WO2009104353A1 - 油中水型乳化日焼け止め化粧料 - Google Patents
油中水型乳化日焼け止め化粧料 Download PDFInfo
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- WO2009104353A1 WO2009104353A1 PCT/JP2009/000257 JP2009000257W WO2009104353A1 WO 2009104353 A1 WO2009104353 A1 WO 2009104353A1 JP 2009000257 W JP2009000257 W JP 2009000257W WO 2009104353 A1 WO2009104353 A1 WO 2009104353A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
Definitions
- the present invention relates to a water-in-oil type emulsion sunscreen cosmetic. More specifically, the present invention relates to a water-in-oil type emulsion sunscreen cosmetic that is excellent in ultraviolet protective ability, does not precipitate crystals of an ultraviolet absorber, and has excellent base stability.
- Sunscreen cosmetics contain UV absorbers or UV scattering agents (zinc oxide, titanium dioxide, etc.) in order to obtain high SPF (Sun Protection Factor) values by blocking UV irradiation on the skin.
- SPF Sun Protection Factor
- octocrylene is a general-purpose ultraviolet absorber, but when used in combination with an ultraviolet scattering agent (zinc oxide, titanium dioxide, etc.) that has been subjected to a hydrophobization treatment in a water-in-oil sunscreen cosmetic, odor changes over time.
- Patent Document 3 describes (a) 0.2 to 10% by mass of octocrylene and (b) 0.2 to 30% by mass of hydrophobized titanium dioxide and / or zinc oxide.
- Patent Document 4 discloses a sunscreen cosmetic containing 1,4-dihydropyridine and 1,4-dihydropyran as ultraviolet absorbers.
- phenylbenzimidazole sulfonic acid, aminomethyl propanol, and the like are described in a wide variety of exemplary ingredients that can be blended in the sunscreen cosmetic. However, there is no description that directly links these two combinations.
- the inventors of the present application have developed (a) dimethyldiethylbenzalmalonate and (b) phenylbenzimidazolesulfone as ultraviolet absorbers in order to develop a new sunscreen cosmetic with reference to the above-mentioned Patent Document 3 by the present applicant.
- the triethanolamine described as the most preferable neutralizing agent in Patent Document 3 was used for the sunscreen cosmetic comprising the water-in-oil emulsion composition, We found a problem that benzimidazolesulfonic acid crystallizes.
- the present invention is an invention obtained as a result of earnest research to solve such problems, and in a sunscreen cosmetic comprising (a) dimethyldiethylbenzalmalonate and (b) phenylbenzimidazolesulfonic acid,
- a sunscreen cosmetic comprising (a) dimethyldiethylbenzalmalonate and (b) phenylbenzimidazolesulfonic acid
- aminomethylpropanol instead of using triethanolamine specifically recommended in Patent Document 3, aminomethylpropanol is used, and a water-in-oil emulsion composition is used.
- the sunscreen cosmetics having an aqueous phase of 40% by mass or less it is quite unexpected that phenylbenzimidazolesulfonic acid does not crystallize and a stable sunscreen cosmetic as a water-in-oil emulsion composition is obtained. It was found for the first time that it was obtained and the present invention was completed.
- An object of the present invention is to provide a water-in-oil type emulsion sunscreen cosmetic comprising (a) dimethyldiethylbenzalmalonate and (b) phenylbenzimidazolesulfonic acid, in which phenylbenzimidazolesulfonic acid does not crystallize, It is to provide a water-in-oil emulsified sunscreen cosmetic that is extremely stable over time.
- the present invention provides (a) 0.1 to 10% by mass of dimethyldiethylbenzalmalonate, (b) 0.02 to 8% by mass of phenylbenzimidazolesulfonic acid, (c) the component (b)
- a water-in-oil type emulsion sunscreen cosmetic comprising a neutralizing agent and having an aqueous phase of 40% by mass or less is provided.
- the present invention also provides the water-in-oil type emulsion sunscreen cosmetic described above, characterized by containing 0.5 to 4% by mass of component (b).
