CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to United States Patent Application Serial No. 62/438,698, filed on December 23, 2016. The entirety of the aforementioned application is incorporated herein in its entirety by reference.

FIELD OF INVENTION

[0001] The present invention relates to topical compositions comprising active ingredients which readily decompose on contact with air and/or water and an amount of a surface modified particulate sufficient to retard that decomposition are disclosed. Methods of stabilizing topical compositions comprising these active ingredients are also disclosed.

BACKGROUND OF INVENTION

[0002] The application of various active ingredients to the skin can provide many benefits to skin health. For example, various active ingredients may help prevent radical-induced damage and/or increase collagen production. These active ingredients are often reactive and undergo various reactive processes which degrade topical utility of the ingredient over time. For example, ascorbic acid provides antioxidant protection, prevents photo-aging, and stimulates collagen production but routinely reacts with various components in an environment (e.g. , oxygen, photons, water). These reactions convert the active ascorbic acid to a non-active reaction product of ascorbic acid. Typically, the formation of this non-active reaction product of ascorbic acid results in a color change of the resultant composition to a more brown or orange color.

[0003] Numerous approaches to achieving stable formulations comprising active ingredients have been attempted. For example formulations may be anhydrous to prevent reactivity with water, placed in air tight and/or opaque packaging to prevent reactivity with air and light, addition of various carriers and buffers to stabilize actives and the pH of compositions, and derivatization of the actives (e.g. , esterification). However, these methods generally are inadequate to prevent degradation of actives for long term storage, for example, for a period of one year at room temperature. As the stability of these actives is generally decreased as humidity and temperature are increased, these methods provide even less stability in these environments. Moreover, derivatization, while assisting in preventing degradation of certain actives, also may result in decreased activity and give rise to other forms of degradation (e.g. , hydrolysis).

SUMMARY

[0004] It is therefore an object of the present invention to provide methods of producing compositions with enhanced stability of certain active ingredients. It is also an object to provide compositions with enhanced or increased stability of various active ingredients.

[0005] It has surprisingly been found that the addition of surface modified particulates to compositions comprising certain active ingredients increases the stability of those active ingredients. Without wishing to be bound by theory, it is believed that the use of surface modified particulates prevents the absorption of various materials from an environment into a composition thereby preventing the active ingredient from decomposing due to interaction with those components. The addition of surface modified particulates to a composition comprising an active ingredient which readily decomposes upon interaction (e.g. reaction, etc.) with components typically found in environments (e.g. , water, oxygen, etc.) may prevent the decomposition of that active ingredient. An active ingredient which readily decomposes will be characterized by a decomposition rate such that less than 95% of the initial concentration (i.e. , on first opening of the container) of the active ingredient remains after four weeks under normal usage conditions (e.g., at least once daily opening of the container). For example, if an active ingredient readily decomposes in water such that 70% of the initial concentration of the active ingredient remains after four weeks of normal use, adding surface modified particulates to a composition may reduce the decomposition rate of that active ingredient such that greater than 95% of the active ingredient will remain after four weeks. Decomposition may occur through one or more chemical reactions including oxidation, hydrolysis, reduction, photoexcitation, etc.

[0006] Various active ingredients are known to undergo a color shift following decomposition ("color shifting active ingredients"). Ascorbic acid is an example of a color shifting active ingredient which undergoes a brownish or yellowish color shift upon decomposition. A shift in color may be used to measure the amount of decomposition which occurs for these actives. In some embodiments, surface modified particulates are present in an amount such that said composition is characterized by reduction in color shift of more than about 70% (e.g., about 80%, about 90%, about 95%, about 99%) when stored at about 35°C and about 90% relative humidity for about four weeks as compared to an otherwise identical composition not comprising said surface modified particulates after four weeks of said storage.

[0007] Topical compositions are provided comprising one or more active ingredients which readily decomposes on contact with air and/or water and an amount of a surface modified particulate sufficient to retard decomposition of said active ingredient. In some embodiments, an active ingredient may readily oxidize on contact with air and/or water. In some embodiments, the active ingredient is an organic compound or polymer. In some embodiments, the active ingredient is an antioxidant. In some embodiments, the active ingredient is ascorbic acid or any derivatives thereof. In some embodiments, the active ingredient may be present in an amount of from about 0.1 % to about 20% (e.g. , about 0.1 % to about 15%, about 1 % to about 15%, about 1% to about 10%, about 0.1% to about 10%, etc.) by weight. In an embodiment the active ingredient may be present in an amount of from about 1% to about 10%. In an embodiment the active ingredient may be present in an amount of from about 4% to about 6%.

[0008] The surface modified particulates may be present in an amount sufficient to retard the decomposition of the one or more active ingredients in the composition. In some embodiments, the surface modified particulates are hydrophobically surface modified particles. In some embodiments, the surface modified particles are particulates of silica, alumina, titania, talc and/or diatomaceous earth (DE). In some embodiments, the surface modified particles are particulates of silica, alumina, titania and/or diatomaceous earth (DE). In some embodiments, the surface modified particles are particulates of silica and/or diatomaceous earth (DE). In some embodiments, the surface modified particles are particulates of diatomaceous earth (DE). In some embodiments, the surface modified particulates may be modified with alkyl chains and/or fluoroalkyl chains and/or perfluoroalkyl chains. In some embodiments, the surface modified particulates may be present in an amount from about 0.1% to about 20% (e.g. , about 0.1% to about 15%, about 1% to about 15%, about 1% to about 10%, about 0.1% to about 10%, etc.) by weight. In an embodiment the surface modified particulates may be present in an amount of from about 4% to about 15%. The ratio of said active ingredient component to said surface modified particulates may be about 1 : 10 to about 10: 1 (e.g., about 1 :5 to about 5: 1, about 1 :3 to about 3: 1, etc.) by weight. In an embodiment the ratio of said active ingredient component to said surface modified particulates is 10: 1. In a further embodiment the ratio of said active ingredient component to said surface modified particulates is 2: 1. In a further embodiment said active ingredient component to said surface modified particulates is 1 : 1.

