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    • 专利摘要:
    1/1 abstract “topical sunscreen compositions containing titanium dioxide and silica” the present invention relates to a topical composition comprising highly porous, uncoated silica spheres with a dv0 particle size greater than 0.3 µm, a dv100 less than 35 µm, a dv50 selected in the 8 to 15 µm range and an oil absorption capacity selected in the 1.2-2.5 cc / g range and a selected double-coated ultrafine titanium dioxide metal oxide and / or coated ultrafine zinc oxide.
    公开号:BR112016006580B1
    申请号:R112016006580-8
    申请日:2014-09-25
    公开日:2020-08-04
    发明作者:Aline HUEBER；Christine Saecker
    申请人:Dsm Ip Assets B.V；
    IPC主号:
    专利说明:

    [001] The present invention relates to a topical composition comprising (1) highly porous, uncoated silica spheres, with a DvO particle size greater than 0.3 pm, a Dv100 less than 35 pm, a Dy50 selected in range from 8 to 15 pm and an oil absorption capacity selected in the range of 1.2-2.5 cc / g and (2) a metallic oxide selected from double-coated titanium dioxide and / or zinc oxide with coating ultrafine.
    [002] Inorganic UV-filter substances, such as titanium dioxide with an ultra-thin coating and zinc oxide, are widely used in sunscreens. These inorganic UV filters, however, have a tendency to release a white film on the skin during and after application, which is highly undesirable. Therefore, there is a need for components that are capable of reducing this bleaching effect.
    [003] Surprisingly, it was found that the use of highly porous silica spheres in a topical composition containing double-coated titanium dioxide or ultra-thin coated zinc oxide significantly reduced the whitening effect.
    [004] Therefore, the present invention relates in a first aspect to topical compositions comprising (1) highly porous, uncoated silica spheres having a DvO particle size greater than 0.3 pm, DvlOO less than 35 pm, Dv50 selected in the range of 8 to 15 pm and an oil absorption capacity selected in the range of 1.2-2.5 cc / g and a metallic oxide selected from titanium dioxide with double ultra-thin coating and / or zinc oxide with coating ultrafine.
    [005] Another subject of the invention is directed to a method of reducing the bleaching effect of a metallic oxide selected from titanium dioxide with double ultrafine coating and / or zinc oxide ultrafine coating in a topical composition, with the aforementioned method comprising the step of addition to the topical uncoated composition, of highly porous silica spheres with particle size DvO greater than 0.3 pm, DvlOO less than 35 pm, Dv50 selected in the range 8 to 15 pm and an oil absorption capacity selected in the range of 1.2-2.5 cc / g and evaluating the effect.
    [006] In another embodiment, the invention relates to the use of highly porous silica spheres, uncoated with a particle size DvO greater than 0.3 pm, DvlOO less than 35 pm, Dv50 selected in the range 8 to 15 pm and an oil absorption capacity selected in the range of 1.2-2.5 cc / g to reduce the bleaching effect of a metallic oxide selected from titanium dioxide with double ultra-thin coating and / or zinc oxide with ultra-thin coating in a topical composition.
    [007] In all embodiments of the present invention, the amount of silica spheres is preferably selected in the range of 0.5 to 10% by weight, more preferably in the range of 1 to 5% by weight, and even more preferably in the range of 2 to 4% by weight, based on the total weight of the composition.
    [008] Uncoated porous silica spheres according to the present invention can be prepared from sodium silicate by emulsion polymerization, according to standard procedures, such as, for example, through the sol-gel method.
    [009] The particle size of the spheres according to the invention (in% volume) is determined with a Coulter LS13320 or Malvern Mastersizer 2000, according to standard methods in the field. In% number, the average size of the Dn50 particles varies from 8 to 15 pm, preferably from 9 to 15 pm.
    [010] The oil absorption capacity (cc / g) [also known as (cm3 / g)] refers to the amount of paraffin (in cc) absorbed by a specific amount (g) of beads, that is, the amount before the dry powder disappears. The oil absorption capacity, according to the present invention, is determined at a temperature of 23 ° C by weighing 2 g of the respective spheres in a 20 ml beaker. Then, liquid paraffin (Paraffinum Perliquidum PH. EUR. CAS 8042-47-5) is added. After adding 4 to 5 drops of the paraffin to the powder, mixing is performed using a spatula, and the paraffin addition is continued until clumps of oil and powder are formed. From this point, the paraffin is added dropwise and the mixture is then ground with a spatula. The addition of oil is interrupted when the dry powder disappears completely and a highly viscous, homogeneous transparent white gel is obtained. The oil absorption capacity (cc / g) is then calculated by the volume of paraffin used (in cc) per g of the respective spheres.
    [O11] In all embodiments of the present invention, the oil-absorbing capacity of the silica spheres is preferably selected in the range of 1.2 to 2.0 cc / g, most preferably in the range of 1.3 to 1 , 8 cc / g.
    [012] Highly porous silica spheres according to the invention are, for example, obtained from VALVANCE ™ Touch210, DSM Nutritional Products Ltd Kaiseraugst.
    [013] In all embodiments of the present invention, the amount of titanium dioxide with double ultrafine coating in the topical composition is preferably selected in the range of 0.5 to 15% by weight, preferably in the range of 1 to 10% in weight, and more preferably in the range of 2 to 5% by weight, based on the total weight of the composition.
    [014] In all embodiments of the present invention, the amount of zinc oxide with ultra-thin coating in the topical composition is preferably selected in the range of 0.5 to 25% by weight, more preferably in the range of 1 to 20% in weight, such as in the range of 1 to 15% by weight, and even more preferably in the range of 2 to 10% by weight, such as in the range of 2 to 5% by weight based on the total weight of the composition.