- the present invention provides the water-in-oil type emulsion sunscreen cosmetic described above, characterized by containing 0.01 to 3% by mass of component (c).
- the present invention also provides the water-in-oil type emulsion sunscreen cosmetic described above, wherein the component (c) is aminomethylpropanol.
- the present invention further provides (d) the water-in-oil type emulsion sunscreen cosmetic described above, which further comprises (d) 0.01 to 20% by mass of a silicone surfactant.
- the present invention further includes (e) a hydrophobized titanium dioxide and / or zinc oxide, containing 10.1 to 25% by mass of the above water-in-oil type emulsion sunscreen cosmetics as described above Is to provide.
- a water-in-oil type emulsion sunscreen cosmetic comprising (a) dimethyldiethylbenzalmalonate and (b) phenylbenzimidazolesulfonic acid, phenylbenzimidazolesulfonic acid does not crystallize and is an extremely stable oil over time
- a water-in-water emulsified sunscreen cosmetic can be provided.
- (A) Dimethyldiethylbenzalmalonate The component (a) dimethyldiethylbenzalmalonate used in the present invention is a known ultraviolet absorber, and is commercially available as, for example, “Parsol SLX” (DSM Nutrition Japan Co., Ltd.). It can be used suitably.
- the amount of component (a) is 0.1 to 10% by mass, preferably 2.5 to 7.5% by mass, based on the total amount of the water-in-oil emulsion sunscreen cosmetic. When the blending amount is out of the above range, the effects of the present invention may not be sufficiently exhibited.
- the component (b) phenylbenzimidazolesulfonic acid used in the present invention is a water-soluble ultraviolet absorber, such as “Neo Heliopan Hydro” (manufactured by Symrise), “Usolex”. 232 (Eusolex232) "(manufactured by Merck) or the like, and these can be suitably used.
- the amount of component (b) is 0.02 to 8% by mass, preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass, based on the total amount of the water-in-oil type emulsion sunscreen cosmetic. It is. When the blending amount is out of the above range, the effects of the present invention may not be sufficiently exhibited.
- (C) Neutralizing agent for component (b) The component (c) used in the present invention is a neutralizing agent for neutralizing the component (b).
- the neutralizing agent is preferably aminomethylpropanol.
- the amount of component (c) is not particularly limited as long as it is an amount sufficient to neutralize component (b).
- the blending amount of the component (c) with respect to the total amount of the sunscreen cosmetic is preferably 0.01 to 3% by mass.
- (D) Silicone surfactant In the present invention, it is preferable to further blend (d) a silicone surfactant as an emulsifier.
- the silicone surfactant is not particularly limited as long as it can be used in a water-in-oil emulsion type system.
- polysiloxane copolymer polyoxyethylene / oxypropylene methyl polysiloxane copolymer
- polyoxyethylene methyl polysiloxane copolymer silicone chain branched methyl polysiloxane copolymer
- alkyl chain branched polyoxyethylene methyl polysiloxane copolymer Copolymer alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer
- cross-linked polyoxyethylene methyl polysiloxane alkyl group-containing cross-linked polyoxyethylene methyl polysiloxane, branched polyglycerin-modified silicone, cross-linked poly
- examples thereof include glycerin-modified silicone, alkyl group-containing cross-linked polyglycerin-modified silicone, and alkyl group branched polyglycerin-modified silicone.
- Examples of the poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer include PEG / PPG-20 / 22 butyl ether dimethicone (“KF-6012”; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG / PPG-20 / 20 dimethicone.
- Examples of the polyoxyethylene methylpolysiloxane copolymer include PEG-11 methyl ether dimethicone (“KF-6011”; manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-9 dimethicone (“KF-6013”; Shin-Etsu Chemical Co., Ltd.).
- silicone chain-branched methylpolysiloxane copolymer examples include PEG-9 polydimethylsiloxyethyl dimethicone (“KF-6028”; manufactured by Shin-Etsu Chemical Co., Ltd.).
