)

Ultraviolet absorbents, oil (unless oil is said ultraviolet absorber) and aerosol composition comprising a non-aqueous stock solution and liquified gas containing alcohol is filled in the pressure vessel,
The ultraviolet absorber does not contain a triazine derivative,
The content of the previous SL ultraviolet absorber, a said non-aqueous stock solution from 20 to 45 wt%,
The alcohol is a monohydric alcohol having 2 to 3 carbon atoms, and is contained in an amount of 30 to 70% by mass in the nonaqueous stock solution.
The oil contains ester oil,
The ester oil includes a diester of a fatty acid and a dihydric alcohol,
The oil content is 1 to 30% by mass in the non-aqueous stock solution,
Aerosol-type sunscreen agent whose content of the said liquefied gas is 50-80 mass% in aerosol composition. Before SL ultraviolet absorber, aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, aerosol sunscreen agent according to claim 1, wherein at least one selected from the group consisting of diphenyl acrylate derivatives and benzophenone derivatives. The non-aqueous stock solution contains an inorganic oxide powder,
The aerosol-type sunscreen agent according to claim 1 or 2 , wherein the content of the inorganic oxide powder is 0.1 to 15% by mass in the nonaqueous stock solution.