    [015] In a particular embodiment of the invention, the ultra-thin double-coated titanium dioxide has an internal inorganic silica coating and an organic external coating.
    [016] Such titanium dioxide nanoparticles can, for example, be prepared according to the process described in example 1 of EP-444798. The internal coating of the titanium dioxide particles with inorganic silica can be prepared, according to the current technique, as, for example, described in EP-44515, EP-98853, EP-1284277, EP-098853, and US-5562897 , JP-2000319128.
    [017] The titanium dioxide surface can be pre-treated before coating to further reduce surface activity. Such pretreatments are well known to a person skilled in the art and can be carried out, for example, with (a) fluoro acids selected from H2SiF6, H2TIFF, H2ZrF6, H2HfF6, H2GeF6, H2SnF6 and / or HBF4; (b) water-soluble carboxylic acid containing> 2 hydroxyl groups per carboxyl group in each mol acid (esp. glyconic acid); (c) water-soluble salts of such carboxylic acids; (d) source of phosphate ions, esp. H3PO4 and / or phosphate salts and / or organophosphoric acids and their salts; (e) inorganic acid, such as H2SO4, HNO3, H3PO4, boric, hydroiodic and / or perchloric acid (f) organic component (s) selected from tannins and / or amino-phenolic polymers; and (h) optional oxide, hydroxide.
    [018] Preferably, the inner coating layer consists of a minimum of 0.5% by weight of inorganic silica (based on titanium dioxide). Most preferably, the inner coating layer consists of 0.5% by weight to 50% by weight, preferably 1% by weight to 20% by weight of inorganic silica (based on titanium dioxide).
    [019] In another modality, titanium dioxide has a coating of internal alumina (aluminum oxide). The internal coating consists of a minimum 0.5% by weight of aluminum oxide (based on titanium dioxide). Preferably, the inner coating layer consists of 0.5% by weight to 50% by weight, more preferably 1% by weight to 20% by weight of aluminum oxide (based on titanium dioxide).
    [020] The outer coating is preferably selected from the class of organic coatings, such as silicone oils (eg, simethicone, methicone, dimethicone, polysilicone-15), alkyl silanes (eg, octyl tri (m) ethoxy silane) , olefinic acids (for example, stearic acid), or polyols (for example, glycerol) and can be applied to the titanium dioxide particle by methods known to a person skilled in the art, for example, described in F157124. Preferably, the outer coating is selected from the group consisting of simethicone, methicone, dimethicone, polysilicones-15, stearic acid and octyl trimethoxy silane. Most preferably, the outer coating is dimethicone. The amount of the outer coating layer is at least 0.25% by weight based on titanium dioxide. Preferably, the amount of outer coating is selected in the range of 0.5% by weight to 50% by weight, more preferably in the range of 0.5% by weight to 10% by weight based on titanium dioxide.
    [021] In all embodiments of the present invention, the ultra-thin double-coated titanium dioxide preferably has a content of titanium dioxide selected in the range of 70-95% by weight and a content of silicon dioxide selected in the range of 5 -20% by weight, such as preferably a content of titanium dioxide selected in the range of 80-90% by weight and a content of selected silicon dioxide in the range of 10 to 15% by weight, established that the total content of titanium dioxide and silicon dioxide are selected in the range of 90-100% by weight.
    [022] The particle size of titanium dioxide is not particularly limited. All particle sizes that are primarily useful for incorporation into sunscreen compositions can be used in topical compositions, in accordance with the present invention. However, in all embodiments of the invention, the primary particle size of titanium dioxide (that is, any TiCç w / o coating) is preferably selected in the range of 2 to 100 nm, most preferably in the range of 5 to 50 nm and the secondary particle size (i.e., TiO2 with double coating) is preferably selected in the range of 0.05 and 50 pm, preferably in the range of 0.1 and 1 pm.
    [023] The crystalline form of titanium dioxide can be of any crystal or amorphous type. For example, titanium dioxide can be any type of amorphous form, rutile, anastasis, brookite or mixtures thereof. Preferably, the crystalline form of titanium dioxide is rutile.
    [024] In particular, suitable titanium dioxide according to the present invention, contains a rutile-type titanium dioxide (TIO2) core with a double coating of silica (inner coating) and dimethicone (outer coating), and has a dioxide content of titanium selected in the range of 82-87% by weight and a content of silicon dioxide selected in the range of 10.5 to 14.5% by weight, which is commercially available as PARSOL® TX (INCI: titanium dioxide, silica , dimethicone) from DSM Nutritional Products Ltd.
    [025] Degrees of titanium dioxide with a suitable double coating featuring an internal alumina and an external stearic acid coating are, for example, commercially available as Tayca micro-titanium dioxide MT-01 or Ishihara TTO-55 (C) Sangyo Kaisha. A suitable double-coated titanium dioxide featuring an inner coating of alumina and an outer coating of simethicone, for example, commercially available as Eusolex-T-2000 from EMD chemicals Inc./Rona.
    [026] In a particular embodiment of the invention, zinc oxide has an ultrafine organic coating, such as dimethicone, octyl tri (m) ethoxy silane (also known as tri (m) ethoxyprilylsilane) or cross-linked dimethoxydiphenylsilanotrietoxicaprilylsilane.
    [027] Particularly suitable zinc oxides according to the present invention include Z-COTE HP1® (ZnO coating with triethoxycaprilylsilane) or Z-COTE MAX (ZnO coated with cross-linked dimethoxydiphenylsilanotrietoxicaprilylsilane polymer), which are commercially available from BASF . Alternatively, Zano 10 Plus® (ZnO coated with octyl triethoxy silane) can be used and is available from Umicore. Alternatively, ZinClear-IM ™, which has an average particle size> 1.0 microns and is hydrophobically modified can be used. It is available as a dispersion using common cosmetic emollients, such as C12-C1.5 alkyl benzoate or caprylic / capric triglycerides.