[0009] In some embodiments, the topical compositions may be in the form of an emulsion where each phase is independently selected from water, oil, silicone, or polyol. In some embodiments, topical composition may be in the form of a foundation, primer, base, cream, gel, or blush. In some embodiments, the topical compositions may further comprise a rheology modifier. In some embodiments, the rheology modifier may be a clay. In some embodiments, the composition may be anhydrous or substantially anhydrous. In a preferred embodiment, the composition is anhydrous. In some embodiments, the topical composition may comprise from about 0.1% to about 25% surface modified particulates by weight, and from about 0.1% to about 20% ascorbic acid by weight in an anhydrous carrier. In some embodiments, the topical composition may comprise from about 1% to about 20% surface modified particulates by weight, and from about 1% to about 10% ascorbic acid by weight in an anhydrous carrier. In some embodiments, the topical composition may comprise from about 1% to about 10% surface modified particulates by weight, and from about 1% to about 10% ascorbic acid by weight in an anhydrous carrier. In some embodiments, the topical composition may comprise from about 4% to about 15% surface modified particulates by weight, and from about 4% to about 6% ascorbic acid by weight in an anhydrous carrier. In some embodiments, the topical composition comprises humectants or water-soluble components (e.g., water-soluble polymers) in an amount less than about 0.1% by weight. In some embodiments, the topical compositions do not comprise humectants or water-soluble components.

[00010] The topical compositions may be characterized by a reduced decomposition rate of any active ingredient included therein. In some embodiments, the surface modified particulate is present in amount to retard the rate of decomposition of said active ingredient by at least about 1% (e.g. , at least about 5%, at least about 10%, at least about 20%, at least about 40%, etc.).

[00011] Methods are also provided for stabilizing compositions comprising active ingredients known to decompose readily. In some embodiments, a method of stabilizing a composition may comprise incorporating an amount of surface modified particulate sufficient to retard oxidation of an active ingredient into a composition. In some embodiments, the surface modified particulates are mixed under high shear before incorporation. In some embodiments, the surface modified particulates are mixed under high shear during incorporation. In some embodiments, the surface modified particulates are mixed under high shear after incorporation. In some embodiments a method for increasing the shelf-life of compositions is provided comprising adding an amount of surface modified particulate sufficient to increase the shelf life by at least about 5% (e.g. , about 10%, about 20%, etc.).

BRIEF DESCRIPTION OF FIGURES

[00012] Fig. 1 shows the changes in each CIELAB color coordinate of compositions comprising 10% ascorbic acid as related to differences in the weight percentages of surface modified particulates in those compositions after four weeks under high humidity and temperature conditions.

DETAILED DESCRIPTION

[00013] Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the invention is intended to be illustrative, and not restrictive. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.

[00014] All percentages given herein refer to the weight percentages of a particular component relative to the entire composition, including the vehicle, unless otherwise indicated. It will be understood that the sum of all weight % of individual components within a composition will not exceed 100%.

[00015] All terms used herein are intended to have their ordinary meaning unless otherwise provided. The phrase physiologically acceptable" is used interchangeably with "cosmetically acceptable," "topically acceptable" and "dermatologically acceptable" and is intended to mean that a particular component is generally regarding as safe and non-toxic for application to a human integument (e.g. , skin) at the levels employed. [00016] The term "alkyl" refers to a saturated hydrocarbon chain that may be a straight chain or branched chain, containing the indicated number of carbon atoms. For example, Ci-C ₆ alkyl indicates that the group may have from 1 to 6 (inclusive) carbon atoms in it. Any atom can be optionally substituted, e.g., by one or more substituents. Examples of alkyl groups include without limitation methyl, ethyl, ^-propyl, wopropyl, fert-butyl, pentyl and hexyl. The term "fluoroalkyl" refers to alkyl hydrocarbon chains with one or more hydrogen atoms substituted with fluorine. The term "perfluoroalkyl" refers to alkyl chains in which all hydrogen atoms are substituted with fluorine atoms. As used herein, the term "siloxane" refers to compounds having silicon atoms bonded to oxygen atoms (Si-O) and so arranged that each silicon atom is linked to at least one oxygen atom.

[00017] "Anhydrous" as used herein means no water has been intentionally added to the composition or to any of the component and that only that amount of water absorbed from the atmosphere or environment will be present in the composition. "Substantially anhydrous" as used herein means containing less than 5% water by weight. In other embodiments, the compositions will comprise less than about 2.5% water by weight or less than about 1% water by weight or less than 0.5% water by weight. The term anhydrous as used herein means that no water is added to the composition and that only that amount of water absorbed from the atmosphere will be present in the composition.

[00018] "About" as used herein when referring to a measurable value such as an amount, a color change, a decomposition rate, etc., is meant indicate an approximate measured value. In some embodiments, "about" to encompasses variations of ±20% or ±10% or ±5% or ±1% or 0.1% of the measured quantity (e.g. about 10% by weight may mean 10±2 % by weight).

[00019] As used herein, the term "color change" includes any visible change in a color attribute, including without limitation, a change in hue, saturation, and/or brightness, as well as complete, substantial, or partial restoration of an original color. As used herein, a "perceptible color change" is a change in color of less than 5 (e.g. , less than 2, less than 1, etc.) on the CIELAB coordinate system.

[00020] The term "prevent," as used herein, includes delaying or slowing the onset of or progression of a particular sign of skin aging. [00021] The phrase "individual in need thereof refers to a human that could benefit from improved dermal appearance or health, including males or females. In some embodiments, the individual in need thereof is a female.