- alkyl chain branched polyoxyethylene methyl polysiloxane copolymer examples include PEG / PPG-10 / 3 oleyl ether dimethicone (“KF-6026”; manufactured by Shin-Etsu Chemical Co., Ltd.).
- alkyl chain / silicone chain branched polyoxyethylene methyl polysiloxane copolymer examples include lauryl PEG-9 polydimethylsiloxyethyl dimethicone (“KF-6038”; manufactured by Shin-Etsu Chemical Co., Ltd.).
- crosslinked polyoxyethylene methylpolysiloxane examples include dimethicone (dimethicone / (PEG-10 / 15)) crosspolymer (“KSG-210”; manufactured by Shin-Etsu Chemical Co., Ltd.), cyclomethicone / PEG-12 dimethicone dimethicone cross. Polymer (“9011 silicone elastomer blend”; manufactured by Toray Dow Corning Silicone Co., Ltd.).
- alkyl group-containing crosslinked polyoxyethylene methylpolysiloxane examples include mineral oil, PEG-15 lauryl dimethicone cross polymer (“KSG-310”, manufactured by Shin-Etsu Chemical Co., Ltd.), isododecane, PEG-15 lauryl dimethicone cross polymer ( “KSG-320”; manufactured by Shin-Etsu Chemical Co., Ltd.), trioctanoin / PEG-15 lauryl dimethicone cross polymer (“KSG-330”; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane / PEG-15 lauryl dimethicone cross Examples include polymers and PEG-10 lauryl dimethicone crosspolymer (“KSG-340”; manufactured by Shin-Etsu Chemical Co., Ltd.).
- branched polyglycerin-modified silicone examples include polyglyceryl-3 disiloxane dimethicone (“KF-6100”; manufactured by Shin-Etsu Chemical Co., Ltd.), polyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6104”; Shin-Etsu Chemical ( Etc.).
- crosslinked polyglycerin-modified silicone examples include dimethicone / (dimethicone / polyglycerin-3) crosspolymer (“KSG-710”; manufactured by Shin-Etsu Chemical Co., Ltd.).
- alkyl group-containing crosslinked polyglycerin-modified silicone examples include mineral oil (lauryl dimethicone / polyglycerin 3) crosspolymer (“KSG-810”; manufactured by Shin-Etsu Chemical Co., Ltd.), isododecane (lauryl dimethicone / polyglycerin 3).
- Crosspolymer (“KSG-820; manufactured by Shin-Etsu Chemical Co., Ltd.”), trioctanoin (lauryl dimethicone / polyglycerin 3) crosspolymer (“KSG-830”; manufactured by Shin-Etsu Chemical Co., Ltd.), squalane -(Lauryl dimethicone / polyglycerin 3) crosspolymer (“KSG-840"; manufactured by Shin-Etsu Chemical Co., Ltd.)
- alkyl group-branched polyglycerin-modified silicone examples include lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (“KF-6105” manufactured by Shin-Etsu Chemical Co., Ltd.).
- polyoxyethylene methyl polysiloxane copolymer poly (oxyethylene oxypropylene) methyl polysiloxane copolymer, silicone chain branched methyl polysiloxane copolymer alkyl chain, silicone chain branched polyoxyethylene methyl A polysiloxane copolymer is preferably used.
- the blending amount of the component (d) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably based on the total amount of the water-in-oil type emulsion sunscreen cosmetic. It is 0.5 mass% or more.
- the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. If the blending amount is less than 0.01% by mass, the stability as an emulsion composition may be deteriorated. On the other hand, when the blending amount greatly exceeds 20% by mass, a sticky feeling is generated and the feeling of use tends to be deteriorated.
- a compounding quantity is suitably determined by the combination of said lower limit and upper limit.
- a preferred blending amount is 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the total amount of the water-in-oil type emulsion sunscreen cosmetic.
- 0.5 to 10% by mass is preferable.