    [028] The particle size of zinc oxide is not particularly limited. All particle sizes that are primarily useful for incorporation into sunscreen compositions can be used in the topical compositions according to the present invention. However, in all embodiments of the invention, the coated zinc oxide particle size is preferably selected in the range of 10 to 200 nm.
    [029] In a particular embodiment, topical compositions according to the present invention comprise double-coated titanium dioxide metal or ultra-thin zinc oxide in the absence of any other ultra-thin metal oxide.
    [030] The term "topical" is understood in the present invention as an external use for keratinous substances, which are particularly the skin, scalp, eyelashes, eyebrows, nails, mucous membranes and hair, most preferably for application to the skin.
    [031] As the compositions of the present invention are for topical use, they comprise a physiologically acceptable medium, that is, a medium compatible with keratinous substances, such as skin, mucous membranes and fibers. In particular, the physiologically acceptable medium is a cosmetically acceptable vehicle.
    [032] The term cosmetically acceptable vehicle refers to all vehicles and / or excipients and / or diluents conventionally used in cosmetic compositions.
    [033] Topical compositions preferably according to the invention are skin care preparations, such as sunscreen preparations or functional preparations.
    [034] Examples of skin care preparations are, in particular, photoprotectors (sunscreens, skin care preparations), anti-aging preparations, preparations for the treatment of photoaging, body oils and lotions, treatment creams, skin protection ointments skin, facial powders, moisturizing gels, sprays (moisturizers), facial and / or body moisturizers, tanning preparations (ie, compositions for natural / artificial tanning and or darkening of human skin), as well as preparations of facial illuminators, as well as BB and CC creams.
    [035] Examples of functional preparations are cosmetic or pharmaceutical compositions containing active components, such as preparations of hormones, vitamins, plant extracts, anti-aging substances, and / or antimicrobial preparations (antibacterial or antifungal) without limitation.
    [036] In a particular embodiment, topical compositions, according to the invention, are skin care preparations, such as body milks, lotions, sprays, hydrodispersions, bases, creams, cream gels, serums, tonics or gels.
    [037] Topical compositions according to the present invention may be in the form of a suspension or dispersion in solvents or fatty substances, or alternatively in the form of an emulsion or microemulsion (in particular of the oil-in-water type (O / A) or water-in-oil (A / O), silicone-in-water (Si / A) or water-in-silicone (A / Si), PIT emulsion, multiple emulsion (for example, oil-in- water in oil (O / W / O) or water-in-oil in water (W / O / W), Pickering emulsion, hydrogel, alcoholic gel, lipogel, one-phase or multifaceted solution, or vesicular dispersion or other forms that can be applied with devices in the form of sticks, masks or as sprays.
    [038] In one embodiment, the topical compositions according to the present invention are advantageously in the form of an oil-in-water (O / W) emulsion comprising an oil phase dispersed in an aqueous phase in the presence of an O / emulsifier THE. The preparation of such O / W emulsions is well known to those skilled in the art.
    [039] If the topical composition according to the invention is an O / A emulsion, then it advantageously contains at least one O / A or Si / A emulsifier selected from the list of PEG-30 dipolyhydroxystearate, PEG dilaurate -4, PEG-8 dioleate, PEG-40 sorbitan peroleate, PEG-7 glyceryl cocoate, PEG-20 glyceride, hydrogenated PEG-25 castor oil, glyceryl stearate (e) PEG-100 stearate, PEG-7 olivate, PEG-8 oleate, PEG-8 laurate, PEG-60 almond glyceride, methyl glucose PEG-20 sesquistearate, PEG-40 stearate, PEG-100 stearate, PEG-80 laurate sorbitan, esteareth-2, esteareth-12, oleth-2, ceteth-2, laureth-4, oleth-10, oleth-10 / polyoxyl 10-oleyl ether, ceteth-10, isoesteareth-20, ceteareth-20, oleth- 20, esteareth-20, esteareth-21, ceteth-20, isoceteth-20, laureth-23, esteareth-100, glyceryl stearate citrate, glyceryl stearate (self-emulsifying), stearic acid, stearic acid, polyglyceryl-3- salts methylglycosediasterate . Suitable emulsifiers are phosphate esters and salts, such as cetyl phosphate (Amphisol® A), cetyl diethanolamine phosphate (Amphisol® DEA), potassium cetyl phosphate (Amphisol® K), sodium cetearyl sulfate, glycerol oleate phosphate sodium, hydrogenated vegetable glyceride phosphate and mixtures thereof. Suitable emulsifiers are sorbitan oleate, sorbitan sesquiolet, sorbitan isostearate, sorbitan trioleate, glycoside cetearyl, lauryl glycoside, decyl glycoside, sodium stearoyl glutamate, sucrose polystearate and hydrated polyisobutene. In addition, one or more synthetic polymers can be used as an emulsifier. For example, eicosene PVP copolymer, cross polymer of acrylate / C10-30 alkyl acrylates, methacrylate / esteareth-20 acrylates copolymer, PEG-22 / dodecyl glycol copolymer, PEG-45 / dodecyl glycol copolymer and mixtures thereof .
    [040] The O / A emulsifier, respectively Si / A is preferably used in an amount of 0.5 to 10% by weight, particularly in the range of 0.5 to 6% by weight, such as in the range of 0 , 5 to 5% by weight, as in the range of 1 to 4% by weight, based on the total weight of the composition.