[00022] The term "retard" in relation to decomposition refers to the lowering of the rate of decomposition. Measurement of the rate of decomposition may be performed by measuring the concentration of an active ingredient after four weeks of normal use or in the environmental conditions of Example 1 or 2. The decomposition is retarded if after four weeks the concentration of active ingredient is greater than an otherwise identical composition that does not comprise a decomposition retardant (i.e. surface modified particulates).

[00023] The term "skin" includes, without limitation, the lips, skin of the face, hands, arms, neck, scalp, and chest.

[00024] The term "stabilized" or "stability" as used herein defines the extent to which a composition retains throughout its period of storage and use (e.g. shelf-life), the same concentration of active ingredient that it possesses at the time of first use. Stability may also refer to the extent to which a product retains its physical characteristics (e.g. color).

[00025] As used herein, the term "consisting essentially of is intended to limit the invention to the specified materials or steps and those that do not materially affect the basic and novel characteristics of the claimed invention, as understood from a reading of this specification.

[00026] The invention is partially premised on the discovery that surface modified particulates may be used to retard the decomposition of various active ingredients which readily decompose upon reaction with environmental components (e.g. , air and/or water). Many active ingredients are known to decompose over time. Such decomposition often results in lowered shelf lives or increased expiration times for compositions comprising these active ingredients which readily decompose on contact with air and/or water and/or oxygen and/or carbon dioxide. Decomposition may occur via oxidation, photochemical decomposition, hydrolysis, epimerization, decarboxylation, etc. Decomposition may occur via a combination of reactive mechanisms. Without wishing to be bound by theory, it is believed that the surface modified particulates prevent atmospheric elements from absorbing into a composition. A surface modification to increase the hydrophobicity of particulates may prevent water, air, oxygen, carbon dioxide, etc. from being absorbed into the composition. These atmospheric elements promote the decomposition of the active ingredients. Examples of these active ingredients include antioxidants, retinoids, esters, amides, etc.

[00027] In some embodiments of the invention, the active ingredient may be botanicals, other keratolytic agents, desquamating agents, keratinocyte proliferation enhancers, collagenase inhibitors, elastase inhibitors, depigmenting agents, anti-inflammatory agents, steroids, antiacne agents, antioxidants, thiodipropionic acid or esters thereof, and advanced gly cation end- product (AGE) inhibitors. Exemplary anti-aging components include, without limitation, botanicals (e.g., Butea Frondosa extract); thiodipropionic acid (TDPA) and esters thereof; retinoids (e.g., all-trans retinoic acid, 9-cis retinoic acid, phytanic acid and others); hydroxy acids (including alpha-hydroxyacids and beta-hydroxyacids), salicylic acid and salicylates; other exfoliating agents (e.g., glycolic acid, 3,6,9-trioxaundecanedioic acid, etc.), estrogen synthetase stimulating compounds (e.g., caffeine and derivatives); compounds capable of inhibiting 5 alpha-reductase activity (e.g., linolenic acid, linoleic acid, finasteride, and mixtures thereof); barrier function enhancing agents (e.g., ceramides, glycerides, cholesterol and its esters, alpha-hydroxy and omega-hydroxy fatty acids and esters thereof, etc.); collagenase inhibitors; and elastase inhibitors; to name a few. In one embodiment, the composition comprises N- Acetyl Tyrosinamide.

[00028] An antioxidant functions, among other things, to scavenge free radicals from skin to protect the skin from environmental aggressors. Examples of antioxidants that may be used in the present compositions include compounds having phenolic hydroxy functions, such as ascorbic acid and its derivatives/esters; beta-carotene; catechins; curcumin; ferulic acid derivatives (e.g., ethyl ferulate, sodium ferulate); gallic acid derivatives (e.g., propyl gallate); lycopene; reductic acid; rosmarinic acid; tannic acid; tetrahydrocur cumin; tocopherol and its derivatives; uric acid; or any mixtures thereof. Other suitable antioxidants are those that have one or more thiol functions (~SH), in either reduced or non-reduced form, such as glutathione, lipoic acid, thioglycolic acid, and other sulfhydryl compounds. The antioxidant may be inorganic, such as bisulfites, metabisulfites, sulfites, or other inorganic salts and acids containing sulfur. In one particular embodiment, the inventive compositions will include TDPA or an ester thereof (e.g., dilauryl thiodipropionic acid), and/or an alpha hydroxyl acid (glycolic acid) and/or beta hydroxyl acid (salicylic acid or a derivative). In some embodiments, the particulate material according to the invention is hydrophobically modified silica (S1O2) powder, including fumed silica or pyrogenic silica (e.g., having a particle size range from about 7 nm to about 40 nm). Other notable particulate materials are hydrophobically modified metal oxides, including without limitation titanium dioxide (TiC ), aluminum oxide (AI2O3), zirconium dioxide (ZrC ), tin dioxide (SnC ), zinc oxide (ZnO), and combinations thereof.

[00029] Advantageously, the particulate material may be one which provides additional functionality to the compositions, including for example, ultraviolet (UV) light absorption or scattering, in the case of, for example, titanium dioxide and zinc oxide particulates, or provide aesthetic characteristics, such as color (e.g., pigments), pearlesence (e.g. mica), or the like. The particulate material may be based, for example, on organic or inorganic particulate pigments. Examples of organic particulate pigments include lakes, especially aluminum lakes, strontium lakes, barium lakes, and the like. Examples of the inorganic particulate pigments are iron oxide, especially red, yellow and black iron oxides, titanium dioxide, zinc oxide, potassium ferricyanide (K3Fe(CN)6), potassium ferrocyanide (K4Fe(CN)6), potassium ferrocyanide trihydrate (K4Fe(CN)6-3H20), and mixtures thereof. The particulate material may also be based on inorganic fillers such as talc, mica, silica, and mixtures thereof, or any of the clays disclosed in EP 1 640 419, the disclosure of which is hereby incorporated by reference.