- (E) Titanium dioxide and / or zinc oxide subjected to hydrophobic treatment it is preferable to mix
- titanium dioxide and zinc oxide are preferably powders prepared in the form of fine particles.
- the fine particle titanium dioxide include those having an average primary particle diameter of preferably 30 nm or less, more preferably 20 nm or less.
- the fine zinc oxide include those having an average primary particle diameter of 40 nm or less, more preferably 30 nm or less. However, it is not limited to these particle sizes.
- the method of hydrophobizing treatment is not particularly limited, and can be treated by a known method.
- treatment with silicones such as methylhydrogenpolysiloxane, methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer, dimethylpolysiloxane; treatment with silane compounds such as octyltriethoxysilane, hexyltrimethoxysilane; palmitic Treatment using fatty acid such as acid or stearic acid; Metal soap treatment using alkali metal salt or alkaline earth metal salt of fatty acid; Perfluoroalkyl phosphate diethanolamine salt, perfluoroalkyltrimethoxysilane, etc. Fluorine treatment etc. are mentioned.
- titanium dioxide subjected to the hydrophobization treatment examples include “TTO-S-4”, “TTO-V-4” (all manufactured by Ishihara Sangyo Co., Ltd.), “MT-100TV”, “MT-014V” ( All of them are manufactured by Teika Co., Ltd.).
- zinc oxide subjected to hydrophobic treatment examples include “FZO-50” (manufactured by Ishihara Sangyo Co., Ltd.), “MZ-700” (manufactured by Teika Co., Ltd.), “Z-Cote HP-1” ( BASF (made by BASF) etc. are mentioned as a commercial item. In the present invention, these commercially available products can be suitably used.
- the amount of the component (e) is 10.1 to 25% by mass based on the total amount of the water-in-oil type emulsion sunscreen cosmetic. Outside this range, it may be unfavorable from the viewpoints of the ultraviolet scattering effect and the feeling of use (squeaking etc.) due to powder blending.
- the very high ultraviolet-ray scattering effect is acquired when the compounding quantity of (e) component is 10.1 mass% or more, generation
- the water phase (becomes the inner phase) be 40% by mass or less based on the total amount of the water-in-oil type emulsion sunscreen cosmetic. Preferably, it is 10 to 40% by mass.
- the constituent component of the aqueous phase is water, but 40% by mass means the total amount of water and an aqueous component dissolved in water (but not including a surfactant).
- the component (c) is included and the components (a), (d), and (e) are not included.
- the oil phase (outer phase) is preferably 60 to 85% by mass with respect to the total amount of the water-in-oil type emulsion sunscreen cosmetic.
- the oil component constituting the oil phase is not particularly limited.
- water-in-oil type emulsion sunscreen cosmetics of the present invention in addition to the above-mentioned components, other components usually used in cosmetics are appropriately blended as necessary, as long as the purpose and effect of the present invention are not impaired.
- Such components include water-soluble polymers, oil-soluble polymers, polymer powders, emulsifiers (other than the above component (e)), waxes, alcohols, liquid oils and fats, ester oils, hydrocarbon oils, silicone oils, Fatty acids, higher alcohols, fatty acid esters, drugs, ultraviolet absorbers (other than the above (a) component and (b) component), ultraviolet scattering agents (other than the above (e) component), organically modified clay minerals, etc. It is done. Examples are given below.
- water-soluble polymer examples include homopolymers or copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as “AMPS”).
- the copolymer is a copolymer composed of a comonomer such as vinyl pyrrolidone, acrylic acid amide, sodium acrylate, or hydroxyethyl acrylate. That is, an AMPS homopolymer, a vinylpyrrolidone / AMPS copolymer, a dimethylacrylamide / AMPS copolymer, an acrylic amide / AMPS copolymer, a sodium acrylate / AMPS copolymer, and the like are exemplified.
- carboxyvinyl polymer ammonium polyacrylate, sodium polyacrylate, sodium acrylate / alkyl acrylate / sodium methacrylate / alkyl methacrylate copolymer, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, glycogen , Gum arabic, sodium hyaluronate, gum tragacanth, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar, etc. Is done.
