WO2011037000A1 - 日焼け止め化粧料 - Google Patents
日焼け止め化粧料 Download PDFInfo
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- WO2011037000A1 WO2011037000A1 PCT/JP2010/065199 JP2010065199W WO2011037000A1 WO 2011037000 A1 WO2011037000 A1 WO 2011037000A1 JP 2010065199 W JP2010065199 W JP 2010065199W WO 2011037000 A1 WO2011037000 A1 WO 2011037000A1
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- titanium oxide
- sunscreen cosmetic
- acid
- resin
- sunscreen
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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
- 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
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0275—Containing agglomerated particulates
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
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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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
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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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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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
- A61K8/88—Polyamides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/612—By organic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/624—Coated by macromolecular compounds
Definitions
- the present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic that prevents contamination due to secondary adhesion to clothes.
- UV absorption wavelength regions by sunscreen cosmetics are the UV-A region (320 to 400 nm) and the UV-B region (290 to 320 nm). UV rays in the UV-A region darken the skin, but it was thought that sunburn occurred like the ultraviolet rays in the UV-B region and did not promote skin aging.
- UV-B region In recent years, ultraviolet rays in the UV-B region stay relatively on the surface of the skin, whereas ultraviolet rays in the UV-A region reach the deep part of the skin, causing skin cancer as well as skin aging. It has been found to be a cause of triggering. Thus, there is an increasing demand for sunscreen cosmetics, particularly in the UV-A region.
- UV absorbers useful in the UV-A region hexyl diethylaminohydroxybenzoylbenzoate, 2,4-bis ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6
- UVA absorbers hexyl diethylaminohydroxybenzoylbenzoate, 2,4-bis ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6
- UV absorbers hexyl diethylaminohydroxybenzoylbenzoate, 2,4-bis ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6
- UVA absorbers hexyl diethylaminohydroxybenzoylbenzoate, 2,4-bis ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6
- UV absorbers hexyl die
- UV absorbers which is useful as diethylaminohydroxybenzoyl hexyl benzoate and the like. UVA absorbers often become contaminated by secondary adhesion.
- octyl methoxycinnamate is known as an ultraviolet absorber useful for sunscreen cosmetics, but octyl methoxycinnamate is easily colored and causes staining.
- octyl methoxycinnamate by combining octyl methoxycinnamate with a specific benzotriazole derivative, it is possible to prevent octyl methoxycinnamate from being stained (colorability) and to have an excellent UV absorption effect in the UV-A region.
- Patent Document 2 A technique for exhibiting the above has been developed (Patent Document 2).
- sunscreen cosmetics containing an ultraviolet absorber are required to eliminate the problem of staining.
- Sunscreen cosmetics comprising a water-in-oil emulsion composition containing a UVA absorber such as diethylaminohydroxybenzoyl hexyl benzoate are known (Patent Documents 3 and 4), and sunscreen cosmetics include UV protection.
- a UVA absorber such as diethylaminohydroxybenzoyl hexyl benzoate
- sunscreen cosmetics include UV protection.
- zinc oxide and / or titanium oxide fine particle powder is often blended as an ultraviolet scattering agent together with the ultraviolet absorber.
- cosmetics containing titanium oxide resin powder containing titanium oxide powder in a resin are widely known as makeup cosmetics.
- the use of metal oxide particles contained in resin powder makes it possible to use the technical difficulties and organicities associated with the use of metal oxide fine particles as a raw material for cosmetics.
- an organic ultraviolet absorber can be obtained by using metal compound particles contained in the resin powder. It is known that the technical difficulties associated with the use of metal compound fine particles as a raw material for cosmetics and the harmful effects associated with the presence of organic ultraviolet absorbers can be eliminated (Patent Document 6). ).
- An object of the present invention is to provide a sunscreen cosmetic that improves the adhesion (dyeability) of clothes in a sunscreen cosmetic formulated with a combination of a UVA absorber and fine-particle titanium oxide.