    [041] Particularly suitable O / W emulsifiers according to the present invention include phosphate esters emulsifiers of formula (II)
    where R5, R6 and R7 can be hydrogen, an alkyl of 1 to 22 carbon atoms, preferably 12 to 18 carbon atoms; or an alkoxylated alkyl having 1 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and having 1 or more, preferably 2 to 25, more preferably 2 to 12 moles of ethylene oxide, established that at least one of R5, R6 and R7 is an alkyl or alkoxylated alkyl as defined above but having at least 6 alkyl carbon in said alkyl or alkoxylated alkyl group.
    [042] Monoesters where R5 and R6 are hydrogen and R7 is selected from alkyl groups of 10 to 18 carbons and alkoxylated fatty alcohols of 10 to 18 carbons and 2 to 12 moles of ethylene oxide are preferred. Among the phosphate ester emulsifiers preferably are C 6 -oyl alkyl phosphate, Co 15 alkyl phosphate, ceteareth-2 phosphate, ceteareth-5 phosphate, ceteth-8 phosphate, ceteth-10 phosphate, cetyl phosphate, phosphate pareth-4 Ce-io, C12-15 pareth-2 phosphate, C12-15 pareth-3 phosphate, DEA-ceteareth-2 phosphate, DEA-cetyl phosphate, DEA-Oleth-3 phosphate, potassium cetyl, deceth-4 phosphate, deceth-6 phosphate and trilaureth-4 phosphate.
    [043] A particular O / A emulsifier used in topical compositions according to the invention is cetyl potassium phosphate, for example, commercially available as Amphisol® K from DSM Nutritional Products Ltd Kaiseraugst.
    [044] Suitable O / W emulsifiers are polyethylene glycol (PEG) esters or diesters, such as, for example [INCI names] PEG-100 stearate, PEG-30 dipyrhydroxystearate, PEG-4 dilaurate, PEG-8 dioleate , PEG-40 sorbitan peroleate, PEG-7 glyceryl cocoate, PEG-20 almond glyceride, hydrogenated PEG-25 castor oil, PEG-7 olivate, PEG-8 oleate, PEG-8 laurate, glycerides almond PEG-60, PEG-20 methyl glucose sesquiestearate, PEG-40 stearate, PEG-100 stearate, PEG-80 sorbitan laurate.
    [045] Particularly preferably, according to the present invention is PEG-100 stearate sold under the trade name Arlacel ™ 165 (INCI glyceryl stearate (e) PEG-100 stearate) by Croda.
    [046] Another suitable class of O / A emulsifiers are non-ionic self-emulsifying systems derived from olive oil, for example, known as (INCI name) cetearyl olivate and sorbitan olivate (chemical composition: sorbitan ester and cetearyl ester of olive oil fatty acids) sold under the trade name CLIVEM 1000.
    [047] In a particular embodiment, the invention relates to topical compositions with all the definitions and preferences provided in the present invention in the form of O / W emulsions comprising an oil phase dispersed in an aqueous phase in the presence of an O / A emulsifier where the O / W emulsifier is selected from the group consisting of potassium cetyl phosphate, glyceryl stearate (e) PEG-100 stearate, cetearyl olivate and sorbitan olivate, as well as mixtures thereof.
    [048] In another particular embodiment, the invention relates to topical compositions in the form of A / O emulsions comprising an aqueous phase dispersed in an oil phase in the presence of an A / 0 emulsifier.
    [049] Suitable A / O emulsifiers include fatty acid polyglycerol esters or diesters also called polyglyceryl ester / diester (i.e., a polymer where fatty acid (s) is / are bonded by esterification with polyglycerin), such as, for example, commercially available from Evonik as Isolan GPS [INCI name diisostearate / polyhydroxystearate / polyglyceryl-4 sebacate (ie diester of a mixture of isostearic, polyhydroxystearic and sebaceic acids with polyglycerin-4)] or Dehymuls PGPH available from Cognis (INCI polyglyceryl-2 dipolehydroxystearate).
    [050] Particularly preferably, according to the present invention are A / O emulsions where the A / O emulsifier is polyglyceryl-2 dipolehydroxystearate.
    [051] Topical compositions according to the present invention advantageously contain at least one cosurfactant, such as, for example, selected from the group of mono- and diglycerides and / or fatty acids. The cosurfactant is generally used in an amount selected in the range of 0.1 to 10% by weight, such as in the range of 0.5 to 5% by weight, as well as in the range of 1 to 3% by weight, based on weight total composition. Particularly suitable cosurfactants are selected from the list of alkyl alcohols, such as cetyl alcohol (Lorol C16, Lanette 16), cetearyl alcohol (Lanette O), stearyl alcohol (Lanette 18), beenyl alcohol (Lanette 22), glyceryl stearate, myristate glycerol (Stall 3650), hydrogenated coco-glycerides (Lipocire NalO) as well as their mixtures.
    [052] Topical compositions in the form of O / W or W / O, according to the invention, can be provided, for example, in the form of serum, milk, emulsion spray, lotion or cream, and are prepared according to with common methods. The compositions of the invention are for topical application and can in particular be dermatological or cosmetic compositions, for example, for protection of human skin against adverse effects of UV radiation (anti-wrinkle, anti-aging, hydration, sun protection and the like).
    [053] According to an advantageous embodiment of the invention, topical compositions constitute a cosmetic composition and are for topical application to the skin.
    [054] The topical cosmetic compositions of the invention may also contain common auxiliaries, additives, vehicles, excipients or diluents conventionally used in cosmetic compositions, such as preservatives / antioxidants, oils / fatty substances, water, organic solvents, silicones, thickeners, softeners, emulsifiers, antifoaming agents, aesthetic components, such as fragrances, surfactants, fillers, chelating and / or sequestering agents, anionic, cationic, nonionic or amphoteric polymers or their mixtures, propellants, acidifying or basifying agents, dyes, abrasives, absorbents, oils essentials, sensory modifiers, astringents, or any other components generally formulated in such compositions. Such cosmetic components commonly used in the skin care industry, which are suitable for use in the compositions of the present invention, are, for example, described in International Cosmetic Ingredient Dictionary & Handbook by Personal Care Product Council (http: //www.personalcarecouncil. org /) accessible via INFO BASE online (http://online.persona1carecouncil.org/jsp/Home.j sp), without limitation.