- oil-soluble polymer examples include trimethylsiloxysilicic acid, alkyl-modified silicone, and polyamide-modified silicone.
- polymer powder examples include dimethicone cross polymer, (dimethicone / vinyl dimethicone) cross polymer, polymethylsilsesquioxane, polyethylene, polymethyl methacrylate, and the like.
- waxes examples include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, jojoballow and the like.
- emulsifier examples include glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
- alcohols examples include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol and hexyldecanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and polybutylene glycol. Examples thereof include monohydric alcohols.
- liquid oils and fats examples include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanca oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
- ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, lactic acid Myristyl, lanolin acetate, isocetyl stearate, isocetyl isostearate, isononyl isononanoate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, dicapric acid Neopentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, tri
- hydrocarbon oil examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.
- silicone oils include dimethylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.
- fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidonic acid and the like.
- Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, aralkyl alcohol, batyl alcohol, chimyl alcohol, carnervir alcohol, ceryl alcohol, coryranyl alcohol, myricyl alcohol, lacteryl alcohol, elayl
- Illustrative examples include zircyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontyl alcohol, ceralkyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, and octyl decanol.
- fatty acid esters examples include myristyl myristate, cetyl palmitate, cholesteryl stearate, beeswax fatty acid 2-octyldodecyl, and the like.
- Examples of the drug include salts of L-ascorbic acid and derivatives thereof, glycyrrhizic acid and derivatives thereof such as dicalylum glycyrrhizinate and monoammonium glycyrrhizinate, glycyrrhetinic acid and derivatives thereof such as stearyl glycyrrhetinate, allantoin, tranexamic acid and derivatives thereof And salts of alkoxysalicylic acid and its derivatives, glutathione and its derivatives, allantoin, azulene and the like.
- ultraviolet absorbers other than the above components (a) and (b) include cinnamic acid derivatives such as ethylhexyl methoxycinnamate, isopropyl methoxycinnamate and isoamyl methoxycinnamate; para-aminobenzoic acid (hereinafter referred to as “ PABA "), PABA derivatives such as ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA; salicylic acid derivatives such as homosalate, ethylhexyl salicylate, dipropylene glycol salicylate, TEA salicylate Benzophenone-1, benzophenone-2, benzophenone-3 or oxybenzone, benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone- Benzophenone derivatives
- Phenylbenzimidazole derivatives Drometrizole trisiloxane, methylenebis (benzotriazolyltetramethylbutylphenol), etc. Phenylbenzotriazole derivatives; anthranyl derivatives such as menthyl anthranilate; imidazoline derivatives such as ethylhexyldimethoxybenzylidenedioxoimidazoline propionate; benzalmalonate derivatives such as polyorganosiloxane having a benzalmalonate functional group; Examples include 4,4-diarylbutadiene derivatives such as dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene.
- Examples of the ultraviolet light scattering agent other than the above component (e) include hydrophobized inorganic pigments such as kaolin and calcium carbonate.
- organically modified clay minerals include quaternary ammonium salt type cation-modified clay minerals.
- the water-in-oil type emulsion sunscreen cosmetics of the present invention include milky products and creamy products. These products can be manufactured by a conventional method by mixing the above-described essential components and components usually blended in cosmetics.
- Example 1, Comparative Examples 1 to 4 Sunscreen cosmetics were prepared according to the formulation shown in Table 1 below. Specifically, (9) [B part] is added to (1) to (8) [A part] and uniformly dispersed, and (10) to (12) [C part] is further added thereto. After uniformly dispersing, (13) to (20) [D parts] were gradually added and emulsified to obtain a water-in-oil type emulsion sunscreen cosmetic.
- the aqueous phases of Example 1 and Comparative Examples 1 to 4 are 30.9 to 31.15% by mass.
- the present invention it is possible to provide a water-in-oil emulsified sunscreen cosmetic that is excellent in UV protection ability, does not precipitate UV absorber crystals, and is extremely excellent in base stability.