- the present invention (1) Diethylaminohydroxybenzoyl hexyl benzoate, 2,4-bis ⁇ [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl ⁇ -6- (4-methoxyphenyl) -1,3,5-triazine
- a UVA absorber selected from one or more of 4-tert-butyl-4-methoxydibenzoylmethane and 2-hydroxy-4-methoxybenzophenone;
- a sunscreen cosmetic characterized in that it contains a spherical resin powder containing 35% or more of ultrafine titanium oxide that has been hydrophobized.
- the present invention also provides the sunscreen cosmetic described above, wherein the hydrophobized ultrafine titanium oxide is treated with fatty acid aluminum.
- the present invention provides the sunscreen cosmetic described above, wherein the sunscreen cosmetic is a water-in-oil emulsified cosmetic.
- the sunscreen cosmetic of the present invention reduces the adhesion to clothes. Therefore, it is possible to highly blend the UVA absorber and the ultrafine titanium oxide in the sunscreen cosmetic. (2) The sunscreen cosmetic of the present invention exhibits an excellent ultraviolet protection effect due to the UVA absorber and the ultrafine titanium oxide.
- Diethylaminohydroxybenzoyl hexyl benzoate Diethylaminohydroxybenzoyl hexyl benzoate used in the present invention is a known UV absorber in the UV-A region (UVA absorber).
- UVA absorber UV absorber
- commercially available products Ubinar A plus: manufactured by BASF can be preferably used.
- 4-tert-butyl-4-methoxydibenzoylmethane used in the present invention is a known UV absorber in the UV-A region (UVA absorber).
- UVA absorber a commercially available product (manufactured by Pulsol 1789 DSM) can be preferably used.
- 2-Hydroxy-4-methoxybenzophenone used in the present invention is a known UV absorber in the UV-A region (UVA absorber).
- UVA absorber a commercially available product (manufactured by Yubinar M40 BASF) can be preferably used.
- the blending amount of the UVA absorber is appropriately determined, but the total blending amount of one, two, three or four is usually 1 to 35% by mass with respect to the total amount of the sunscreen cosmetic. 3 to 30% by mass is preferable, and 5 to 20% by mass is more preferable.
- blend octyl methoxycinnamate with a sunscreen cosmetics of this invention as a UVB absorber other than said UVA absorber.
- the blending amount is appropriately determined, but is usually 1 to 40% by weight, preferably 5 to 20% by weight, based on the total amount of the sunscreen cosmetic.
- the resin spherical powder used in the present invention is a resin spherical powder containing 35% or more of ultrafine titanium oxide that has been hydrophobized inside.
- ultrafine titanium oxide is ultrafine titanium oxide powder having an average particle size of 10 nm to 100 nm.
- the average particle diameter is a value measured by a conventional method using a laser particle size distribution meter.
- the resin of the resin spherical powder is a resin powder containing 41% by mass or more of ultrafine titanium oxide that has been subjected to a hydrophobic treatment inside the spherical resin.
- a resin powder in which ultrafine titanium oxide is encapsulated in a spherical resin powder is known, but if the content is 34% by mass or less, the content is too small. Even when blended to give UV protection ability to cosmetics, a large amount of resin powder must be blended in order to achieve sufficient performance, and the blending design of the cosmetics becomes extremely difficult.
- ultrafine titanium oxide that has not been hydrophobized the viscosity of the dispersion becomes very high at the stage of producing the dispersion before polymerization, and the dispersion energy is effectively given to the fine particles of the metal compound. However, it becomes difficult to make the metal compound fine particles highly dispersed. For this reason, aggregates of the metal compound remain or become non-uniform, making it impossible to produce a uniform resin powder.
- a powder containing ultrafine titanium oxide at a high content of 41% by mass or more has never been used as a cosmetic raw material.
- ⁇ Production method of spherical resin powder> In order to produce a resin spherical powder, a suspension polymerization method, an emulsion polymerization method, a method of mechanically dispersing or emulsifying a resin solution, a method of depositing fine particles from the resin solution, and the like are known.
- the method for dispersing the hydrophobized fine particle titanium oxide having a content of more than 35% by mass inside the base material particles is, for example, when the base material particles are nylon resin, heating and dissolving the cyclic lactam in paraffin or the like, A desired amount of titanium dioxide fine powder is added to this, and while stirring, a polymerization accelerator such as phosphorus trichloride is added to cause alkali polymerization, and the resulting particles are filtered off, and an organic solvent such as benzene or isopropyl is added.