    [055] According to the present invention, topical compositions can also comprise cosmetically active components, such as skin brightening agents; agents for preventing skin darkening; agents for the treatment of hyperpigmentation; agents for preventing or reducing acne, wrinkles, lines, atrophy and / or inflammation; anti-cellulite and slimming agents (eg phthanic acid), firming, moisturizing and energizing agents, self-tanning agents, soothing agents, as well as agents to improve skin elasticity and barrier and / or other UV-filter substances, as well as others pigments or nanopigments, for example, those suitable to provide a photoprotective effect by physical blocking of ultraviolet radiation. The required amounts of such skin protection agents, based on the desired product, can be easily determined by experts in the field. Additional components can be added to the oil phase, the aqueous phase or separately as appropriate. The form of action can easily be adapted by a specialist in the field.
    [056] The cosmetically active components useful in the present invention may in some instances provide more than one benefit or operate through more than one form of action.
    [057] Preferably, topical compositions according to the invention comprise UV-filter substances which are preferably selected from broad-spectrum UV-filter substances and / or UVA and / or UVB known to be added in compositions topical products such as cosmetic or dermatological sunscreen products. Such UV-filter substances comprise all groups that absorb light in the wavelength range from 400 nm to 320 nm (UVA) and 320 nm to 280 nm (UVB) or even shorter wavelengths (UVC) and which are either can be used as cosmetically acceptable UV-filter substances. Such UV filter substances are, for example, listed in the International Cosmetic Ingredient Dictionary & Handbook by Personal Care Product Council (http://www.personalcarecouncil.org/) accessible through INFO BASE online (http://online.personalcarecouncil.org/ jsp / Home.jsp), without limitation.
    [058] Suitable UV-filter substances can be organic or inorganic compounds. Examples of organic UV-filter substances include, for example, acrylates, such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene, PARSOL® 340 from DSM Nutritional Products Ltd.), 2-cyano-3, Ethyl 3-diphenylacrylate; camphor derivatives, such as, for example, 4-methyl benzylidene camphor (PARSOL® 5000 from DSM Nutritional Products Ltd.), 3-benzylidene camphor, camphor benzalkonium methosulfate, camphor polyacrylamidomethyl, camphor sulfur, benzyl acid, sulphomyl sulfonic dicaphorph terephthalene (Mexoryl® SX); cinnamate derivatives, such as, for example, ethylhexyl methoxycinnamate (PARSOL® MCX from DSM Nutritional Products, Ltd.), ethoxyethyl methoxycinnamate, isoamyl methoxycinnamate, as well as siloxane-linked cinnamic acid derivatives; derivatives of p-aminobenzoic acid, such as, for example, p-aminobenzoic acid, 2-ethylhexyl p-dimethylaminobenzoate. Ethyl-oxypropylenated p-aminobenzoate, glyceryl p-aminobenzoate; benzophenones, such as, for example, benzophenone-3, benzophenone-4, 2,2 ', 4,4'-tetrahydroxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; benzalmalonic acid esters, such as, for example, di- (2-ethylexyl) 4-methoxybenzalmalonate; organosiloxane compounds with chromophore groups, such as, for example, polysilicones-15 (PARSOL® SLX from DSM Nutritional Products Ltd), drometrizole trisiloxane (Mexoryl® XL); salicylate derivatives, such as, for example, isopropylbenzyl salicylate, benzyl salicylate, butyl salicylate, ethylhexyl salicylate (PARSOL® EHS from DSM Nutritional Products Ltd.), isooctyl salicylate or homomentyl salicylate (homosalate, PAR® HOL DSM Nutritional Products Ltd.); triazine derivatives, such as, for example, ethylhexyl triazone (Uvinul® T-150 from BASF), diethylhexyl butamido triazone (Uvasorb® HEB), bis-ethylexyloxyphenol methoxyphenyl triazine (Tinosorb® S) and tris-biphenyl triazine (nano) BASF Tinosorb® A2B); benzotriazole derivatives, such as, for example, 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) - 4- (1,1,3,3-tetramethylbutyl) -phenol (Tinosorb® BASF M); encapsulated UV-filters, such as, for example, encapsulated ethylhexyl methoxycinnamate (Eusolex® pearl-UV from EMD Chemicals Inc) or microcapsules loaded with UV-filters as, for example, described in EP 1471995; dibenzoylmethane derivatives , such as, for example, 4-tert-butyl-4'-methoxydibenzoylmethane (PARSOL® 1789 from DSM Nutritional Products Ltd), dimethoxydibenzoylmethane, isopropylbenzoylmethane; substituted amino hydroxybenzophenones, such as, for example, 2- (4-diethylamino-2-hydroxy-benzoyl) benzoic (aminobenzophenone, Uvinul® A Plus from BASF); benzoxazole derivatives, such as, for example, 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2- il- (4-phenyl) -imino] -6- (2-ethylexyl) -imino-1,3,5-triazine (Uvasorb® K2A from 3V);
    [059] To improve the photostability of sunscreen products, it may be desirable to add a photostabilizer. Examples of photo-stabilizers known to experts in the field include, for example, 3,3-diphenylacrylate derivatives, such as octocrylene (PARSON® 340 from DSM Nutritional Products Ltd) or polyester-8 (Polycrylene® from HallStar); benzylidene camphor derivatives, such as 4-methyl benzylidene camphor PARSON® 5000 from DSM Nutritional Products Ltd); dialkyl naphthalates, such as diethylhexyl naphthalate (Symrise's Corapan® TQ) without limitation. An overview of other stabilizers is, for example, provided in "SPF Boosters & Photostability of Ultraviolet Filters"; HAPPI, October 2007, p 77-83, which is included in the present invention as a reference. Photostabilizers are generally used in an amount of 0.05 to 10% by weight with respect to the total weight of the topical composition.
    [060] Generally, the amount of each UV-filter substance in the topical compositions according to the invention is selected in the range of about 0.1 to 10% by weight, preferably in the range of about 0.2 to 7% by weight, and more preferably in the range of about 0.5 to 5% by weight with respect to the total weight of the topical composition.
    [061] The total amount of the UVA filter substance (s), in particular butyl methoxydibenzoylmethane, in the topical compositions according to the invention is preferably selected from the range of about 0.5 to by weight, such as, for example, in the range of 2 to 8% by weight particularly in the range of about 1 to 6% by weight, such as, for example, in the range of 2.5 to 6% by weight, and even more preferably in the range of about 3 to 5% by weight with respect to the total weight of the topical composition.
    [062] The total amount of UV-filter substances in the topical compositions according to the invention is preferably in the range of about 1 to 40% by weight, preferably in the range of about 5 to 30% by weight particularly in the range of 12 to 30% by weight, such as, for example, in the range of 20 to 30% by weight with respect to the total weight of the topical composition.
    [063] The UVB-filter substances used in topical compositions, according to the invention, include octocrylene, ethylhexyl methoxycinnamate, hexylsalicylate and / or ethyl homosalate.
    [064] Broad spectrum UV-filter substances used in topical compositions according to the invention cover asymmetric s-triazine derivatives, such as 2,4-bis - {[4- (2-ethylhexyloxy) -2- hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, certain benzophenones, such as 2-hydroxy-4-methoxy-benzophenone and / or 2,2'-methylene-bis- (6 - (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl-butyl) -phenol).
    [065] The substance of the UVA filter preferably used in the topical compositions according to the invention is butyl methoxydibenzoylmethane.
    [066] In a particular preferred embodiment, the present invention relates to topical compositions comprising at least one additional UV filter selected from the group of butyl methoxydibenzoylmethane, octocrylene, homosalate, 2-phenylbenzimidazole sulfonic acid or ethylhexyl salicylate, as well as their mixtures. In this case, if the amount of titanium dioxide with ultrafine double coating is selected in the range of 2-5% by weight, the amount of butyl methoxydibenzoylmethane is selected in the range of 3-5% by weight, the amount of octocrylene is selected in the range of 6-15% by weight, the amount of homosalate is selected in the range of 2-13% by weight, the amount of 2-phenylbenzimidazole sulfonic acid is selected in the range of 0.5-2% by weight, and the The amount of ethylhexyl salicylate is selected in the range of 2-8% by weight, with respect to the total weight of the topical composition. In these compositions, the amount of silica spheres is preferably selected in the range of 2 to 4% by weight, based on the total weight of the composition.
    [067] Topical compositions particularly preferably are those which comprise only ultra-thin double-coated titanium dioxide, butyl methoxydibenzoylmethane, octocrylene, homosalate, 2-phenylbenzimidazole sulfonic acid or titanium dioxide, butyl methoxybenzylmethane, octocrylene, homosalate as UV filters and ethylhexyl salicylate, and more preferably in the quantities indicated in the previous paragraph.
    [068] In another particularly preferred embodiment, the present invention relates to topical compositions comprising as UV-filters only zinc oxide with an ultra-thin coating and ethylhexyl methoxycinnamate. In this case, if the emulsifier is polyglyceryl-2-dipolehydroxystearate, and the amount of zinc oxide with ultra-thin coating is selected in the range of 5-15% by weight, and the amount of ethylhexyl methoxycinnamate is selected in the range of 5-12 % by weight, it is preferably that the amount of zinc oxide with ultrafine coating is selected in the range of 8-12% by weight, and the amount of ethylhexyl methoxycinnamate is selected in the range of 6-10% by weight, with respect to to the total weight of the topical composition. In these compositions, the amount of silica beads is also preferably selected in the range of 2-4% by weight, based on the total weight of the composition.
    [069] The required quantities of cosmetic, dermatological and additive aids can, based on the desired product, be easily chosen by experts in the field, and will be illustrated in the examples, without limitation.
    [070] It is clear that a person skilled in the art will carefully select the compound or additional compounds mentioned above and / or their quantities so that the advantageous properties intrinsically associated with the combination according to the invention are not adversely affected by the addition or additions considered.
    [071] Topical compositions according to the invention generally have a pH in the range of 3 to 10, preferably in the range of 4 to 8 and even more preferably in the range of 4 to 7.5. The pH can easily be adjusted as desired with suitable acids, such as citric acid or bases, such as sodium hydroxide (eg, as an aqueous solution), triethanolamine (TEA Care), tromethamine (Trizma Base) and aminomethyl propanol (AMP- Ultra PC 2000), according to standard methods in the field.
    [072] The amount of topical composition to be applied to the skin is not critical and can easily be adjusted by an expert in the field. Preferably, the amount is selected in the range of 0.1 to 3 mg / cm2 of skin, as preferably in the range of 0.1 to 2 mg / cm2 of skin and even more preferably in the range of 0.5 to 2 mg / cm2 of skin.
    [073] The following examples are provided to illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.
    [074] The term "control", as used in the experimental part, refers to formulations without a bleaching reducing agent, that is, without any silica sphere.
    [075] The term "reference (Ref)", as used in the experimental part, refers to formulations with silica spheres that are not in accordance with the invention (coated silica spheres).
    [076] The term "invention (Inv)", as used in the experimental part, refers to formulations with silica spheres that are not in accordance with the invention (coated silica spheres). Example 1: Table 1: Formulation

    Sensory evaluation
    [077] The samples were prepared as described in table 1 and tested in a blind study with a sensory panel consisting of at least 8 people (preferably 12) with the following conditions:
    [078] The evaluation was performed on the inside of the forearm; the panel leader applies 50 pL of the respective sample. The evaluator spreads the product inside a defined circle with a diameter of 5 cm using the index or middle finger, with circular movements, at a rate of 2 revolutions / second. After 12 rubs, the phase continues until a resistance signals the end of this phase. After this point, the immediate whitening and after 20 minutes are evaluated. The bleaching was quantified on a scale from 0 to 100 in comparison with well-defined and defined whitening intensity patterns. Table 2: Results of the whitening assessment

    [079] As can be seen from the results in Table 2, only the uncoated silica spheres showed a significantly reduced total lightening. Example 2: Table 3: Formulation


    Sensory evaluation
    [080] The samples were prepared as described in table 3 and tested in a blind study with a sensory panel consisting of at least 8 people (preferably 12) with the following conditions:
    [081] The evaluation was performed on the inside of the forearm; the panel leader applies 50 pL of the respective sample. The evaluator spreads the product within a defined circle with a diameter of 5 cm using the index or middle finger, with circular movements, at a rate of 2 revolutions / second. After 12 rubs, the phase continues until a resistance signals the end of this phase. After this point, immediate lightening is evaluated. The bleaching was quantified on a scale from 0 to 100 in comparison with well-defined and defined whitening intensity patterns. Table 4: Results of the whitening assessment


    [082] As can be seen from the results in Table 4, only the uncoated silica spheres showed a significantly reduced bleaching. Example 3 Table 5: formulation

    Sensory evaluation
    [083] The samples were prepared as described in table 5 and tested in a blind study with a sensory panel with 5 people with the following conditions:
    [084] The evaluation was performed on the inside of the forearm; the panel leader applies 75 pL of the respective sample. The evaluator spreads the product within a defined circle with a diameter of 5 cm using the index or middle finger, with circular movements, at a rate of 2 revolutions / second. After 12 rubs, the phase continues until a resistance signals the end of this phase. After this point, immediate lightening is evaluated. The bleaching was quantified on a scale from 0 to 100 in comparison with well-defined and defined whitening intensity patterns. Table 6: Results of the whitening assessment
    权利要求:
    Claims (11)
    [0001]
    1. Topical compositions comprising (1) highly porous, uncoated silica spheres, having a DvO particle size greater than 0.3 pm, a DvlOO less than 35 pm, a Dv50 selected in the range 8 to 15 pm, determined with a Coulter LS13320 or a Malvern Mastersizer 2000, and an oil absorption capacity selected in the range of 1.2-2.5 cc / g and (2) an ultra-thin double-coated titanium dioxide, CHARACTERIZED by the fact that dioxide double-coated titanium is rutile and has an internal silica coating and an external dimethicone coating.
    [0002]
    2. Topical composition, according to claim 1, CHARACTERIZED by the fact that the quantity of the silica spheres is selected in the range of 0.1-5% by weight, based on the total weight of the cosmetic composition.
    [0003]
    3. Topical composition according to claim 1 or 2, CHARACTERIZED by the fact that the oil absorption capacity of the silica spheres is selected in the range of 1.3 to 1.8 cc / g.
    [0004]
    4. Topical composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that the amount of titanium dioxide with ultra-thin double coating is selected in the range of 0.5 to 15% by weight.
    [0005]
    Topical composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that the primary particle size (any w / o coating) of titanium dioxide is selected in the range of 2 to 100 nm, and the size of the secondary particle (with double coating) is selected in the range of 0.05 and 50 pm.
    [0006]
    6. Topical composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that the primary particle size of titanium dioxide is selected in the range of 5 to 50 nm, and the secondary particle size is selected in the range from 0.1 to 1 pm.
    [0007]
    Topical composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that the composition also comprises at least one additional UV filter selected from the group of butyl methoxydibenzoylmethane, octocrylene, homosalate, 2-phenylbenzimidazole acid sulfonic acid, ethylhexyl methoxycinnamate and ethylhexyl salicylate, as well as their mixtures.
    [0008]
    8. Topical composition according to any one of claims 1 to 7, characterized by the fact that the topical composition is in the form of an oil-in-water (O / W) emulsion, comprising an oil phase dispersed in an aqueous phase in the presence of an O / W emulsifier or an W / O emulsion comprising an aqueous phase dispersed in an oil phase in the presence of an A / O emulsifier.
    [0009]
    9. Topical composition according to claim 8, CHARACTERIZED by the fact that the O / A emulsifier is potassium cetyl phosphate, and the A / O emulsifier is polyglyceryl-2 dipyrhydroxystearate.
    [0010]
    10. Use of highly porous, uncoated silica spheres, having a DvO particle size greater than 0.3 pm, a DvlOO less than 35 pm, a Dv50 selected in the range 8 to 15 pm, determined with a Coulter LS13320 or a Malvern Mastersizer 2000, and an oil absorption capacity selected in the range of 1.2-2.5 cc / g to reduce the bleaching effect of an ultra-thin double-coated titanium dioxide in a topical composition CHARACTERIZED by the fact that that the double-coated titanium dioxide is rutile and has an internal silica coating and an external dimethicone coating.
    [0011]
    11. Method for reducing the bleaching effect of an ultra-thin double-coated titanium dioxide CHARACTERIZED by the fact that the ultra-thin double-coated titanium dioxide is of the rutile type and has an internal silica coating and an external dimethicone coating in a composition topical, said method comprising the step of adding to the topical composition of uncoated silica spheres, having a DvO particle size greater than 0.3 pm, a Dv100 less than 35 pm, a Dv50 selected in the range of 8 to 15 pm, determined with a Coulter LS13320 or Malvern Mastersizer 2000, and an oil absorption capacity selected in the range of 1.2-2.5 cc / g, evaluating the effect.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP3265111B2|1994-02-16|2002-03-11|ポーラ化成工業株式会社|UV protective cosmetics|
    JP2943056B2|1994-12-30|1999-08-30|ミキアメリカインコーポレイテド|Granular composite material, its production method and cosmetics containing the granular composite material|
    FR2746302B1|1996-03-20|1998-12-24|Oreal|COSMETIC COMPOSITIONS COMPRISING NANOPIGMENTS|
    WO1998047476A1|1997-04-18|1998-10-29|Showa Denko K.K.|Cosmetic preparation, silica-coated metal oxide powder, and process for producing the same|
    JP2002154915A|2000-09-11|2002-05-28|Showa Denko Kk|Cosmetic|
    US20030219391A1|2002-02-28|2003-11-27|L'oreal|Dispersed powders providing ultraviolet light protection, suitable for use in cosmetic compositions|
    US20060045890A1|2004-08-27|2006-03-02|Gonzalez Anthony D|Topical skin care compositions|
    JP2009518329A|2005-12-09|2009-05-07|ディーエスエムアイピーアセッツビー．ブイ．|Novel cosmetic or dermatological composition comprising modified titanium dioxide particles|
    JP2007320916A|2006-06-01|2007-12-13|Shiseido Co Ltd|Sunscreen cosmetic|
    US20090018200A1|2007-07-12|2009-01-15|L'oreal|Composition containing a phenanthrenol|
    JP5631530B2|2007-12-07|2014-11-26|日揮触媒化成株式会社|Porous silica-based particles having surface smoothness, a method for producing the same, and a cosmetic comprising the porous silica-based particles|
    JP5532648B2|2008-04-03|2014-06-25|信越化学工業株式会社|Powder surface-treated with carboxyl group-containing organopolysiloxane, dispersion of the powder, and cosmetic comprising the powder|
    JP2010100580A|2008-10-24|2010-05-06|Kose Corp|Water-based makeup cosmetic|
    EP2501438B1|2009-11-18|2018-03-28|DSM IP Assets B.V.|Topical compositions|
    BR112013031107A2|2011-06-08|2016-09-06|Dsm Ip Assets Bv|sunscreens|DE102015223260A1|2015-11-25|2017-06-01|Beiersdorf Ag|Titanium dioxide-containing sunscreen|
    DE102015223261A1|2015-11-25|2017-06-01|Beiersdorf Ag|Sunscreen containing titanium dioxide|
    WO2017102588A1|2015-12-16|2017-06-22|Dsm Ip Assets B.V.|Novel use|
    JP6682950B2|2016-01-29|2020-04-15|住友大阪セメント株式会社|Surface treated zinc oxide particles, dispersion, cosmetics and zinc oxide particles|
    WO2017130632A1|2016-01-29|2017-08-03|住友大阪セメント株式会社|Surface-treated zinc oxide particles, dispersion liquid, cosmetic, and zinc oxide particles|
    EP3474817A1|2016-06-27|2019-05-01|DSM IP Assets B.V.|Compositions comprising micropigments|
    TWI733910B|2016-09-30|2021-07-21|南韓商愛茉莉太平洋股份有限公司|Makeup cosmetic composition containing a capsule comprising a dye|
    EP3520767A4|2016-09-30|2020-05-13|Amorepacific Corporation|Capsules comprising pigments, and method for producing same|
    JP2019534257A|2016-10-11|2019-11-28|ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ．|Cosmetic composition|
    KR102099209B1|2016-11-11|2020-04-10|한국콜마주식회사|Method for manufacturing stick-type cosmetic composition|
    CN106580758B|2016-12-16|2019-09-27|广州市科能化妆品科研有限公司|A kind of oil-control water-setting cream and preparation method thereof|
    JP6922529B2|2017-08-01|2021-08-18|住友大阪セメント株式会社|Surface treatment method for producing zinc oxide particles|
    CN108524309B|2018-07-17|2021-04-09|如薇化妆品有限公司|Sunscreen cosmetic with water resistance and preparation method thereof|
    EP3937883A1|2019-03-12|2022-01-19|Basf Se|Sunscreen compositions containing porous metal oxide spheres|
    DE102019217883A1|2019-11-20|2021-05-20|Beiersdorf Ag|Sunscreen containing silica to protect against blue light|
    DE102019217885A1|2019-11-20|2021-05-20|Beiersdorf Ag|New, silica-containing sunscreen to protect against blue light|
    DE102020206056A1|2020-05-13|2021-11-18|Beiersdorf Aktiengesellschaft|Sunscreen with low stickiness and high UV protection|
    法律状态:
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-02| B09A| Decision: intention to grant|
    2020-06-02| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: A61K 8/25 , A61K 8/29 , A61Q 17/04 , A61K 8/02 , A61K 8/27 Ipc: A61K 8/02 (2006.01), A61K 8/25 (2006.01), A61K 8/2 |
    2020-08-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13186725|2013-09-30|
    EP13186729.3|2013-09-30|
    EP13186729|2013-09-30|
    EP13186725.1|2013-09-30|
    PCT/EP2014/070561|WO2015044306A1|2013-09-30|2014-09-25|Topical sun screen compositions titanium dioxide and silica|
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