- the present invention is particularly preferably used as an emulsion sunscreen product.
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Abstract
Description
本発明に用いる(a)成分のジメチルジエチルベンザルマロネートは、公知の紫外線吸収剤であり、例えば「パルソールSLX(Parsol SLX)」(DSMニュートリションジャパン(株))として市販されており、これを好適に用いることができる。
配合量が上記範囲外では、本発明の効果が十分に発揮されない場合がある。
本発明に用いる(b)成分のフェニルベンズイミダゾールスルホン酸は、水溶性の紫外線吸収剤であり、例えば「ネオ・ヘリパン・ハイドロ(Neo Heliopan Hydro)」(シムライズ(Symrise)社製)、「ユーソレックス232(Eusolex232)」(メルク(Merck)社製)等として市販されており、これらを好適に用いることができる。
配合量が上記範囲外では、本発明の効果が十分に発揮されない場合がある。
本発明に用いる(c)成分は、上記(b)成分を中和するための中和剤である。当該中和剤はアミノメチルプロパノールが好ましい。
本発明においては、乳化剤としてさらに(d)シリコーン系界面活性剤を配合することが好ましい。シリコーン系界面活性剤としては、油中水型乳化タイプの系に用いられ得るものであれば特に限定されるものでない。例えば、ポリ(オキシエチレン・オキシプロピレン)メチルポリシロキサン共重合体、ポリオキシエチレンメチルポリシロキサン共重合体、シリコーン鎖分岐型メチルポリシロキサン共重合体、アルキル鎖分岐型ポリオキシエチレンメチルポリシロキサン共重合体、アルキル鎖・シリコーン鎖分岐型ポリオキシエチレンメチルポリシロキサン共重合体、架橋型ポリオキシエチレンメチルポリシロキサン、アルキル基含有架橋型ポリオキシエチレンメチルポリシロキサン、分岐型ポリグリセリン変性シリコーン、架橋型ポリグリセリン変性シリコーン、アルキル基含有架橋型ポリグリセリン変性シリコーン、アルキル基分岐型ポリグリセリン変性シリコーン等が挙げられる。
配合量が0.01質量%未満では乳化組成物としての安定性が悪くなる場合がある。一方、配合量が20質量%を大きく超える場合はべとつき感が生じて使用感が悪くなる傾向がある。配合量は、上記の下限値及び上限値の組み合わせにより適宜決定される。
好ましい配合量は、油中水型乳化日焼け止め化粧料全量に対して、0.01~20質量%であり、さらに好ましくは0.05~10質量%である。乳化組成物として安定性を優先させる場合は、0.5~10質量%が好ましい。
本発明においては、(e)成分としての疎水化処理を施した、二酸化チタン及び/又は酸化亜鉛の粉末を配合することが好ましい。これらは紫外線散乱剤であり、疎水化処理を施すことにより効率よく油相(外相)中に分散され、本発明の紫外線防止効果を高めることが出来る。
また、疎水化処理を施した酸化亜鉛としては、例えば「FZO-50」(石原産業(株)製)、「MZ-700」(テイカ(株)製)、「Z-Cote HP-1」(バスフ(BASF)社製)等が市販品として挙げられる。
本発明においては、これらの市販品を好適に用いることができる。
なお、(e)成分の配合量が10.1質量%以上では非常に高い紫外線散乱効果が得られるが、通常、紫外線吸収剤とこれらの粉末の相互作用による変臭の発生も当然予想される。しかし、本発明においては、変臭を安定して効果的に防止・抑制することが可能である。
水相の構成成分は水であるが、40質量%は水と、水に溶解する水性成分(但し界面活性剤は含まない)の合計量を意味する。(b)(c)成分を含み、(a)(d)(e)成分は含めない。
下記表1に示す処方により日焼け止め化粧料を調製した。具体的には、(1)~(8)[Aパーツ]に、(9)[Bパーツ]を添加して均一分散し、さらにここに(10)~(12)[Cパーツ]を添加して均一分散した後、(13)~(20)[Dパーツ]を徐添し乳化して、油中水型乳化日焼け止め化粧料を得た。
なお、実施例1、比較例1~4の水相は、30.9~31.15質量%である。
得られた日焼け止め化粧料(試料)について、それぞれフェニルベンズイミダゾールスルホン酸の結晶化の有無について、下記により評価した。結果を表1に示す。
<試験法>
0℃と40℃を1時間ごとにサイクルする条件下で1ヶ月間静置した各試料を顕微鏡観察(OLYNPUS社製 BX-50-33PHD ×400)により、結晶の存在を下記評価基準により評価した。
<評価基準>
結晶が観察される :有
結晶が観察されない:無
得られた日焼け止め化粧料(試料)について、それぞれ変臭防止・抑制効果について下記により評価した。結果を表1に示す。
<試験方法>
50℃の恒温層内に1ヶ月間静置した各試料を女性パネル(10名)に実際に使用させて、塗布時の臭いを下記評価基準により評価した。
<評価基準>
◎:10名中、9名以上が許容内の臭いであると回答した。
○:10名中、6~8名が許容内の臭いであると回答した。
△:10名中、3~5名が許容内の臭いであると回答した。
×:10名中、3名未満が許容内の臭いであると回答した。
(*2)ジメチルジエチルベンザルマロネート:「パルソールSLX」(DSMニュートリションジャパン(株)製)
(*3)メトキシケイ皮酸エチルヘキシル:「パルソールMCX」(DSMニュートリションジャパン(株)製)
(*4)オクトクリレン:「パルソール340」(DSMニュートリションジャパン(株)製)
(*5)アルキル鎖・シリコーン鎖分岐型ポリオキシエチレンメチルポリシロキサン共重合体:「KF6038」(信越化学工業(株)製)
(*6)有機変性粘土鉱物:「ベントン38VCG」(エレメンティススペシャリティーズ製)
(*7)パルミチン酸デキストリン処理酸化亜鉛:「WSX-MZ-700」(テイカ(株)製)
(*8)ステアリン酸処理二酸化チタン:「TTO-V-4」(石原産業(株)製)
(*9)フェニルベンズイミダゾールスルホン酸:「Eusolex232」(メルク社製)
Claims (6)
- (a)ジメチルジエチルベンザルマロネートを0.1~10質量%、(b)フェニルベンズイミダゾールスルホン酸を0.02~8質量%、(c)前記(b)成分の中和剤を含有し、かつ、水相が40質量%以下であることを特徴とする油中水型乳化日焼け止め化粧料。
- (b)成分を0.5~4質量%含有することを特徴とする請求項1記載の油中水型乳化日焼け止め化粧料。
- (c)成分を0.01~3質量%含有することを特徴とする請求項1または2記載の油中水型乳化日焼け止め化粧料。
- (c)成分がアミノメチルプロパノールであることを特徴とする請求項1~3のいずれか1項に記載の油中水型乳化日焼け止め化粧料。
- さらに(d)シリコーン系界面活性剤を0.01~20質量%含有することを特徴とする請求項1~4のいずれか1項に記載の油中水型乳化日焼け止め化粧料。
- さらに(e)疎水化処理を施した、二酸化チタン及び/又は酸化亜鉛を10.1~25質量%含有することを特徴とする請求項1~5のいずれか1項に記載の油中水型乳化日焼け止め化粧料。
Priority Applications (7)
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US12/812,460 US20100291011A1 (en) | 2008-02-19 | 2009-01-23 | Water-In-Oil Emulsion Type Sunscreen Cosmetic |
KR1020107011410A KR101524026B1 (ko) | 2008-02-19 | 2009-01-23 | 유중수형 유화 선스크린 화장료 |
AU2009216500A AU2009216500B2 (en) | 2008-02-19 | 2009-01-23 | Water-in-oil emulsion type sunscreen cosmetic |
CN2009801062040A CN101951876B (zh) | 2008-02-19 | 2009-01-23 | 油包水型乳化防晒化妆品 |
ES09712714.6T ES2567707T3 (es) | 2008-02-19 | 2009-01-23 | Cosmético protector solar de tipo emulsión de agua en aceite |
EP09712714.6A EP2243465B1 (en) | 2008-02-19 | 2009-01-23 | Water-in-oil emulsion type sunscreen cosmetic |
HK11102378.5A HK1148214A1 (en) | 2008-02-19 | 2011-03-09 | Water-in-oil emulsion type sunscreen cosmetic |
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JP2008036798A JP5382904B2 (ja) | 2008-02-19 | 2008-02-19 | 油中水型乳化日焼け止め化粧料 |
JP2008-036798 | 2008-02-19 |
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US (1) | US20100291011A1 (ja) |
EP (1) | EP2243465B1 (ja) |
JP (1) | JP5382904B2 (ja) |
KR (1) | KR101524026B1 (ja) |