[00030] In some embodiments, particulate materials are surface-treated to impart a hydrophobic coating thereon. Hydrophobically modified particulates and methods for preparing hydrophobically modified particulates are well-known in the art, as described in, for example, U.S. Patent No. 3,393,155 to Schutte et al, U.S. Patent No. 2,705,206 to Wagner et al, U.S. Patent No. 5,500,216 to Wagner et al, U.S. Patent No. 6,683,126 to Keller et al, and U.S. Patent No. 7,083,828 to Muller et al., U.S. Patent Pub. No. 2006/0110541 to Russell at al, and U.S. Patent Pub. No. 2006/0110542 to Dietz et al., the disclosures of which are hereby incorporated by reference. In one embodiment, a hydrophobic particle in accordance with an embodiment of the present invention may be formed from an oxide particle (e.g., a metal oxide, silicon dioxide, etc.) having its surface covered with (e.g., covalently bonded to) non-polar radicals, such as for example alkyl groups, silicones, siloxanes, alkylsiloxanes, organosiloxanes, fluorinated siloxanes, perfluorosiloxanes, organosilanes, alkylsilanes, fluorinated silanes, perfluorinated silanes and/or disilazanes and the like. U.S. Patent No. 6,315,990 to Farer, et al, the disclosure of which is hereby incorporated by reference, described suitable fluorosilane coated particulates which are formed by reacting a particulate having a nucleophilic groups, such as oxygen or hydroxyl, with a silicon-containing compound having a hydrocarbyl group substituted by at least one fluorine atom and a reactive hydrocarbyloxy group capable of displacement by a nucleophile. An example of such a compound is tridecafluorooctyltriethoxy silane, available from Sivento, Piscataway, N.J., under the trade name DYNASILANE™ F 8261. The hydrophobically modified silica materials described in U.S. Patent Pub. 2006/0110542 to Dietz et al, incorporated herein by reference, are contemplated to be particularly suitable.

[00031] Any of the hydrophobically modified particulate materials described in U.S. Patent No. 6,683,126 to Keller et al, the disclosure of which is hereby incorporated by reference herein, are also contemplated to be useful, including without limitation those obtained by treating an oxide material (e.g., SiC , TiC , etc.) with a (perfluoro)alkyl-containing compound that contains at least one reactive functional group that undergoes a chemical reaction with the near-surface OH groups of the oxide support particle, including for example hexamethyldisilazane, octyltrimethoxysilane, silicone oil, chlorotrimethylsilane, and dichlorodimethylsilane.

[00032] Suitable hydrophobically modified fumed silica particles include, but are not limited to AEROSIL™ R 202, AEROSIL™ R 805, AEROSIL™ R 812, AEROSIL™ R 812 S, AEROSIL™ R 972, AEROSIL™ R 974, AEROSIL™ R 8200, AEROXIDE™ LE-1, AEROXIDE™ LE-2, and AEROXIDE™ LE-3 from Evonik Industries AG, N.J. Other suitable particulates include the particulate silicon wax sold under the trade name Tegotop™ 105 (Evonik/Goldschmidt Chemical Corporation) and the particulate vinyl polymer sold under the name Mincor™ 300 (BASF). While silica (S1O2) and hydrophobically-modified silicas are contemplated to be particularly useful in some embodiments, in other embodiments the compositions will be substantially free of silica or hydrophobically-modified silica. By substantially free of silica or hydrophobically-modified silica means that these components comprise less than about 2%, preferably less than about 1%, and more preferably less than about 0.5% by weight of the one or more particulate materials. A suitable hydrophobically modified alumina particulate is ALU C 805 from Evonik.

[00033] The one or more particulate materials may also comprise particulate organic polymers such as polytetrafluoroethylene, polyethylene, polypropylene, nylon, polyvinyl chloride, and the like which have been formed into fine powders. Alternatively, the particulate material may be a microcapsule comprising any of the shell materials described in U.S. Patent Pub. 2005/0000531, the disclosure of which is hereby incorporated by reference herein.

[00034] The one or more particulate materials will typically be in the form of a powder having a median particle size between about 1 nm (nanometers) and about 1 mm (millimeters), more typically between about 5 nm and about 500 μηι (micrometer), preferably between about 7 nm and about 1 μιτι, 5 μιτι, 20 μιτι, 50 μηι or about 100 μηι. Where more than one particulate material is employed (e.g., modified TiC and modified SiC ), the median particle size of each powder is preferably within the foregoing ranges.

[00035] Another particulate suitable for use is diatomaceous earth ("DE"). Surface modified diatomaceous earth ("SMDE") has been described in U.S. Patent. Nos. 8,216,674 and 8,497,021, each herein incorporated by reference. Surface modification of the diatomaceous may occur through the formation of a self-assembled monolayer ("SAM") on the surface without alteration of the frustule topography of the DE. Adhesion may occur through the formation of a covalent bond between the surface and the one or more reactive groups. The compounds of the monolayer then orient certain moieties away from the surface and toward the air interface. These moieties help impart the desired surface properties, such as hydrophobicity or oleophobicity. The SAM precursors which may be used to surface modify the DE may have a structure with one end of the molecule capable of adsorbing to the surface and another end comprising a moiety capable of imparting the desired hydrophobic and/or oleophobic properties at the air interface. The SAM precursor may have a reactive moiety capable of reacting with the multiple OH groups on the DE surface such as, for example, a silane group (e.g., trialkoxy silanes such as trimethoxy silane or triethoxysilane). The moiety may be fluorinated or perfluorinated. In some embodiments, the moiety is alkyl, fluoroalkyl, or perfluoroalkyl. For example, the moiety may be Ci-6 alkyl, Ci-6 fluoroalkyl, or Ci-6 perfluoroalkyl. In some embodiments, the SAM precursor may comprise a silane group. The surface may be from about 0.01%-100% (e.g. , about 0.1%-50%, about l%-25%, or about 2- 15%, or about 5-10%, etc.) modified. Suitable surface-modified DE is available from Dry Surface Technologies (Guthrie, OK).