- a method of washing with alcohol and drying is exemplified.
- the base material particle is a silicone resin
- a fine powder of titanium dioxide or zinc oxide is added to and mixed with an aqueous solution of ammonia or amine, and further hydrolyzable silane such as chlorosilane, hydrogensilane, alkoxysilane, acetoxy
- the method include adding silane to cause hydrolysis and condensation reaction, filtering the obtained particles, washing with water, and drying.
- the base material particles are silicon oxide
- a suspension is prepared by adding fine powder of titanium dioxide or zinc oxide to sodium silicate, and further, a surfactant and an oily dispersant such as benzene are added.
- a salt such as ammonium sulfate or ammonium chloride to add sodium silicate
- a salt such as ammonium sulfate or ammonium chloride
- Examples include a method of reacting and filtering the obtained particles, washing with water, washing with an organic solvent such as methanol, and drying.
- a water-insoluble thermoplastic resin is made into a liquid at a high temperature of about 200 ° C., and the fine particle titanium oxide hydrophobized is dispersed therein.
- the average particle diameter of the resin spherical powder is 1 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
- the average particle diameter is a value measured by a conventional method using a laser particle size distribution meter.
- the treatment agent for the hydrophobic treatment is not limited, but aluminum stearate, methylhydrogenpolysiloxane, alkyltriethoxysilane and the like are preferable, and the hydrophobic treatment is performed by a conventional method.
- the compounding amount of the resin spherical powder is usually 1 to 40% by mass with respect to the total amount of the sunscreen cosmetic. 3 to 30% by mass is preferable, and 5 to 20% by mass is more preferable.
- the sunscreen cosmetics of the present invention are usually used in cosmetics, such as whitening agents, moisturizers, antioxidants, alcohols, thickeners, colorants, various powder components, It is preferable to appropriately mix various oily components and various aqueous components as necessary, and adjust the emulsion composition by a conventional method, and it is preferable to prepare a water-in-oil emulsion composition.
- the compounding quantity of the water which comprises a water-in-oil emulsion composition or an oil-in-water emulsion composition is arbitrary, and is suitably determined according to a product.
- the emulsifier is optional.
- As the emulsifier POE / methyl polysiloxane copolymer, silicone chain branched POE / methyl polysiloxane copolymer, cross-linked POE / methyl polysiloxane copolymer, alkyl / POE co-modified methyl polysiloxane copolymer, silicone Examples include a chain-branched alkyl / POE co-modified methylpolysiloxane copolymer, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.
- preferred emulsifiers for the present invention are alkyl / POE co-modified methyl polysiloxane copolymers or acrylic acid / alkyl methacrylate copolymers.
- Higher alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cholesterol, phytosterol.
- Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid.
- Moisturizers such as polyethylene glycol, glycerin, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate and chitosan.
- Thickeners such as methylcellulose, ethylcellulose, gum arabic, and polyvinyl alcohol.
- a liquid constituting an aqueous phase such as ethanol or 1,3-butylene glycol.
- Antioxidants such as butylhydroxytoluene, tocopherol and phytic acid.
- Antibacterial preservatives such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid esters (such as ethylparaben and butylparaben), and hexachlorophene.
- Amino acids and hydrochlorides such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine.
- Organic acids such as acyl sarcosine acid (eg, lauroyl sarcosine sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid.
- Vitamin A and its derivatives vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbic acid, ascorbic acid phosphate ( Salt), vitamin C such as ascorbic acid dipalmitate, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, vitamin E acetate, vitamin E nicotinate and other vitamin E, vitamin D, vitamin H, pantothenic acid, pantethine, etc.
- vitamin A and its derivatives vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B
- Vitamins Nicotinamide, benzyl nicotinate, ⁇ -oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, thymol, inositol, saponins (psychosaponin, carrot saponin, loofah)
- Various drugs such as saponin, muclodisaponin, etc.), pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, cephalanthin, placenta extract.
- Cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and laurylamine oxide.
- Metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate and gluconic acid.
- the sunscreen cosmetics of the present invention include product forms such as ointments, creams, emulsions, lotions and the like.
- a compounding quantity is the mass% with respect to the whole quantity unless there is particular notice.
- the sunscreen water-in-water emulsified cosmetics (milky sunscreen) shown in each table were produced by a conventional method.
- the cleaning removal effect against the adhesion was confirmed by the following method.
- Table 3 shows oil-in-water emulsified cosmetics (milky sunscreen).
- the obtained aqueous dispersion was continuously filtered through 5C filter paper.
- the recovered filtrate was again dispersed in water to 5% by weight and further filtered. This operation was repeated 3 times for washing and drying to obtain titanium oxide-containing polyamide particles (average particle size 5 ⁇ m).
- this dispersion was transferred to a reactor equipped with a stirrer and a thermometer, and the temperature was raised to 55 ° C. to initiate polymerization. Furthermore, after making it superpose
- the sunscreen cosmetic is an oil-in-water emulsion composition
- the hydrophobized titanium oxide powder by replacing the hydrophobized titanium oxide powder with the spherical resin powder used in the present invention, the dyeing property is reduced, and Excellent adhesion.
- the present invention it is possible to provide a sunscreen cosmetic that has a high UV protection effect and prevents contamination due to secondary adhesion to clothes.
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Abstract
Description
そしてこの課題は、前記特定のUVA吸収剤を内部に疎水化処理された超微粒子酸化チタンを35%以上含有した樹脂球状粉末と組み合わせて配合すると見事に解決できることを見出し、本発明を完成するに至った。
(1)ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、2,4-ビス{[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル}-6-(4-メトキシフェニル)-1,3,5-トリアジン、4-tert-ブチル-4-メトキシジベンゾイルメタン、2-ヒドロキシ4-メトキシベンゾフェノンの一種又は二種以上から選ばれるUVA吸収剤と、
(2)内部に疎水化処理された超微粒子酸化チタンを35%以上含有した樹脂球状粉末と
を配合することを特徴とする日焼け止め化粧料を提供するものである。
(2)本発明の日焼け止め化粧料は、UVA吸収剤と超微粒子酸化チタンにより優れた紫外線防御効果を発揮する。
本発明に用いるジエチルアミノヒドロキシベンゾイル安息香酸ヘキシルは、公知のUV-A領域の紫外線吸収剤(UVA吸収剤)である。本発明においては、市販品(ユビナールA plus:BASF製)を好ましく利用できる。
本発明に用いる2,4-ビス{[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル}-6-(4-メトキシフェニル)-1,3,5-トリアジンは、公知のUV-A領域の紫外線吸収剤(UVA吸収剤)である。本発明においては、市販品(チノソーブS チバスペシャルケミカルズ製)を好ましく利用できる。
本発明に用いる4-tert-ブチル-4-メトキシジベンゾイルメタンは、公知のUV-A領域の紫外線吸収剤(UVA吸収剤)である。本発明においては、市販品(パルソール1789 DSM製)を好ましく利用できる。
本発明に用いる2-ヒドロキシ4-メトキシベンゾフェノンは、公知のUV-A領域の紫外線吸収剤(UVA吸収剤)である。本発明においては、市販品(ユビナールM40 BASF製)を好ましく利用できる。
本発明に用いる樹脂球状粉末は、内部に疎水化処理された超微粒子酸化チタンを35%以上含有した樹脂球状粉末である。
本発明において、超微粒子酸化チタンとは、その平均粒子径が10nm~100nmの超微粒子酸化チタン粉末である。平均粒子径はレーザー粒度分布計を用いて常法により測定される値である。
樹脂球状粉末の樹脂とは、球状樹脂の内部に疎水化処理された超微粒子酸化チタンを41質量%以上含有する樹脂粉末である。球状樹脂粉末に超微粒子酸化チタンが内包された樹脂粉末は公知であるが、含有率が34質量%以下では含有量が少なすぎ、例えば、超微粒子酸化チタンを含有する樹脂粉体を化粧料に配合して紫外線防御能を化粧料に与えようとしても、十分に性能を発揮させるためには樹脂粉体を大量に配合しなければならず、化粧料の配合設計が極めて難しくなる。
また、疎水化処理されていない超微粒子酸化チタンでは、重合前の分散液を製造する段階で、この分散液の粘度が非常に高くなり、金属化合物の微粒子に対し効果的に分散エネルギーを与えることができずに、金属化合物の微粒子を高分散状態にすることは困難になる。このため、金属化合物の凝集物が残ったり、不均一になったりして均一な樹脂粉体を製造することはできなくなる。
超微粒子酸化チタンを41質量%以上もの高い含有率で内包された粉末は化粧料原料として使用されたことなない。
樹脂球状粉末を製造するには、懸濁重合法、乳化重合法、樹脂溶液を機械的に分散又は乳化する方法、樹脂溶液から微粒子を析出させる方法等が知られている。母材粒子の内部に含有率が35質量%を超える疎水化処理微粒子酸化チタンを分散させる方法は、例えば、母材粒子がナイロン樹脂の場合には、パラフィン等に環状ラクタムを加熱、溶解し、これに所望量の二酸化チタン微粉末を添加し、かき混ぜながら、重合促進剤、例えば三塩化リンを添加してアルカリ重合を行わせ、得られた粒子をろ別し、有機溶剤、例えばベンゼンやイソプロピルアルコールで洗浄し、乾燥する方法が挙げられる。
母材粒子がシリコーン樹脂の場合には、アンモニアやアミン等の水溶液に二酸化チタンや酸化亜鉛の微粉末を添加、混合し、更に、加水分解性シラン、例えばクロロシラン、ハイドロジェンシラン、アルコキシシラン、アセトキシシランを加えて加水分解、縮合反応を行わせ、得られた粒子をろ別し、水洗し、乾燥する方法が挙げられる。
また、母材粒子が酸化ケイ素の場合には、まず、ケイ酸ナトリウムに二酸化チタンや酸化亜鉛の微粉末を添加して懸濁液を調製し、更に界面活性剤とベンゼン等の油性分散剤との混合液を調製し、この混合液に上述した懸濁液を加え、乳化させて油中水分散型エマルジョンを得た後、それを硫酸アンモニウムや塩化アンモニウム等の塩を添加してケイ酸ナトリウムと反応させ、得られた粒子をろ別、水洗し、メタノール等の有機溶剤で洗浄し、乾燥する方法などが挙げられる。
さらに、好適な製法として非水溶性の熱可塑性樹脂を200℃程度の高温下で液状にしておき、そこに疎水化処理した微粒子酸化チタンを分散させた後、当該分散液を水溶性材料(オリゴ糖など)に分散して冷却固化した後、水洗により水溶性材料を除去して、非水溶性の熱可塑性樹脂と疎水化処理した微粒子酸化チタンからなる樹脂球状粉末を得る方法が挙げられる。
疎水化処理するための処理剤は限定されないがステアリン酸アルミニウム・メチルハイドロジェンポリシロキサン・アルキルトリエトキシシランなどが好ましく、常法により疎水化処理される。
本発明の日焼け止め化粧料は、上記必須成分以外に、通常化粧料に用いられる成分、例えば、美白剤、保湿剤、酸化防止剤、アルコール類、増粘剤、色剤、各種の粉末成分、各種の油性成分、各種の水性成分を必要に応じて適宜配合して、常法により乳化組成物を調整することが好ましく、油中水型乳化組成物に調製することが好ましい。
なお、油中水型乳化組成物又は水中油型乳化組成物を構成する水の配合量は任意であり、製品に応じて適宜決定される。
これらの中で本発明に好ましい乳化剤は、アルキル・POE共変性メチルポリシロキサン共重合体、又は、アクリル酸・メタクリル酸アルキル共重合体である。
デカメチルシクロペンタシロキサン、ジメチルポリシロキサン、ヘプタメチルオクチルトリシロキサン、トリメチルシロキシケイ酸、流動パラフィン、スクワラン、アボカド油、マカデミアナッツ油、トウモロコシ油、オリーブ油、ナタネ油、月見草油、ヒマシ油、ヒマワリ油、茶実油、コメヌカ油、ホホバ油、カカオ脂、ヤシ油、スクワレン、牛脂、モクロウ、ミツロウ、キャンデリラロウ、カルナバロウ、鯨ロウ、ラノリン、流動パラフィン、ポリオキシエチレン(8モル)オレイルアルコールエーテル、モノオレイン酸グリセリル、シクロメチコン、ジメチルポリシロキサン、ジフェニルポリシロキサンなどの油分。
カプリルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、コレステロール、フィトステロールなどの高級アルコール。
カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、ラノリン脂肪酸、リノール酸、リノレン酸などの高級脂肪酸。
ポリエチレングリコール、グリセリン、ソルビトール、キシリトール、マルチトール、ムコ多糖、ヒアルロン酸、コンドロイチン硫酸、キトサンなどの保湿剤。
メチルセルロース、エチルセルロース、アラビアガム、ポリビニルアルコールなどの増粘剤。
エタノール、1,3-ブチレングリコールなどの水相を構成する液体。
ブチルヒドロキシトルエン、トコフェロール、フィチン酸などの酸化防止剤。
安息香酸、サリチル酸、ソルビン酸、パラオキシ安息香酸エステル(エチルパラベン、ブチルパラベンなど)、ヘキサクロロフェンなどの抗菌防腐剤。
グリシン、アラニン、バリン、ロイシン、セリン、トレオニン、フェニルアラニン、チロシン、アスパラギン酸、アスパラギン、グルタミン、タウリン、アルギニン、ヒスチジンなどのアミノ酸と塩酸塩。
アシルサルコシン酸(例えばラウロイルサルコシンナトリウム)、グルタチオン、クエン酸、リンゴ酸、酒石酸、乳酸などの有機酸。
ビタミンA及びその誘導体、ビタミンB6塩酸塩、ビタミンB6トリパルミテート、ビタミンB6ジオクタノエート、ビタミンB2及びその誘導体、ビタミンB12、ビタミンB15及びその誘導体などのビタミンB類、アスコルビン酸、アスコルビン酸リン酸エステル(塩)、アスコルビン酸ジパルミテートなどのビタミンC類、α-トコフェロール、β-トコフェロール、γ-トコフェロール、ビタミンEアセテート、ビタミンEニコチネートなどのビタミンE類、ビタミンD類、ビタミンH、パントテン酸、パンテチンなどのビタミン類。
ニコチン酸アミド、ニコチン酸ベンジル、γ-オリザノール、アラントイン、グリチルリチン酸(塩)、グリチルレチン酸及びその誘導体、ヒノキチオール、ムシジン、ビサボロール、ユーカリプトール、チモール、イノシトール、サポニン類(サイコサポニン、ニンジンサポニン、ヘチマサポニン、ムクロジサポニンなど)、パントテニルエチルエーテル、エチニルエストラジオール、トラネキサム酸、セファランチン、プラセンタエキスなどの各種薬剤。
ギシギシ、クララ、コウホネ、オレンジ、セージ、タイム、ノコギリソウ、ゼニアオイ、センキュウ、センブリ、トウキ、トウヒ、バーチ、スギナ、ヘチマ、マロニエ、ユキノシタ、アルニカ、ユリ、ヨモギ、シャクヤク、アロエ、クチナシ、サワラなどの有機溶剤、アルコール、多価アルコール、水、水性アルコールなどで抽出した天然エキス。
ステアリルトリメチルアンモニウムクロライド、塩化ベンザルコニウム、ラウリルアミンオキサイドなどのカチオン界面活性剤。
エデト酸二ナトリウム、エデト酸三ナトリウム、クエン酸ナトリウム、ポリリン酸ナトリウム、メタリン酸ナトリウム、グルコン酸等の金属封鎖剤。
〔製造例1〕
ポリアミド12 25重量部、ステアリン酸アルミニウム処理微粒子酸化チタン(平均粒径 15nm、TTO S4 石原産業株式会社)25重量部を超音波分散機を用いて分散した後、オリゴ糖100重量部と200℃に加温混合し、押出機で溶融混練しながらストランド状に押し出した。これを搬送し、450重量部の水の入った容器中に供給して、オリゴ糖を水に溶解させ、酸化チタン内包ポリアミド粒子の水分散液を得た。
次いで、得られた水分散液を連続的に5Cの濾紙で濾過した。回収濾物は再度5重量%となるように水中に分散し、さらに濾過を行った。この操作を3回繰り返すことにより洗浄を行い、乾燥して酸化チタン内包ポリアミド粒子(平均粒径5μm)を得た。
〔製造例2〕
樹脂モノマー相
ステアリン酸アルミニウム処理微粒子酸化チタン
(平均粒径 15nm MT-100T テイカ社製)45重量部
酢酸ビニル(樹脂モノマー) 10重量部
メチルメタクリレート(樹脂モノマー) 34.8重量部
エチレングリコールジメタクリレート(樹脂モノマー)10重量部
2,2アゾビス 2,4ジメチルバレロニトリル(重合開始剤) 0.2重量部
水相
水 500重量部
ポリビニルアルコール(ケン化度87%) 10重量部
樹脂モノマー相を超音波分散機を用いて分散した後、水相に加えてホモミキサーで撹拌してモノマー粒子が4μmになるように調整した。次に、この分散体を攪拌機および温度計を備えた反応装置に移し、55℃に昇温して重合を開始させた。さらに、5時間、この温度で重合させたのち、室温まで冷却し、吸引濾過にて得られた樹脂粉体を分離した。適量の温水そしてメタノールで洗浄したのち、室温にて乾燥させてステアリン酸アルミ処理酸化チタンが45%内包された樹脂球状粉末を得た。
図1に示すように、サンプルを腕に厚めに塗布し、ブロード綿の中央に転写し(転写量約0.06g)、一日室内に放置した後、通常の衣類用洗剤(アタック:花王株式会社)を使用して洗濯し、分光測色計(ミノルタ(株):現コニカミノルタセンシング(株)製CM-2002)で、ΔE及びΔYIを測定した。結果を各表及び各図に示す。
下記実施例において、疎水化処理微粒子酸化チタンを本発明の樹脂内包酸化チタンに置き換えることで染着性が低減され、耐汚着に優れる。
平均粒子径5μm、内包されている超微粒子酸化チタンの平均粒子径15nm)
*2:TTO S4(石原産業株式会社) ステアリン酸アルミニウムで疎水化処理された平均粒子径 15nmの酸化チタン粉末
*3:パルソール1789(DSM製)
*4:ユビナールA+(BASF製)
*5:チノソーブS(チバ製)
*6:ユビナールN539T(BASF製)
平均粒子径4μm、内包されている超微粒子酸化チタンの平均粒子径15nm)
*2:MT-100T(テイカ株式会社製)ステアリン酸アルミニウムで疎水化処理された平均粒子径 15nmの酸化チタン粉末
*3:ユビナールM40 BASF社製
*2:MT-100T(テイカ株式会社製)ステアリン酸アルミニウムで疎水化処理された平均粒子径 15nmの酸化チタン粉末
*3:製造例2で得られた内部にステアリン酸アルミニウムで疎水化処理された超微粒子酸化チタンを45%含有したポリアクリル酸球状粉末
Claims (3)
- (1)ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、2,4-ビス{[4-(2-エチルヘキシルオキシ)-2-ヒドロキシ]-フェニル}-6-(4-メトキシフェニル)-1,3,5-トリアジン、4-tert-ブチル-4-メトキシジベンゾイルメタン、2-ヒドロキシ4-メトキシベンゾフェノンの一種又は二種以上から選ばれるUVA吸収剤と、
(2)内部に疎水化処理された超微粒子酸化チタンを35%以上含有した樹脂球状粉末と
を配合することを特徴とする日焼け止め化粧料。 - 前記疎水化処理された超微粒子酸化チタンが脂肪酸アルミニウムによって処理されたものであることを特徴とする請求項1記載の日焼け止め化粧料。
- 前記日焼け止め化粧料が油中水型乳化化粧料であることを特徴とする請求項1又は2記載の日焼け止め化粧料。
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JP5888937B2 (ja) * | 2011-10-31 | 2016-03-22 | 富士フイルム株式会社 | 化粧料 |
JP5908699B2 (ja) | 2011-10-31 | 2016-04-26 | 富士フイルム株式会社 | 化粧料 |
ES2765208T3 (es) * | 2013-05-30 | 2020-06-08 | Oreal | Composición cosmética |
DE102014207924A1 (de) | 2014-04-28 | 2015-10-29 | Beiersdorf Ag | Sonnenschutzmittel mit reduzierter Neigung zur Textilverfleckung IV |
DE102014207919A1 (de) | 2014-04-28 | 2015-10-29 | Beiersdorf Ag | Sonnenschutzmittel mit reduzierter Neigung zur Textilverfleckung I |
DE102014207935A1 (de) * | 2014-04-28 | 2015-10-29 | Beiersdorf Ag | Sonnenschutzmittel mit reduzierter Neigung zur Textilverfleckung III |
DE102014207916A1 (de) * | 2014-04-28 | 2015-10-29 | Beiersdorf Aktiengesellschaft | Sonnenschutzmittel mit reduzierter Neigung zur Textilverfleckung II |
CN107847407B (zh) * | 2015-07-22 | 2020-12-29 | 兰达拉伯斯(2012)有限公司 | Uv防护组合物 |
JP6263244B2 (ja) * | 2015-10-09 | 2018-01-17 | 株式会社 資生堂 | 噴霧型日焼け止め化粧料 |
DE102015223261A1 (de) | 2015-11-25 | 2017-06-01 | Beiersdorf Ag | Sonnenschutzmittel enthaltend Titandioxid |
DE102017201235A1 (de) | 2017-01-26 | 2018-07-26 | Beiersdorf Ag | Verwendung von Dimethylaminohydroxybenzoylhexylbenzoat in kosmetischen Sonnenschutzmitteln |
KR102067514B1 (ko) | 2017-02-16 | 2020-01-17 | 가톨릭대학교 산학협력단 | 생체 적합성 자외선 차단 고분자, 이를 포함하는 조성물 및 이의 제조방법 |
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2009
- 2009-09-24 JP JP2009218818A patent/JP5553377B2/ja active Active
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2010
- 2010-09-06 KR KR1020187003445A patent/KR20180016632A/ko not_active Application Discontinuation
- 2010-09-06 WO PCT/JP2010/065199 patent/WO2011037000A1/ja active Application Filing
- 2010-09-06 US US13/393,716 patent/US20120156149A1/en not_active Abandoned
- 2010-09-06 AU AU2010299305A patent/AU2010299305B2/en not_active Ceased
- 2010-09-06 KR KR1020177002925A patent/KR20170016999A/ko not_active Application Discontinuation
- 2010-09-06 CN CN201080042258.8A patent/CN102510751B/zh active Active
- 2010-09-06 KR KR1020117029578A patent/KR101738179B1/ko active IP Right Grant
- 2010-09-06 EP EP10818676.8A patent/EP2481393B1/en active Active
- 2010-09-06 ES ES10818676.8T patent/ES2605961T3/es active Active
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2012
- 2012-10-12 HK HK12110096.8A patent/HK1169323A1/zh not_active IP Right Cessation
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JPH0853568A (ja) | 1994-08-12 | 1996-02-27 | Sumitomo Osaka Cement Co Ltd | 球状樹脂粉体およびその製造方法ならびに化粧料 |
JPH09208437A (ja) | 1996-02-07 | 1997-08-12 | Sumitomo Osaka Cement Co Ltd | 化粧料 |
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See also references of EP2481393A4 * |
Also Published As
Publication number | Publication date |
---|---|
KR20180016632A (ko) | 2018-02-14 |
KR20170016999A (ko) | 2017-02-14 |
KR20120065272A (ko) | 2012-06-20 |
JP2011068567A (ja) | 2011-04-07 |
EP2481393A4 (en) | 2015-06-24 |
US20120156149A1 (en) | 2012-06-21 |
CN102510751B (zh) | 2016-08-24 |
JP5553377B2 (ja) | 2014-07-16 |
KR101738179B1 (ko) | 2017-05-19 |
CN102510751A (zh) | 2012-06-20 |
AU2010299305A1 (en) | 2012-03-29 |
EP2481393A1 (en) | 2012-08-01 |
ES2605961T3 (es) | 2017-03-17 |
EP2481393B1 (en) | 2016-11-02 |
HK1169323A1 (zh) | 2013-01-25 |
AU2010299305B2 (en) | 2016-03-24 |
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