CN (1) | CN101951876B (ja) |
AU (1) | AU2009216500B2 (ja) |
ES (1) | ES2567707T3 (ja) |
HK (1) | HK1148214A1 (ja) |
TW (1) | TWI439290B (ja) |
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US20140205552A1 (en) * | 2011-08-26 | 2014-07-24 | Shiseido Company, Ltd. | Water-in-Oil Emulsified Sunscreen Cosmetic |
WO2019172107A1 (ja) * | 2018-03-08 | 2019-09-12 | 株式会社 資生堂 | 離漿防止用油中水型化粧料組成物 |
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JP5607916B2 (ja) * | 2009-11-30 | 2014-10-15 | 株式会社 資生堂 | 日焼け止め化粧料 |
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EP4082625A4 (en) * | 2019-12-24 | 2024-02-28 | Shiseido Company, Ltd. | COSMETIC PREPARATION WITH WATER-IN-OIL EMULSION FOR THE SKIN |
KR20220163443A (ko) * | 2020-05-14 | 2022-12-09 | 카오카부시키가이샤 | 유중수형 유화 선스크린 화장료 |
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US20140205552A1 (en) * | 2011-08-26 | 2014-07-24 | Shiseido Company, Ltd. | Water-in-Oil Emulsified Sunscreen Cosmetic |
US9192547B2 (en) * | 2011-08-26 | 2015-11-24 | Shiseido Company, Ltd. | Water-in oil emulsified sunscreen cosmetic |
WO2019172107A1 (ja) * | 2018-03-08 | 2019-09-12 | 株式会社 資生堂 | 離漿防止用油中水型化粧料組成物 |
JP2019156735A (ja) * | 2018-03-08 | 2019-09-19 | 株式会社 資生堂 | 離漿防止用油中水型化粧料組成物 |
JP7084166B2 (ja) | 2018-03-08 | 2022-06-14 | 株式会社 資生堂 | 離漿防止用油中水型化粧料組成物 |
US11844850B2 (en) | 2018-03-08 | 2023-12-19 | Shiseido Company, Ltd. | Water in oil type cosmetic composition for preventing syneresis |
Also Published As
Publication number | Publication date |
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JP5382904B2 (ja) | 2014-01-08 |
AU2009216500B2 (en) | 2014-01-09 |
CN101951876A (zh) | 2011-01-19 |
TW200944242A (en) | 2009-11-01 |
KR101524026B1 (ko) | 2015-05-29 |
EP2243465A1 (en) | 2010-10-27 |
KR20100122072A (ko) | 2010-11-19 |
TWI439290B (zh) | 2014-06-01 |
AU2009216500A1 (en) | 2009-08-27 |
JP2009196896A (ja) | 2009-09-03 |
ES2567707T3 (es) | 2016-04-26 |
US20100291011A1 (en) | 2010-11-18 |
HK1148214A1 (en) | 2011-09-02 |
EP2243465A4 (en) | 2014-03-19 |
CN101951876B (zh) | 2013-01-16 |
EP2243465B1 (en) | 2016-01-20 |
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