[00036] Many particulates have a tendency to agglomerate. Individual particles may agglomerate to form larger secondary particles that can range in size from hundreds of nanometers to hundreds of microns in diameter. In some embodiments, the particulates are not in the form of large agglomerates. Analysis of compositions to determine the presence of agglomerates is easily performed with optical micrographs. Large agglomerates scatter light resulting in opaque portions of the micrograph. Compositions without large agglomerates do not have these opaque regions when optically measured with visible light. In some embodiments, the composition is substantially free of large agglomerates (i.e. , agglomerates with a size greater than about 50 μηι or 100 μιτι, or 500 μιτι, etc.). In some embodiments, the particulates have an average particle size of less than about 100 μηι (e.g. , less than about 50 μιη, less than about 20 μιτι, less than about 15 μιτι, etc.). In some embodiments, the particulates haves an average particle size of from about 0.1 μηι to about 50 μηι (e.g. , about 1 μιη to about 30 μηι, about 0.1 μηι to about 30 μιτι, about 1 μιη to about 20 μιτι, about 5 μηι to about 20 μιτι, about 10 μηι to about 20 μιτι, about 10 μηι to about 15 μιτι, about 15 μηι to about 20 μιτι, etc.). As used herein "particle size" is meant to refer the average particle size of the agglomerates, and not the individual particles unless otherwise specified.

[00037] The compositions of the invention will typically include a cosmetically acceptable or physiologically compatible vehicle, which may be in the form of, for example, a serum, a cream, a lotion, a gel, or a stick. The vehicle may comprise an emulsion (e.g. , water-in-oil, oil- in-water, water-in-silicone, silicone-in-water, polyol-in-silicone, silicone-in-polyol emulsion, etc.), or may comprise an aqueous or ethanolic vehicle, volatile and/or non-volatile silicone (e.g. , cyclomethicone, methicone, amodimethicone, dimethicone, carpylyl methicone, trisiloxane, cyclopentasiloxane, stearyl methicone, phenyl trimethicone etc.), hydrocarbon (e.g. , petrolatum, isododecane, etc.), ester oil (e.g. , isopropyl myristate, myristyl myristate), or the like. The vehicle may comprise mixtures of hydrocarbon oils, ester oils and silicone oils in any proportion thereof. The vehicle may be in form of an emulsion (e.g., an oil-in-water or oil- in- water emulsion). The oil phase of the emulsion may comprise silicone fluids, as the major or only component, or in the combination with other oils, such as ester oils and/or hydrocarbons, and/or fatty alcohols, and/or acids. When formulated as an emulsion, an emulsifier is typically included. In other embodiments, the composition is substantially free or free of an emulsifier. Examples of silicone emulsifiers include Cetyl/PEG/PPG-10/1 Dimethicone, Cetyl Diglyceryl Tris(Trimethylsiloxy)silylethyl Dimethicone, PEG/PPG-18/18 Dimethicone, PEG- 10 Dimethicone, PEG/PPG-20/15 Dimethicone, Bis-PEG/PPG-20/5 PEG/PPG-20/5 Dimethicone, Methoxy PEG/PPG-25/4 Dimethicone and PEG/PPG- 19/19 Dimethicone. By substantially free of an emulsifier is meant that no emulsifier is deliberately added to the composition and/or the amounts present, if any, are so low as to not have a measureable impact on the stability of an emulsion. The vehicle may further comprise an emulsifier, gelling agent, structuring agent, rheology modifier (e.g., a thickener), film former, or the like. The compositions of the invention may optionally include additional skin benefit agents such as emollients (dimethicone oils, ester oils, or hydrocarbon oils), humectants (e.g. , polyols, including propylene glycol, glycerin, propanediol, butylene glycol, pentylene glycol etc.), antioxidants (e.g. , BHT, ascorbic acid, sodium ascorbate, ascorbyl palmitate, beta- carotene, etc.), vitamins (e.g., tocopherol, tocopheryl acetate, etc.), beta-hydroxy acids (e.g. , salicylic acid), retinoids (e.g. , retinoic acid, all-trans-retinoic acid, retinaldehyde, retinol, and retinyl esters such as acetates or palmitates), other anti-aging ingredients (e.g., collagen stimulators), as well as additional depigmenting agents (e.g. , kojic acid, TDPA, Niacinamide, etc.).

[00038] The vehicle may be anhydrous. In some implementations, the anhydrous vehicle may include a gelling agent, structuring agent, rheology modifier (e.g., a thickener), film former, or the like. In some embodiments, the amount of thickener is sufficient to retard or prevent settling (e.g. the amount of thickener produces a viscosity of the composition of about 10,000 cps and 1,000,000 at a shear rate of 1 s ^"1 ). In some embodiments the vehicle is a silicone fluid having a viscosity of from about 50 cSt to about 1,000 cSt (e.g. SF-96). In some embodiments, the thickener may be a polysaccharide, protein, alcohol, silicone, wax, clay (e.g., organoclay, quaternary ammonium salt, garamite clay, mixed mineral thixotropes, sepiolite, bentonite etc.), or combinations thereof. In an embodiment the thickener is garamite clay.

[00039] In some embodiments, the composition may be in the form of a water-in-oil, oil-in- water, water-in-silicone, or silicone-in-water emulsion. In some embodiments, the emulsion may further comprise one or more ester oils, one or more silicone oils, silicone fluids, and/or any silicone based polymers. In some embodiments, the oil phase of a oil-in-water emulsion may comprise from about 0.0001% to 100% (e.g., about 0.01% to about 50%, about 0.1% to about 30%, about 50% to about 90%, about 60% to about 80%, about 40% to about 60%, about 1% to about 10%, etc.) by weight silicones and/or ester oils. Silicone based polymers refer to polymerized siloxane with organic side chains (e.g., dimethicone and dimethicone cross- polymers). The organic side chains may be for example Ci-26 alkyl, alkenyl, aryl, or arylalkyl. In some embodiments a silicone fluid comprises from about 0.001 to about 30.0% by weight of the entire composition (e.g. about 0.01 to about 20.0% by weight, about 0.1 to about 10% by weight, about 1 to about 5% by weight, etc.). The silicone oils may be volatile and/or nonvolatile. Volatile silicones include cyclic and linear volatile dimethylsiloxane silicones. In one embodiment, the volatile silicones may include cyclodimethicones, including tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicones, or mixtures thereof. Particular mention may be made of the volatile cyclomethicones, hexamethyl cyclotrisiloxane, octamethyl- cyclotetrasiloxane, and decamethyl-cyclopentasiloxane. Suitable dimethicones are available from Dow Corning under the name Dow Coming 200 RTM fluid and have viscosities ranging from 0.65 to 600,000 centistokes or higher. Suitable non-polar, volatile liquid silicone oils are disclosed in U.S. Pat. No. 4,781,917, herein incorporated by reference in its entirety. Additional volatile silicones materials are described in Todd et al, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, 91 :27-32 (1976), herein incorporated by reference in its entirety. Linear volatile silicones generally have a viscosity of less than about 5 centistokes at 25°C, whereas cyclic silicones typically have viscosities of less than about 10 centistokes at 25°C. Examples of volatile silicones of varying viscosities include Dow Corning 200, Dow Corning 244, Dow Corning 245, Dow Corning 344, and Dow Coming 345, (Dow Coming Corp.); SF-1204 and SF-1202 Silicone Fluids (G.E. Silicones), GE 7207 and 7158 (General Electric Co.); and SWS-03314 (SWS Silicones Corp.). Linear, volatile silicones include low molecular weight polydimethylsiloxane compounds such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane, to name a few.

[00040] The oil-containing phase may be composed of a singular oil or mixtures of different oils. Essentially any oil is contemplated to be useful, although highly hydrophobic oils are preferred. Suitable non-limiting examples include vegetable oils; esters such as octyl palmitate, isopropyl myristate and isopropyl palmitate; ethers such as dicapryl ether; fatty alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol; isoparaffins such as isooctane, isododecane and isohexadecane; silicone oils such as dimethicones, cyclic silicones, and polysiloxanes; hydrocarbon oils such as mineral oil, petrolatum, isoeicosane and polyisobutene; natural or synthetic waxes; and the like.

[00041] Suitable hydrophobic hydrocarbon oils may be saturated or unsaturated, have an aliphatic character and be straight or branched chained or contain alicyclic or aromatic rings. Hydrocarbon oils include those having 6-20 carbon atoms, more preferably 10-16 carbon atoms. Representative hydrocarbons include decane, dodecane, tetradecane, tridecane, and Ce- 20 isoparaffins. Paraffinic hydrocarbons are available from Exxon under the ISOPARS trademark, and from the Permethyl Corporation. In addition, C8-20 paraffinic hydrocarbons such as C12 isoparaffin (isododecane) manufactured by the Permethyl Corporation having the tradename Permethyl 99A™ are also contemplated to be suitable. Various commercially available Ci6 isoparaffins, such as isohexadecane (having the tradename Permethyl R™) are also suitable. Examples of preferred volatile hydrocarbons include polydecanes such as isododecane and isodecane, including for example, Permethyl-99A (Presperse Inc.) and the C7- C8 through C12-C15 isoparaffins such as the Isopar Series available from Exxon Chemicals. A representative hydrocarbon solvent is isododecane.

[00042] Various fillers and additional components may be added. Suitable fillers include without limitation silica, treated silica, talc, zinc stearate, mica, kaolin, Nylon powders such as Orgasol™, polyethylene powder, Teflon™, starch, boron nitride, copolymer microspheres such as Expancel™ (Nobel Industries), Polytrap™ (Dow Corning) and silicone resin microbeads (Tospearl™ from Toshiba), and the like.

[00043] Additional pigment/powder fillers include, but are not limited to, inorganic powders such as gums, chalk, Fuller's earth, kaolin, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, lithia mica, vermiculite, aluminum silicate, starch, smectite clays, alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminum silicate, organically modified montmorillonite clay, hydrated aluminum silicate, aluminum starch octenyl succinate barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica alumina, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxy apatite, ceramic powder, metallic soap (zinc stearate, magnesium stearate, zinc myristate, calcium palmitate, and aluminum stearate), colloidal silicone dioxide, and boron nitride; organic powder such as polyamide resin powder (nylon powder), cyclodextrin, methyl polymethacrylate powder, copolymer powder of styrene and acrylic acid, benzoguanamine resin powder, poly(ethylene tetrafluoride) powder, and carboxyvinyl polymer, cellulose powder such as hydroxyethyl cellulose and sodium carboxymethyl cellulose, ethylene glycol monostearate; inorganic white pigments such as magnesium oxide; and stabilizers/ rheology modifiers, for example, Bentone Gel and Rheopearl TT2. Other useful powders are disclosed in U.S. Pat. No. 5,688,831, the disclosure of which is hereby incorporated by reference. [00044] The compositions of the invention may optionally comprise other active and inactive ingredients typically associated with cosmetic and personal care products, including, but not limited to, excipients, fillers, emulsifying agents, surfactants, film formers, chelating agents, gelling agents, thickeners, emollients, humectants, moisturizers, vitamins, minerals, viscosity and/or rheology modifiers, sunscreens, keratolytics, depigmenting agents, retinoids, hormonal compounds, alpha-hydroxy acids, alpha-keto acids, anti-mycobacterial agents, antifungal agents, antimicrobials, antivirals, analgesics, lipidic compounds, anti-allergenic agents, HI or H2 antihistamines, anti-inflammatory agents, anti-irritants, antineoplastics, immune system boosting agents, immune system suppressing agents, anti-acne agents, anesthetics, antiseptics, insect repellents, skin cooling compounds, skin protectants, skin penetration enhancers, exfollients, lubricants, fragrances, colorants, staining agents, depigmenting agents, hypopigmenting agents, preservatives, stabilizers, pharmaceutical agents, photostabilizing agents, and mixtures thereof. In some embodiments, these other active and inactive ingredients readily decompose on contact with additives typically found in an environment (e.g. air and/or water). In some embodiments, the compositions may not comprise preservatives, stabilizers, and/or photostabilizing agents. In some embodiments, the compositions may comprise preservatives, stabilizers and/or photostabilizing agents in an amount less than about 10% or less than about 5% or less than about 1% or less than 0.1% by weight of the composition.

[00045] Cosmetic and/or topical compositions according to the invention include, but are not limited to, color cosmetics, skin care products, hair care products, and personal care products. Color cosmetics include, for example, foundation and mascara. Skin care products include, but are not limited to, sunscreens, after-sun products, lotions, and creams. Additional applications include use in hair care products, insect repellents, deodorants, anti-perspirants, lipstick, ear canal product, baby wipes, baby creams or lotions, top coats to impart water-proofing or water- resistance to a previously applied cosmetic product, personal care product, hair care product, or first aid product. For example, the composition according to the invention could be applied as a top coat for a sunscreen or sunblock/insect repellant lotion previously applied to the skin to improve water-proofing or water-resistance. Alternatively, the composition could be applied as a top coat over a first aid product such as an antibiotic ointment or spray, bandage, or wound dressing.

[00046] In one embodiment, the compositions are applied to the skin, preferably the skin of the face. Such compositions may be formulated as a foundation, a blush, etc. In another embodiment, the compositions are provided as a water-resistant, oil-resistant, transfer-resistant lip product (e.g., a lipstick or lip gloss). Color cosmetics will optionally comprise one or more colorants, including dyes, lakes, pigments, or combinations thereof.

[00047] Other optional ingredients include, without limitation, silicone elastomers which may be incorporated to provide conditioning properties to the hair or improve the tactile properties of the film. Silicone elastomers are crosslinked flexible silicones that can undergo large reversible deformations. Such elastomers may be formed, for example, by platinum metal catalyzed reactions between SiH containing diorganopolysiloxanes and organopolysiloxanes having silicon bonded vinyl groups. Suitable silicone elastomers include dimethicone/vinyl dimethicone crosspolymers, vinyl dimethicone/methicone silsesquioxane crosspolymers, and dimethicone/phenyl vinyl dimethicone crosspolymers. Further examples include PEG- 12 Dimethicone/PPG-20 Crosspolymer, PEG- 12 Dimethicone Crosspolymer, Bis- Vinyldimethicone/PEG-10 Dimethicone Crosspolymer, PEG-15/Lauryl Dimethicone Crosspolymer, Dimethicone/Polyglycerin-3 Crosspolymer and Dimethicone/PEG-10/15 Crosspolymer. Commercial examples include Dow Corning 9040, 9041, and 9506, and Shin- Etsu KSG-15, 16, and 17, and Shin-Etsu KSP-100, 101, 102, 103, 104, 105, 200 and 300. The elastomers are preferably present at a concentration of 0.01% to 10%, more preferably at a concentration of 0.1% to 5%, and most preferably at a concentration of 1% to 3%. Vinyl dimethicone/Methicone/Silsesquioxane crosspolymer is one such silicone elastomer that has been found particularly useful. Other ingredients that can optionally be present include, without limitation, conditioners (e.g., Polyquaternium-37/PG Dicaprylate/Trideceth blend), aesthetic modifiers (e.g., Polymethyl Methacrylate spherical powder having a diameter of 4-8 μιτι), silicone resins (such as trimethylsiloxysilicate), thickeners (e.g., PEG-150/decyl alcohol/SMDI copolymer), sunscreens, preservatives, fragrances, etc.

[00048] In some embodiments, the particulates are incorporated into the composition with agitation, such as with an ultrasonic processor, high pressure homogenizer, colloid mill, or high shell mixer. In some embodiments, the particulates are subject to high shear mixing for a period of time before use. By "high shear," it is meant that the shear applied is equal to the shear applied by DISPERMAT CN10 disperser with a rotation speed of at least 750 rpm (e.g. , about 1000 rpm to about 10,000 rpm, 1500 rpm to about 5000 rpm, about 2000 rpm to about 2500 rpm, etc.). In some embodiments, the high shear is applied for at least one minute (e.g. , at least two minutes, five minutes, 10 minutes, 20 minutes, 60 minutes, etc.). In some embodiments, the compositions, or portions of the compositions contacting particulates may be prepared in a mixer operating at a propeller rotation speed of at least 500 rpm (e.g. , about 500 rpm to about 50,000 rpm about 1000 rpm to about 10,000 rpm, 1500 rpm to about 7500 rpm, about 2000 rpm to about 5000 rpm, etc.).

[00049] The compositions may be applied to a keratinous surface. The keratinous surface may be hair, skin, eyelashes, or nails. In some embodiments, the keratinous surface may be wet or dry at the time of application of the composition. The topical composition of the present invention may be in the form of make-ups or color cosmetics such as foundation, foundation primer base, blush, lipstick, eyeshadow, eye liner, nail enamel, concealer, mascara, body makeup product, a sunscreen, or hair makeup product. The topical compositions may be in the form of topically acceptable vehicles, such as, but not limited to, liquid (e.g. suspension or solution), gel, emulsion, emulsified gel, mousse, cream, ointment, lotion, spray, wipe, paste, serum, milk, foam, balm, aerosol, liposomes, solid (e.g. pressed powders), cake, mask, anhydrous oil and wax composition. More specifically, the cosmetic may include an anti-sun product such as sunscreen or a skin coloring product such as a self-tanning product. The composition may also be a hair care product, especially for thickening, holding or shaping the hair or hairstyle.

[00050] The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described therein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. All publications cited herein are incorporated by reference in their entirety.

EXAMPLES

[00051] The following examples illustrate specific aspects of the instant description. These examples should not be construed as limiting, as these examples merely provide specific understanding and practice of the embodiments and its various aspects.

EXAMPLE 1

[00052] Spectrophotometric measurements of ascorbic acid stabilized by surface modified diatomaceous earth. [00053] Compositions comprising ascorbic acid and diatomaceous earth (DE) were prepared with the formulations shown in Table 1. Formulations A, B, and C each have varying amounts of DE while the control is an otherwise identical formulation prepared without DE. In each formulation, the DE was milled at 2500 rpm on DISPERMAT mixer for five minutes.

Table 1

aGaramite 7308 XR from Eckart America Corporation

b Banian™ from Dry Surface Technologies (Guthrie, OK) surface modified DE (SMDE)

c Imerys ImerCare™ non-surface modified DE

[00054] Each formulation shown in Table 1 was individually placed into two separate containers. These containers exposed the compositions contained therein to their atmospheric environment (i.e. non air tight containers). One container of each formulation was stored at 90% relative humidity at 37°C. The containers in the high humidity environment were stirred to visual uniformity once a week over the course of four weeks. The other container of each formulation was stored at -22°C in a non-humid environment for four weeks. Each sample was stored in an environment without light to prevent any potential photoreactions of the ascorbic acid. This non-oxidized sample is used to show the color difference ("ΔΕ") for each composition.

[00055] After four weeks, spectrophotometric measurements were performed on each container. Spectrophotometric measurements were performed with a X-Rite RM200QC imaging spectrophotometer. Measurements were performed in the CIELab color space ("Lab color space"). The Lab color space designates colors through a measured lightness ("L*" or "L") value, the color position between red/magenta and green ("a*" or "a"), and the color position between yellow and blue ("b*" or "b"). The relative differences between any two colors in the Lab space can be approximated by treating each color as point in three- dimensional space with coordinate position L*, a*, and b*, and measuring the distance between points. Color difference measurements were performed with an X-Rite RM200QC operating in CIE LAB mode for the ΔΕ calculation. Typically a color difference of around 1 is perceptible to the human eye. The Lab color space values measured for each composition at -22°C and 37°C and the corresponding measured ΔΕ are given below in Tables 2-3.

Table 2

Table 3

[00056] As can be seen in Table 2 and Table 3, compositions without surface modified diatomaceous earth (Control) resulted in a color difference of 42.7 and 31.2 respectively over four weeks. As can be seen in Table 3, Formulations A, B and C, which comprised compositions of non-surface modified diatomaceous earth from about 1% to about 10% by weight of the composition resulted in color differences comparable to that of compositions not comprising diatomaceous earth. This indicates substantial oxidation of ascorbic acid in compositions not comprising surface modified diatomaceous earth over that period. However, as seen in Table 2, formulations A, B, and C, which comprised from about 1% to about 10% SMDE by weight of the composition, resulted in less color variation of ascorbic acid containing compositions. The 1% formulation resulted in about 70% reduction in color shift, while the 5% and 10% formulations resulted from about 90-95% reduction in color shift. Increasing the amount of surface modified particulate in compositions comprising ascorbic acid prevented the oxidation of ascorbic acid in the compositions. The change for each color coordinate and ΔΕ from Table 2 is shown in Figure 1. As can be seen, the addition of surface modified particulates to a composition decreases the change of each color coordinate for compositions.

EXAMPLE 2

[00057] Spectrophotometric measurements of ascorbic acid stabilized by surface modified silica.

[00058] Compositions comprising surface modified silica were prepared according to formulations A-C. In each otherwise identical composition, surface modified silica (KOBO MSS-500N-FS, available from KOBO, NJ) was used instead of SMDE. Spectrophotometric measurements were performed on the silica compositions following as performed in Example 1 following one week of storage in low temperature and high temperature environments. The Lab color space values measured for each composition at -22°C and 37°C and the corresponding measured ΔΕ are given below in Table 4.

Table 4

0% Silica 1% Silica 5% Silica 10% Silica

T=- T=- T=-

T=37°C T=37°C T=37°C T=-22°C T=37°C 22°C 22°C 22°C

L* 69.4 64.2 69.4 68.3 70.4 68.9 70.5 69.2 a* 0.6 1.7 0.4 0.9 0.7 1.0 0.8 1.0 b* 18.6 18.6 8.9 10.1 9.8 10.3 9.8 10.6

ΔΕ 10.4 1.6 1.6 1.5 [00059] As can be seen, compositions without surface modified silica (Control) resulted in a color difference of 10.4 over one week while compositions comprising from about 1% to about 10% silica by weight of the composition resulted in less color variation of ascorbic acid containing compositions. Each formulation comprising surface modified silica resulted in more than about 85% (i.e. 0.85=(10.4-1.6)/10.4) reduction in color shift over one week. Moreover, each formulation comprising surface modified silica resulted in compositions with substantially imperceptible variations in color shift after one week. Increasing the amount of surface modified particulate in compositions comprising ascorbic acid prevented the oxidation of ascorbic acid in the compositions.

[00060] As various changes can be made in the above-described subject matter without departing from the scope and spirit of the present invention, it is intended that all subject matter contained in the above description, or defined in the appended claims, be interpreted as descriptive and illustrative of the present invention. Many modifications and variations of the present invention are possible in light of the above teachings. Accordingly, the present description is intended to embrace all such alternatives, modifications, and variances which fall within the scope of the appended claims.

[00061] All references including patent applications and publications cited herein are incorporated herein by reference in their entirety and for all purposes to the same extent as if each individual publication or patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety for all purposes. Many modifications and variations of this invention can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. The specific embodiments described herein are offered by way of example only, and the invention is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled.