HK1145981B - Cosmetic compositions for imparting superhydrophobic films - Google Patents

Description

Cosmetic composition for imparting superhydrophobic film

Technical Field

The present invention relates to methods and compositions for imparting a film onto a surface. More particularly, the present application relates to cosmetic compositions and methods for forming superhydrophobic films on skin or hair.

Background

The leaves of the lotus plant show surprising water resistance and self-cleaning properties. Although lotus plants preferably grow in muddy rivers and lakes, leaves and flowers remain clean and substantially non-wettable. This effect is achieved by the lotus plant by the leaves and flowers having a very hydrophobic surface. When the leaves come into contact with water, the water droplets contract into substantially spherical beads which roll off the surface and the dust particles encountered are swept free.

On a very hydrophilic surface, the water droplet will spread out completely and provide an effective contact angle of substantially 0 °. This occurs on surfaces that have a high affinity for water, including materials that absorb water. On many hydrophilic surfaces, water droplets exhibit contact angles of about 10 ° to about 30 °. Conversely, on hydrophobic surfaces, which are incompatible with water, larger contact angles are observed, typically ranging from about 70 ° to about 90 ° and higher. Some very hydrophobic substances, e.g. Teflon^TMWhich is widely used as a benchmark for hydrophobic surfaces, provides contact angles with water of up to 120 deg. -130 deg..

Against this background, it is surprising that lotus leaf flowers and leaves are capable of producing a contact angle with water of about 160 °, which is substantially greater than Teflon^TMAnd is more hydrophobic. Thus, lotus leaf is an example of a "superhydrophobic" surface. For this purpose, a superhydrophobic surface can be said to provide a contact angle with water of more than about 140 °. This effect is believed to be due to the three-dimensional surface structure of the leaves, where the wax crystals self-organize to provide nanometersOr roughness on the order of microns. The protrusion of the hydrophobic surface reduces the effective surface contact area with water and thus prevents the adhesion and spreading of water on the leaves.

The above mentioned findings of the properties of lotus leaf and elucidation of its mechanism lead to various engineered superhydrophobic surfaces. Such superhydrophobic surfaces have water contact angles ranging from 140 ° to nearly 180 °. Such surfaces are very difficult to wet. On these surfaces, the water droplets simply rest on the surface, virtually without wetting to any significant extent. Superhydrophobic surfaces have been obtained by various methods. Some of these very hydrophobic materials are found in nature. Other superhydrophobic materials are synthetically prepared, sometimes as simulated natural materials.

U.S. Pat. No.6,683,126 describes a coating composition for preparing difficult to wet surfaces comprising a finely divided powder whose particles are porous and have a hydrophobic surface, combined with a film binder, the ratio of the powder to the binder being 1: 4.

U.S. Pat. No.6,852,389 describes a method for preparing superhydrophobic materials for self-cleaning applications.

Us patent 6,946,170 describes a self-cleaning display device.

U.S. Pat. No.7,056,845 describes a method for applying a water repellent finish for use in fabrics, fibers and paper.

U.S. Pat. No.6,800,354 describes a method for preparing self-cleaning substrates of glass, ceramic and plastic.

U.S. patent No.5,500,216 describes a method of reducing water permeation by applying a film of coarse particles of a hydrophobic metal oxide, wherein the particles have two different size range distributions.

Although hydrophobic or superhydrophobic materials have been described above, there remains a need for hydrophobic or superhydrophobic materials in cosmetic compositions that impart a superhydrophobic film on surfaces such as skin, hair, or nails. Conventional water-resistant or water-repellent cosmetic compositions are generally prepared from oil-in-water or water-in-oil emulsions. Water-in-oil emulsions tend to have a greasy feel, thus limiting their use. Conventional approaches to formulating water-resistant or water-repellent cosmetic compositions rely on the use of hydrophobic film formers (e.g., waxes) to form a water-repellent barrier. Such conventional cosmetics are at best hydrophobic relative to the superhydrophobic films of the present invention.

Conventional water-resistant or water-repellent topical compositions are not superhydrophobic, primarily because they lack surface roughness on a nanometer or micrometer scale. In the absence of roughness on the nano-or micro-scale, smooth films made from currently known hydrophobic materials exhibit contact angles that are not in the superhydrophobic range, i.e., they are less than 140 °. It is desirable to provide cosmetic films that impart superhydrophobic films to improve water repellency, self-cleaning performance, and long-lasting performance.

Accordingly, it is an object of the present invention to provide a cosmetic composition for application to skin, hair or nails and forming a superhydrophobic film thereon. It is another object of the present invention to provide a method of imparting a superhydrophobic film to skin, hair, or nails to achieve water repellency, self-cleaning, and/or long lasting properties.

Summary of The Invention

In accordance with the foregoing objects and others, the present invention provides compositions and methods for forming a superhydrophobic film on a surface, preferably a biological integument, such as skin, nails, or hair. The compositions of the present invention are in the form of water-in-oil or water-in-silicone emulsions. It is unexpected that superhydrophobic films can be produced from aqueous compositions because water (which is defined as hydrophilic) is expected to reduce the hydrophobicity of the surface. However, it has been surprisingly found that water-based emulsion formulations are capable of providing superhydrophobic films if certain other ingredients are maintained within critical ranges. Thus, various products can be formulated in emulsion form having aesthetic and functional characteristics not attainable with anhydrous-based compositions.

In one aspect of the invention, a composition comprising a water-in-oil emulsion is provided for imparting a hydrophobic film on a surface. The water-in-oil emulsion comprises (i) a continuous oil phase; (ii) a discontinuous (internal) aqueous phase; (iii) an emulsifier having an HLB value of less than 10, preferably less than 8.5; (iv) (iv) one or more hydrophobic film formers and (v) one or more hydrophobic particulate materials having a median particle size of from about 5nm to about 1 mm.

In a related aspect of the invention, a composition comprising a water-in-silicone emulsion is provided for imparting a hydrophobic film on a surface. Water-in-silicone emulsions comprise (i) a continuous oil phase; (ii) a discontinuous aqueous phase; (iii) an emulsifier comprising an organosiloxane polymer having side chains, wherein the side chains comprise- (EO)_m-and/or- (PO)_n-groups wherein n and m are integers from 0 to about 25 and wherein the sum of n and m is at least 1 but about 50 or less, the side chains may be terminated by hydrogen or lower alkyl; (iv) (iv) one or more hydrophobic film formers and (v) one or more hydrophobic particulate materials having a median particle size of from about 5nm to about 1 mm.

In water-in-oil and water-in-silicone emulsions, the weight ratio of the one or more hydrophobic film formers to the one or more hydrophobic particulate materials is suitably from about 1: 5 to about 5: 1, with higher concentrations of particulate materials being preferred; and the one or more hydrophobic film formers and the one or more hydrophobic particulate materials collectively comprise at least about 1%, preferably at least about 2%, more preferably at least about 5%, by weight of a water-in-oil or water-in-silicone emulsion.

To achieve the desired superhydrophobic effect, the combined weight percentage of all non-volatile water-soluble or water-dispersible organic components (i.e., non-volatile hydrophilic organic molecules) in the emulsion should be less than 15%, preferably less than 5% and ideally less than 2%; and the combined weight percentage of all polyols, including humectant glycerin, should be less than 5%, preferably less than 2% and ideally less than 1% by weight, based on the total weight of the emulsion; as such components tend to attract water as well as coat the surface of the film and thus reduce its hydrophobicity.

The one or more hydrophobic particulate materials typically comprise oxide particles selected from the group consisting of silica, titania, alumina, zirconia, tin dioxide, zinc oxide, and iron oxide, and combinations thereof, the oxide particles having hydrophobic moieties, such as alkyl, fluoroalkyl, perfluoroalkyl, siloxane, alkylsiloxane, fluoroalkylsiloxane, and/or perfluoroalkylsiloxane, covalently bonded to their surfaces. Preferred hydrophobic particles are surface treated fumed (pyrogenic) silica particles or surface treated fumed (pyrogenic) alumina particles, typically having a median particle size of from about 7nm to about 40 nm.

The one or more hydrophobic film formers include any hydrophobic film former compatible with the human skin and may be, for example, selected from the group consisting of (alkyl) acrylates, polyurethanes, fluoropolymers, polysiloxanes, and copolymers thereof. Acrylate/polydimethylsiloxane copolymers are currently preferred.

The composition is capable of providing a film on a surface upon evaporation of its volatile components characterized by a contact angle with water of greater than about 140 °, preferably greater than about 145 ° and most preferably greater than about 150 °.

The emulsions can be used in a variety of products, including cosmetic products (mascara, foundation, etc.); a skin care product; a sunscreen agent; hair care products, pet care products, and the like.

Also provided are methods of providing a hydrophobic film on skin or hair. The method generally comprises depositing an emulsion of the invention on skin or hair and allowing the volatile components to evaporate, thereby forming a hydrophobic film characterized by a contact angle with a water droplet of at least 140 °.

These and other aspects of the present invention will become apparent to those skilled in the art upon a reading of the following detailed description of the invention, including the drawings and the appended claims.

Brief Description of Drawings

FIG. 1 is a photograph showing a water droplet resting on a glass slide on which a superhydrophobic film has been deposited by application of an emulsion of the invention.

Detailed description of the invention

The term "superhydrophobic" as used herein generally refers to any surface having a contact angle with water of greater than 140 °. Superhydrophobicity can be assessed quantitatively by measuring the contact angle with water using a contact angle goniometer or similar methods known in the art, or qualitatively by visual inspection and observation of water repellency (i.e., observing the rolling off of a water bead from a cast film).

Superhydrophobicity provides water repellency to surfaces and thus can affect longevity and self-cleaning of the cosmetic composition after application to the skin, nails, or hair. Furthermore, it is believed that the compositions of the present invention result in reduced adherence of contaminants, dust, etc. to the skin, nails or hair due to the mismatch in surface energies. As a result, contaminants, dust, etc. are easily removed with or without water, resulting in self-cleaning. More importantly, the composition provides a barrier layer to water so that the skin or hair does not become wet or is only poorly wetted when in contact with water, such as sweat, rain, and the like.

The cosmetic compositions of the present invention for imparting a superhydrophobic film generally comprise a water-in-oil emulsion comprising one or more cosmetic film formers, one or more hydrophobically or hydrophobically modified particulate materials having a median particle size of from about 10nm to about 1mm, and one or more emulsifiers. As used herein, "water-in-oil emulsion" includes water-in-silicone emulsions.

The composition is preferably capable of providing a film on a surface upon evaporation of its volatile solvent, characterized by a contact angle with a drop of water of greater than about 140 °, preferably greater than about 145 ° and most preferably greater than about 150 °. The contact angle is a measure of the hydrophobicity of a surface and is the angle at which the liquid/vapor interface contacts a solid surface. The contact angle is suitably measured using a contact angle goniometer.

The first desired component in the compositions of the present invention is a film former. The film former preferably comprises a hydrophobic material. The hydrophobic film former may be any hydrophobic film former suitable for use in cosmetic compositions, including but not limited to hydrophobic film-forming polymers. The term "film-forming polymer" may be understood to mean a polymer capable of forming, by itself or in the presence of at least one auxiliary film-forming agent, a continuous film which adheres to a surface and acts as a binder for the particulate material. The term "hydrophobic" film-forming polymer typically refers to a polymer having a solubility in water at 25 ℃ of less than about 1% by weight or wherein each monomeric unit of the polymer has a solubility in water at 25 ℃ of less than about 1% by weight. Alternatively, a "hydrophobic" film-forming polymer can be said to be one that partitions significantly into the octanol phase when shaken with a mixture of equal volumes of water and octanol. By "significantly" it is meant that more than 50% by weight, and preferably more than 75% by weight, and more preferably more than 95% by weight will partition into the octanol phase.

Film formers may be natural or synthetic, polymeric or non-polymeric resins, binders, with low or high molar masses. Polymeric film formers may be natural or synthetic, addition or condensation, homo-or hetero-chain, mono-or poly-disperse, organic or inorganic, homopolymer or copolymer, linear or branched or cross-linked, charged or uncharged, thermoplastic or thermosetting, elastomeric, crystalline or amorphous or both, isotactic or syndiotactic or atactic.

Polymeric film formers include polyolefins, polyvinyls, polyacrylates, polyurethanes, polysiloxanes, polyamides, polyesters, fluoropolymers, polyethers, polyacetates, polycarbonates, polyimides, rubbers, epoxies, formaldehyde resins, and homopolymers and copolymers thereof.

Suitable hydrophobic (lipophilic) film-forming polymers include, but are not limited to, those described in U.S. Pat. No.7,037,515 to Kalafsky et al, U.S. Pat. No.6,685,952 to Ma et al, U.S. Pat. No.6,464,969 to De La Poterie et al, U.S. Pat. No.6,264,933 to Bodelin et al, U.S. Pat. No.6,683,126 to Keller et al, and U.S. Pat. No.5,911,980 to Samour et al, the disclosures of which are incorporated herein by reference.

Mention may in particular be made of polyolefins, in particular C₂-C₂₀Olefin copolymers, such as polybutene; with saturated or unsaturated C being straight-chain or branched₁-C₈Alkyl celluloses of the alkyl group such as ethyl cellulose and propyl cellulose; copolymers of Vinylpyrrolidone (VP) and in particular vinylpyrrolidone and C₂-C₄₀And preferably C₃-C₂₀Copolymers of olefins, including copolymers of vinylpyrrolidone and eicosene or dodecane monomers sold under the trade names Ganex V220 and Ganex V216 Polymers (ISP inc. nj, Wayne); polysiloxane polymers and polyorganosiloxanes including, but not limited to, polyalkylsiloxanes, polyarylsiloxanes or polyalkylarylsiloxanes, mention may be made in particular of polydimethylsiloxanes; polyanhydride resins such as those available from Chevron under the trade name PA-18; derived from maleic anhydride and C₃-C₄₀Copolymers of olefins such as octadecene-1; polyurethane polymers such as Performa V825 (New phase technologies) and those described in U.S. Pat. No.7,150,878 to Gonzalez et al, the contents of which are incorporated herein by reference; and polymers and copolymers prepared from esters of vinyl acid monomers, including but not limited to (meth) acrylates (also referred to as (meth) acrylates), such as alkyl (meth) acrylates in which the alkyl group is selected from linear, branched, and cyclic (C)₁-C₃₀) Alkyl radicals, e.g. (meth) acrylic acid (C)₁-C₂₀) Alkyl ester, and more preferably (meth) acrylic acid (C)₆-C₁₀) An alkyl ester. Mention may be made, among the alkyl (meth) acrylates, of those chosen from methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylateEsters, and the like. Mention may be made, among the aryl (meth) acrylates, of those chosen from benzyl acrylate, phenyl acrylate and the like. The alkyl group in the above esters may be selected from, for example, fluorinated and perfluorinated alkyl groups, that is, some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. Mention may also be made of amides of acid monomers, such as (meth) acrylamides, for example N-alkyl (meth) acrylamides, for example (C)₁-C₂₀) Alkyl groups including, but not limited to, N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide, and N-undecylacrylamide. The vinyl polymer used for the hydrophobic film-forming polymer may also be obtained by homopolymerization or copolymerization of at least one monomer selected from vinyl esters, olefins (including fluorinated olefins), vinyl ethers, and styrene monomers. For example, these monomers may be copolymerized with, for example, at least one of the above-mentioned acid monomers, esters thereof, and amides thereof. Non-limiting examples of vinyl esters which may be mentioned are selected from vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl tert-butylbenzoate. Among the olefins that may be mentioned are those chosen, for example, from ethylene, propylene, butene, isobutene, octene, octadecene, and polyfluorinated olefins chosen, for example, from tetrafluoroethylene, 1-difluoroethylene, hexafluoroethylene and chlorotrifluoroethylene. Styrene monomers which may be mentioned are selected, for example, from styrene and alpha-methylstyrene. The list of monomers given is non-limiting and any monomer known in the art to fall within the class of acrylic and vinyl monomers (including polysiloxane chain modified monomers) that can result in a hydrophobic film can be used. In this connection, mention may be made in particular of the commercially available film former cyclopentasiloxane (and) acrylate/polydimethylsiloxane copolymer (KP-545, Shinetsu Chemical co., Ltd).

Other film formers known in the art may be advantageously used in the composition. These include acrylate copolymers, acrylates C_12-22Alkyl methacrylate copolymers, acrylate/octylacrylamide copolymers, acrylate/VA copolymers, amino-terminated polydimethylsiloxanes, AMP/acrylate copolymersCopolymers, behenyl/isostearyl, butylated PVP, butyl ester copolymer of PVM/MA, calcium/sodium PVM/MA copolymer, polydimethylsiloxane copolymer, polydimethylsiloxane/mercaptopropylmethylsiloxane copolymer, polydimethylsiloxane propylethylenediamine behenate, dimethiconol ethylcellulose, ethylene/acrylic acid copolymers, ethylene/MA copolymers, ethylene/VA copolymers, fluorinated C_2-8Alkyl polydimethylsiloxane, C_30-38Olefin/isopropyl maleate/MA copolymer, hydrogenated styrene/butadiene copolymer, hydroxyethyl ethyl cellulose, isobutylene/MA copolymer, methyl methacrylate crosspolymer, methacryloyl ethyl betaine/acrylate copolymer, octadecene/MA copolymer, octadecene/maleic anhydride copolymer, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, oxidized polyethylene, perfluoropolymethyl isopropyl ether, polyethylene, polymethyl methacrylate, polypropylene, PVM/MA decadiene crosspolymer, PVM/MA copolymer, PVP/decene copolymer, PVP/eicosene copolymer, PVP/hexadecene copolymer, PVP/MA copolymer, PVP/VA copolymer, hydrogenated styrene/butadiene copolymer, hydroxyethyl ethyl cellulose, isobutylene/MA copolymer, isobutylene/methyl methacrylate crosspolymer, isobutylene/styrene copolymer, isobutylene copolymer, sodium acrylate/vinyl alcohol copolymer, stearyloxypolydimethylsiloxane, stearyloxytrimethylsilane, stearyl alcohol, stearyl vinyl ether/MA copolymer, styrene/DVB copolymer, styrene/MA copolymer, tetramethyltetraphenyltrisiloxane, melissyl/PVP, trimethylpentaphenyltrisiloxane, trimethylsiloxysilicate, VA/crotonate copolymer, VA/crotonate/vinylpropionate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, vinyldecanolactam/PVP/dimethylaminoethyl methacrylate copolymer and vinyl polydimethylsiloxane.

Further non-limiting representative hydrophobic film-forming poiyurethanes include at least one condensation polymer selected from the group consisting of polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, and polyurea/polyurethanes. The polyurethane may be, for example, at least one selected from the group consisting of: aliphatic, cycloaliphatic, and aromatic urethane, polyurea urethane and polyurea copolymers comprising at least one of the following: at least one sequence of aliphatic, cycloaliphatic and aromatic polyester origin, for example at least one branched or unbranched siloxane sequence derived from polydimethylsiloxane and polymethylphenylsiloxane, and at least one sequence comprising fluorinated groups. Further non-limiting representative condensation polymers may be selected from polyesters, polyesteramides, fatty chain polyesters, polyamide resins, epoxy ester resins, arylsulfonamide-epoxy resins, and resins resulting from the condensation of formaldehyde and arylsulfonamides.

Hydrophobic films may also be formed in situ by the use of a post-cured resin applied to the skin, nail or hair, including, for example, the formation of polydimethylsiloxane films by the hydrosilylation of hydrosilanes with alkene-substituted siloxanes or by the in situ polycondensation of alkoxy-functionalized siloxanes.

Preferred polymeric film formers include acrylates, alkyl acrylates, polyurethanes, fluoropolymers such as fluoomer (polyperfluoro perhydrophenanthrene), and silicone polymers. Particularly preferred are silicone acrylates, such as acrylate/polydimethylsiloxane copolymers sold under the tradenames KP-545 or KP550 (Shin-Etsu).

Other film formers that may be used include, but are not limited to, natural, mineral, and/or synthetic waxes. Natural waxes are those of animal origin, including but not limited to beeswax, spermaceti, lanolin, and shellac wax, and those of vegetable origin, including but not limited to carnauba wax, candelilla wax, bay, and sugarcane wax, and the like. Mineral waxes that may be used include, but are not limited to, ozokerite, ceresin, lignite, paraffin, microcrystalline, petrolatum, and petrolatum waxes. Synthetic waxes include, for example, Fischer Tropsch (FT) waxes and polyolefin waxes, such as ethylene homopolymers, ethylene-propylene copolymers, ethylene-hexene copolymers. Representative ethylene homopolymer waxes are under the trade namePolyeVinylene (baker Hughes incorporated) is commercially available. Commercially available ethylene-alpha-olefin copolymer waxes include those under the trade nameThose sold by copmers (bakerhughes incorporated). Other suitable waxes are dimethiconol beeswax, which may be ULTRABEE^TMThe polydimethylsiloxane alcohol ester was obtained from Noveon.

In some embodiments, it is desirable to add hydrophilic or water soluble film forming agents (e.g., cellulosics, polysaccharides, polyquats, etc.) to the composition to improve spreadability, emulsion stability, and the like. Although not so preferred, it is within the scope of the present invention to include such hydrophilic or water soluble film forming agents. The amount of hydrophilic or water soluble film former is not limited, but at high concentrations (e.g., greater than 20% by weight based on the total weight of the film former) it is desirable to increase the ratio of hydrophobic particles to film former to counter the decrease in surface hydrophobicity. In some embodiments, the overall weight percentage of hydrophilic or water soluble film former will be less than about 20%, preferably less than about 15%, more preferably less than about 10% and most preferably less than about 5% by weight based on the total weight of the total film former. In a preferred embodiment, the hydrophilic film former comprises less than about 2% by weight of the total weight of film formers in the emulsion. In one embodiment, the dairy industry is substantially free of water soluble film forming agents, meaning that the amount of water soluble film forming agent present does not impart a measurably different contact angle with water relative to the same composition in the absence of the water soluble film forming agent.

Combinations of any of the foregoing film formers are also considered suitable, including combinations of polymeric and non-polymeric film formers.

The second essential component of the present invention is a particulate material which is hydrophobic in nature or which has been hydrophobically modified by surface treatment or the like. Without wishing to be bound by theory, it is believed that the particulate material provides a surface roughness or structure on the membrane on a nanometer scale (1nm to 1,000nm) or micrometer scale (1 μm to 200 μm) which imparts superhydrophobicity by providing protrusions on which water droplets can rest, thereby minimizing contact of water with the surface from a maximum, i.e., reducing surface adhesion. The surface roughness can be observed or measured by AFM, SEM, or the like. In some, but not all embodiments, the particulate material is not porous.

Preferred particulate materials of the present invention are hydrophobically modified Silicas (SiO)₂) Powders, including fumed silica or fumed silica (e.g., having a particle size range of about 7nm to about 40 nm). Other noteworthy particulate materials are hydrophobically modified metal oxides, including but not limited to titanium dioxide (TiO)₂) Alumina (Al)₂O₃) Zirconium dioxide (ZrO)₂) Tin dioxide (SnO)₂) Zinc oxide (ZnO), and combinations thereof.

Advantageously, the particulate material may be one that provides additional functionality to the composition, including, for example, Ultraviolet (UV) light absorption or scattering, in this case, for example, titanium dioxide and zinc oxide particles, or aesthetic features such as color (e.g., pigments), pearlescence (e.g., mica), and the like. The particulate material may be based on, for example, organic or inorganic particulate pigments. Examples of organic particulate pigments include lakes, especially aluminum lakes, strontium lakes, barium lakes, and the like. Examples of inorganic particulate pigments are iron oxides, especially red, yellow and black, titanium dioxide, zinc oxide, potassium ferricyanide (K)₃Fe(CN)₆) Potassium ferrocyanide (K)₄Fe(CN)₆) Potassium ferrocyanide trihydrate (K)₄Fe(CN)₆·3H₂O) 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 1640419, the disclosure of which is incorporated herein by reference.

In one embodiment, the particulate material is surface treated to impart a hydrophobic coating thereon. Hydrophobically modified particles and methods for making hydrophobically modified particles are known in the art, for example, as described in U.S. Pat. No.3,393,155 to Schutte et al, Wagner et alU.S. Pat. No.2,705,206, U.S. Pat. No.5,500,216 to Wagner et al, U.S. Pat. No.6,683,126 to Keller et al, and U.S. Pat. No.7,083,828 to Muller et al, U.S. patent publication No.2006/0110541 to Russell et al, and U.S. patent publication No.2006/0110542 to Dietz et al, the disclosures of which are incorporated herein by reference. In one embodiment, hydrophobic particles according to embodiments of the present invention may be formed from oxide particles (e.g., metal oxides, silica, etc.) whose surfaces are covered (e.g., covalently bonded) with non-polar groups. Such as alkyl groups, polysiloxanes, siloxanes, alkyl siloxanes, organosiloxanes, fluorinated siloxanes, perfluorinated siloxanes, organosilanes, alkyl silanes, 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 incorporated herein by reference, describes suitable fluorinated silane-coated particles formed by reacting particles having a nucleophilic group such as oxygen or hydroxyl with a silicon-containing compound having a hydrocarbyl group substituted with at least one fluorine atom and a reactive hydrocarbyloxy group capable of being substituted with the nucleophilic group. An example of such a compound is tridecafluorooctyltriethoxysilane, which is available under the trade name DYNASILANE^TMF8261 was purchased from Sivento, Piscataway, n.j. The hydrophobically modified silica materials described in U.S. patent publication 2006/0110542 to Dietz et al, which is incorporated herein by reference, are particularly suitable.

Any of the hydrophobically modified particulate materials described in U.S. Pat. No.6,683,126 to Keller et al, the disclosure of which is incorporated herein by reference, are also useful, including but not limited to, by treating oxide materials (e.g., SiO) with compounds containing (perfluorinated) alkyl groups₂、TiO₂Etc.) containing at least one reactive functional group that can undergo a chemical reaction with the adjacent-surface OH groups of the oxide support particles, including, for example, hexamethyldisilazane, octyltrimethoxysilane, silicone oil, trimethylsilyl chloride, and dichlorodimethylsilane.

Suitable hydrophobically modified fumed silica particles include, but are not limited toLimited to AEROSIL from Degussa corporation of Parsippany, N.J^TM R 202、AEROSIL^TM R 805、AEROSIL^TMR 812、AEROSIL^TM R 812 S、AEROSIL^TM R 972、AEROSIL^TM R 974、AEROSIL^TM R 8200、AEROXIDE^TM LE-1、AEROXIDE^TMLE-2 and AEROXIDE^TMLE-3. Other suitable particles include Tegotop^TM105(Degussa/Goldschmidt Chemical Corporation) and under the name Mincor^TM300(BASF) commercially available vinyl polymer pellets. Silica (SiO)₂) And hydrophobically modified silicas are particularly useful in some embodiments, and in other embodiments, the compositions are substantially free of silica or hydrophobically modified silica. By "substantially free of silica or hydrophobically modified silica" is meant that these components comprise less than about 2%, preferably less than about 1%, and more preferably less than about 0.5% of the one or more particulate materials. A suitable hydrophobically modified alumina particle is ALU C805 from Degussa.

The one or more particulate materials may also include 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 microcapsules comprising a shell material as described in U.S. patent publication 2005/0000531, the disclosure of which is incorporated herein by reference.

The one or more particulate materials are typically in the form of a powder having a median particle size of from about 1nm (nanometers) to about 1mm (millimeters), more typically between about 5nm to about 500 μm (micrometers), preferably from about 7nm to about 1 μm, 5 μm, 20 μm, 50 μm, or about 100 μm. When more than one particulate material is used (e.g. modified TiO)₂And modified SiO₂) The median particle size of each powder is preferably within the above range.

Particulate materials having a median particle size in excess of about 1mm may be too large unless the particles themselves contain a surface roughness in a suitable size range. For example, surface treatment of larger particles with polymer chains in the 20nm range may provide acceptable surface roughness. The roughness of the resulting film may be characterized by the size of the primary particles, the size of the agglomerated particles in the aggregate, or the distribution of particle sizes.

The proportions of the individual components in the compositions of the present invention are controlled to produce compositions having the desired superhydrophobic effect. For example, the weight ratio of hydrophobic film former to particulate material may be from about 1: 2 to about 2: 1, including ratios of about 1: 2, about 1: 1.75, about 1: 1.5, about 1: 1.25, about 1: 1, about 1.25: 1, about 1.5: 1, about 1.75: 1, and about 2: 1. Particularly good results are obtained when the weight ratio of hydrophobic film former to particulate material is about 1: 1.

The hydrophobic film former and the particulate material may together comprise at least about 50%, at least about 60%, at least about 70%, or at least about 80% by weight of the non-volatile portion of the emulsion. Typically, the hydrophobic film former and particulate material together comprise less than about 95%, less than about 90%, or less than about 85% by weight of the non-volatile portion of the emulsion. In one embodiment, the hydrophobic film former and particulate material together comprise from about 80% (or greater than 80%) to about 90% by weight of the non-volatile portion of the emulsion.

Water-in-oil emulsions

The compositions of the present invention are preferably formulated as water-in-oil emulsions. These emulsions comprise an oil-containing continuous phase and an aqueous discontinuous phase.

The oil-containing phase typically comprises from about 10% to about 99%, preferably from about 20% to about 85%, and more preferably from about 30% to about 70% by weight of the total weight of the emulsion, and the aqueous phase typically comprises from about 1% to about 90%, preferably from about 5% to about 70%, and more preferably from about 20% to about 60% by weight of the total weight of the emulsion. The aqueous phase typically comprises from about 25% to about 100%, more typically from about 50% to about 95%, by weight, of water.

The oil-containing phase may consist of a single oil or a mixture of different oils. Essentially any oil can be used, but 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 didecyl ether; fatty alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol; isoparaffins such as isooctane, isododecane, and isohexadecane; silicone oils such as polydimethylsiloxane, cyclosiloxane and polysiloxane; hydrocarbon oils such as mineral oil, vaseline, isoeicosane and polyisobutylene; natural or synthetic waxes, and the like.

Suitable hydrophobic hydrocarbon oils may be saturated or unsaturated, have aliphatic character and are straight or branched chain or contain alicyclic or aromatic rings. The hydrocarbon oils include those having 6 to 20 carbon atoms, and those having 10 to 16 carbon atoms are particularly preferred. Representative hydrocarbons include decane, dodecane, tetradecane, tridecane and C_8-20An isoparaffin. Useful paraffinic hydrocarbons are available under the trademark ISOPARS from Exxon, and from permethyl corporation. In addition, C_8-20Paraffinic hydrocarbons, such as Permethyl 99A, manufactured by Permethyl Corporation, having the trade name^TMC of (A)₁₂Isoparaffins (isododecane) are also suitable. Various commercially available C₁₆Isoparaffins, such as isohexadecane (having the trade name Permethyl R)^TM) Are also suitable. Examples of preferred volatile hydrocarbons include polydecanes, such as isododecane and isodecane, including, for example, Permethyl-99A (Presperse Inc.) and C₇-C₈To C₁₂-C₁₅Isoparaffins, such as Isopar series from Exxon Chemicals. A representative hydrocarbon solvent is isododecane.

It is critical that the emulsion have little or no non-volatile hydrophilic components, including some conventional humectants. Components such as glycerol and polyols (including propylene glycol, ethoxydiglycol, glycerol, butylene glycol, pentylene glycol and hexylene glycol) should be removed or should be kept in a concentration such that the total amount of non-volatile hydrophilic components does not exceed 15% by weight and preferably is less than 10%, less than 5%, less than 2% or less than 1% by weight. Glycerol has been found to be particularly detrimental to achieving superhydrophobicity, and therefore the concentration should be kept below 2% by weight or completely removed.

It has been found that the choice and amount of emulsifier is important to obtain a membrane that provides superhydrophobic properties. Because the emulsifier itself may be detrimental to the formation of a superhydrophobic film, the composition preferably has a minimum concentration of emulsifier capable of producing a stable emulsion. The amount of emulsifier is typically from about 0.001 wt% to about 10 wt%, and preferably ranges from about 0.01 to about 5 wt%, and most preferably from about 0.1 wt% to about 1 wt%, based on the total weight of the composition.

For water-in-oil emulsions, the emulsifier itself should have a low HLB, preferably below 10, more preferably below 8.5. Although a combination of more than one emulsifier is within the scope of the present invention, each emulsifier should individually have a low HLB. Thus, it is also less desirable to use a combination of high and low HLB emulsifiers to bring about a low HLB (e.g., less than 8.5) because higher HLB emulsifiers are detrimental to the formation of superhydrophobic films even if the combined HLB of the system is less than 8.5. If present, the amount of emulsifier having an HLB above 10 will be less than 1% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.2% by weight.

When the emulsifier is of the polyethoxylated type (for example polyoxyethylene ethers or esters) it comprises- (CH)₂CH₂O)_n-chains of the form n generally less than 20, preferably less than 10, more preferably less than 7 and most preferably less than 5. Propoxylated emulsifiers are also considered suitable. Propoxylated emulsifiers typically have less than 20, more preferably less than 10, and most preferably less than 5 propylene oxide repeat units.

Emulsifiers that may be used in the compositions of the present invention include, but are not limited to, one or more of the following: sorbitan esters, polyglyceryl-3-diisostearate, sorbitan monostearate, sorbitan tristearate, sorbitan sesquioleate, sorbitan monooleate; glycerides, such as glycerol monostearate and glycerol monooleate; polyoxyethylene phenols such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol; polyoxyethylene ethers such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether; polyoxyethylene glycol ester; polyoxyethylene sorbitan esters; a dimethicone copolyol; polyglyceryl esters, such as polyglyceryl-3-diisostearate; glyceryl laurate; stearyl polyoxyethylene (2) ether and stearyl polyoxyethylene (6) ether. Additional emulsifiers are provided in INCI Ingredient Dictionary and Handbook, 11 th edition, 2006, the disclosure of which is incorporated herein by reference.

An example of a very low HLB emulsifier suitable in accordance with the present invention is Span 83, a 2: 1 molar ratio sesquiester of mono-and dioleic acid having an HLB of 3.7. Sorbitan monostearate (INCI) is another suitable emulsifier having an HLB value of 4.7.

The aqueous phase may include one or more additional solvents, preferably volatile solvents, including lower alcohols, such as ethanol, isopropanol, and the like. The volatile solvent may also be a cosmetically acceptable ester, such as butyl acetate or ethyl acetate; ketones such as acetone or ethyl methyl ketone, and the like. When present in the aqueous phase, the volatile solvent typically comprises from about 0.1% to about 75% by weight of the aqueous phase, more typically up to about 35% by weight and preferably up to about 15% by weight. Water and optionally volatile solvents are believed to enhance the formation of superhydrophobic films because the particles tend to be pushed to the surface of the film as the solvent evaporates.

Water-in-silicone emulsions

One type of water-in-oil emulsion that has been found to be useful is a water-in-silicone emulsion having a continuous phase comprising silicone oil and a discontinuous phase of water.

The silicone-containing phase typically comprises from about 20% to about 95%, preferably from about 25% to about 85%, and more preferably from about 35% to about 70% by weight of the total emulsion, and the aqueous phase typically comprises from about 5% to about 90%, preferably from about 10% to about 70%, and more preferably from about 20% to about 60% by weight of the total emulsion. The aqueous phase typically comprises from about 25% to about 100%, more typically from about 50% to about 95%, by weight, of water.

The silicone oil phase can include volatile silicone oils, non-volatile silicone oils, and combinations thereof. By "volatile silicone oil" is meant an oil that is readily volatile at ambient temperatures. Typically, the volatile silicone oil has a vapor pressure in the range of from about 1Pa to about 2kPa at 25 ℃, preferably has a viscosity of from about 0.1 to about 10 centistokes or less at 25 ℃, preferably about 5 centistokes or less, more preferably about 2 centistokes or less, and a boiling point at atmospheric pressure in the range of from about 35 ℃ to about 250 ℃.

Volatile silicones include cyclic and linear volatile dimethylsiloxane polysiloxanes. In one embodiment, the volatile siloxane may include cyclomethicone, including tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicone, or mixtures thereof. Mention may in particular be made of the volatile cyclomethicones hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. A suitable polydimethylsiloxane may be Dow Corning from Dow CorningFluid and have a viscosity of 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, the entire contents of which are incorporated herein by reference. Additional Volatile Silicone materials are described in Todd et al, "Volatile Silicone Fluids for Cosmetics," Cosmetics and Toiletries, 91: 27-32(1976), the entire contents of which are incorporated herein by reference. Linear volatile silicones generally have viscosities of less than about 5 centistokes at 25℃, while cyclic silicones have viscosities of less than about 10 centistokes at 25℃. Examples of volatile silicones of various viscosities include Dow Corning 200, Dow Corning 244, Dow Corning 245, Dow Corning 344 and Dow Corning 345(Dow Corning Corp.); SF-1204 and SF-1202 Silicone Fluids (G.E. silicones), GE 7207 and 7158(General Electric Co.); and SWS-03314(SWS Silicones Corp.). The linear volatile siloxane includes low molecular weight polydimethylsiloxane compounds such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like.

The non-volatile silicone oil typically comprises a polyalkylsiloxane, a polyarylsiloxane, a polyalkylarylsiloxane, or a mixture thereof. Polydimethylsiloxane is the preferred non-volatile silicone oil. The non-volatile silicone oil typically has a viscosity of from about 10 to about 60,000 centistokes at 25 ℃, preferably from about 10 to about 10,000 centistokes, and more preferably from about 10 to about 500 centistokes; and a boiling point greater than 250 ℃ at atmospheric pressure. Non-limiting examples include dimethylpolysiloxane (polydimethylsiloxane), phenyl trimethicone, and diphenyl polydimethylsiloxane.

The volatile and nonvolatile silicone oils may optionally be substituted with a variety of functional groups, such as alkyl, aryl, amine, vinyl, hydroxyl, haloalkyl, alkylaryl, and acrylate groups, among others.

The water-in-silicone emulsion is emulsified using a nonionic surfactant (emulsifier). Suitable emulsification systems include polydiorganosiloxane-polyoxyalkylene block copolymers, including those described in U.S. Pat. No.4,122,029, the disclosure of which is incorporated herein by reference. These emulsifiers usually comprise a polydiorganosiloxane backbone, typically polydimethylsiloxane, having an inclusion of- (EO)_m-and/or- (PO)_nSide chains of radicals in which EO is ethyleneoxy and PO is 1, 2-propyleneoxy, typically with hydrogen or lower alkyl (e.g. C)_1-6Typical of C_1-3) Blocking or end-capping. Such side chains preferably comprise 50 EO and/or PO units or less (e.g., m + n < 50), preferably 20 or less, and more preferably 10 or less. In addition to alkoxylated side chains, silicone emulsifiers may also comprise alkyl chains pendant from the silicone backbone. Other suitable water-in-silicone emulsifiers are disclosed in U.S. Pat. No.6,685,952, the disclosure of which is incorporated herein by reference. Commercially available water-in-silicone emulsifiers include 3225C and 5225C FORMULATION AID from Dow Corning; SILICONE SF-1528 from General Electric; ABIL EM 90 and EM 97 from Goldschmidt Chemical Corporation (Hopewell, Va.); and SILWET sold by OSI Specialties (Danbury, CT)^TMA series of emulsifiers.

Examples of water-in-silicone emulsifiers include, but are not limited to, dimethicone PEG10/15 crosspolymer, dimethicone copolyol, cetyl dimethicone copolyol, PEG-15 lauryl dimethicone crosspolymer, lauryl methicone crosspolymer, cyclomethicone and dimethicone copolyol, dimethicone copolyol (and) caprylic/capric triglyceride, polyglyceryl (4) isostearate (and) cetyl dimethicone copolyol (and) hexyl laurate, and dimethicone copolyol (and) cyclopentasiloxane.

Preferred examples of water-in-silicone emulsifiers include, but are not limited to, PEG/PPG-18/18 dimethicone (trade name 5225C, Dow Corning), PEG/PPG-19/19 dimethicone (trade name BY25-337, Dow Corning), cetyl PEG/PPG-10/1 dimethicone (trade name AbileM-90, Goldschmidt Chemical Corporation), PEG-12 dimethicone (trade name SF 1288, General Electric), lauryl PEG/PPG-18/18 methicone (trade name 5200FORMULATION AID, Dow Corning), PEG-12 dimethicone crosspolymer (trade name 9010 and 9011 silicone elastomer blends, Dow Corning), PEG-10 dimethicone crosspolymer (trade name KSG-20, Shin-Etsu), and dimethicone PEG-10/15 crosspolymer (trade name KSG G 210, Shin-Etsu).

The water-in-silicone emulsifier is typically present in the composition in an amount of from about 0.001% to about 10% by weight, specifically from about 0.01% to about 5% by weight and more preferably less than 1% by weight.

Various fillers and additional components may be added. Suitable fillers include, but are not limited to, silica, treated silica, talc, zinc stearate, mica, kaolin, Nylon powder such as Orgasol^TMPolyethylene powder, Teflon^TMStarch, boron nitride, copolymer microspheres such as Expancel^TM(Nobel Industries)、Polytrap^TM(Dow Corning) and silicone resin microbeads (Tospearl from Toshiba)^TM) And so on.

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, lepidolite, vermiculite, aluminum silicate, starch, smectite clay, alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminum silicate, organically modified montmorillonite clay, hydrated aluminum silicate, aluminum starch octenyl barium succinate silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica alumina, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powders, metal soaps (zinc stearate, magnesium stearate, zinc myristate, calcium palmitate, and aluminum stearate), colloidal silica, and boron nitride; organic powders such as polyamide resin powder (nylon powder), cyclodextrin, polymethyl methacrylate powder, copolymer powder of styrene and acrylic acid, benzoguanamine resin powder, poly (tetrafluoroethylene) 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 such as Bentone Gel and rheoparrl TT 2. Other suitable powders are described in U.S. patent No.5,688,831, the disclosure of which is incorporated herein by reference.

The compositions of the present invention may optionally comprise other active or inactive ingredients typically associated with cosmetic and personal care products, including, but not limited to, excipients, fillers, emulsifiers, antioxidants, surfactants, film formers, chelating agents, gelling agents, thickeners, emollients, humectants, moisturizers, humectants, vitamins, minerals, viscosity and/or rheology modifiers, sunscreen agents, keratolytic agents, depigmenting agents, retinoids, hormonal compounds, alpha-hydroxy acids, alpha-keto acids, antimycotics, antifungal agents, antimicrobial agents, antiviral agents, analgesics, lipid compounds, antiallergic agents, H1 or H2 antihistamines, anti-inflammatory agents, anti-irritants, anti-neoplastic agents, immune system adjuvants, immune system inhibitors, anti-acne agents, anesthetics, antibacterial agents, insect repellents, skin cooling compounds, Skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, colorants, depigmenting agents, pigment reducing agents, preservatives, stabilizers, pharmaceutical agents, light stabilizers, and mixtures thereof. The concentration of such additional components, if present, should be judiciously selected so as not to adversely affect the ability of the emulsion to form a superhydrophobic film. Overall, all such additional components preferably comprise less than 5% by weight of the total composition, more preferably less than about 2% by weight and most preferably less than about 1% by weight.

Cosmetic compositions of the present invention include, but are not limited to, color cosmetics, skin care products, hair care products, and personal care products. Color cosmetics include, for example, foundations and mascaras. Skin care products include, but are not limited to, sunscreens, after-sun products, lotions, and creams. Further applications include topcoats in hair care products, insect repellents, deodorants, antiperspirants, lipsticks, in otolith products, baby wipes, baby creams or lotions, to impart water resistance or water repellency to previously applied cosmetic products, personal care products, hair care products or first aid products. For example, the compositions of the present invention may be applied as a top coat of a sunscreen or sunscreen/insect repellent emulsion previously applied to the skin to improve water resistance or water repellency. Alternatively, the composition may be applied as a top coat to a first ancillary product such as an antibiotic ointment or spray, a bandage or a wound dressing.

In one embodiment, the composition is formulated as a sunscreen comprising hydrophobically modified (i.e., surface treated) titanium dioxide. The hydrophobically modified titanium dioxide may comprise at least about 50%, more typically at least about 75%, preferably at least about 85% and more preferably at least about 95% of the total weight of the one or more particulate materials. In one embodiment, the particulate material consists of, or consists essentially of, hydrophobically modified titanium dioxide. The sunscreen agent optionally includes one or more organic UVA and/or VUB filters (hydrophobic or hydrophilic), but the concentration of hydrophilic organic sunscreen agent in the emulsion should not be so high as to adversely affect the ability to form a superhydrophobic surface and the amount of agglomerates of such organic sunscreen agent is preferably less than about 10% by weight, more preferably less than about 5% by weight. The sunscreen agents of the present invention exhibit improved water resistance relative to conventional emulsion-based sunscreens.

The compositions of the present invention may have one or more active sunscreen agents. Such sunscreen actives may be organic or inorganic and water or oil soluble. Such active agents include those used for UVA and UVB protection (290 to 400 nm solar radiation). Such sunscreen actives include, but are not limited to, one or more of the following: dibenzoylmethane, oxybenzone, sulfoisobenzone (sulisobenzone), dioxybenzophenone, methyl anthranilate, p-aminobenzoic acid (PABA), octyl methoxycinnamate, DEA methoxycinnamate, octocrylene, triazololtrisiloxane, octyl salicylate, monothicylsalicylate, octyldimethyl PABA, TEA salicylate, 4-methylphenylene camphor, octyltriazone, p-xylylene dicamphor sulfonic acid, phenylbenzimidazole sulfonic acid, ethyl PABA, hydroxymethylphenylbenzotriazole, methylenebis-benzotriazolyl tetramethylbutylphenol, bis-ethylhexyloxyphenol, methoxyphenol triazine, titanium dioxide, zinc oxide, or any derivative or any combination thereof. Other useful sunscreen actives include those disclosed in U.S. patent No.5,000,937, the disclosure of which is incorporated herein by reference. Preferred sunscreens include octyl methoxycinnamate, octyl salicylate, octocrylene, avobenzone, benzophenone-3 and silicone-15 (Parsol slx).

In one embodiment, the composition is applied to the skin, preferably facial skin. Such compositions may be formulated as foundations, blushes, and the like. In another embodiment, the composition is provided as a water-resistant, transfer-resistant lip product (e.g., lipstick or lip gloss). The color cosmetic optionally comprises one or more colorants including dyes, lakes, pigments, or combinations thereof.

In another embodiment, the composition is applied to the hair and provides anti-wetting properties. Thus, for example, the composition is applied to the hair before swimming so that the hair is not wetted, or is only minimally wetted, after immersion in water. By "minimally wetted" is meant that the weight of the hair after immersion is increased by 100% or less, preferably 50% or less, more preferably 25% or less and most preferably 10% or less, relative to the weight before immersion in water. Furthermore, after one or two vigorous shakes of the hair, the hair is substantially dry. By "substantially dry" is meant that the weight of the hair is increased by less than about 5% or less than about 2.5% relative to the weight of the hair prior to immersion. The above can be tested using hair samples treated with the composition of the present invention. The composition may also be applied to the hair of a pet, such as a dog, prior to swimming, so that after swimming, without the need for a towel wipe or the like, the pet is substantially dry, or on livestock, so that it is not wet by snow, rain or mud.

The additional components may be incorporated in the form of fillers or the additional components may have various functional purposes that are conventional in the cosmetic field. However, while additional components for formulating the above cosmetic compositions may be included, the inclusion of additional components is defined as those that do not interfere with the formation of the superhydrophobic film.

Examples

Example 1

This embodiment provides an emulsion for imparting a superhydrophobic film on hair. Emulsion formulations 1A, 1B and 1C were prepared according to table 1.

TABLE 1

¹Cyclomethicone from Dow Corning;²silmer UR-5050 from Siltech;³q2-1403Fluid from Dow Corning;⁴KP 545SiliconeAcrylat polymer from Shin-Etsu;⁵aeroxide Alu C805 fumed Alumina from Degussa;⁶aeroxide LE3 from Degussa;⁷iron Oxide Black NF 11S2 from Kobo;⁸DowCorning 5225C；⁹all amounts given are weight percentages.

Emulsions 1A, 1B, and 1C were applied as thin films on glass slides and the volatiles were allowed to evaporate. The contact angles with the water droplets were measured as 141.7(1A), 145(1B) and 143.3 (1C). In this and subsequent examples, contact angles were measured using a Kruss Drop Shape Analysis System DSA 10MK 2. The contact angle was calculated by the instrument software using a circle fitting method. The volume of water (i.e., droplet size) was set to 5 μ l.

Example 2

This example provides an emulsion-based mascara for imparting a superhydrophobic film on eyelashes. Emulsions were prepared according to the formulations provided in table 2.

TABLE 2

INCI name/description	By weight%
		Isododecane (IDD)	50
Beeswax (Cera flava)	2.5
		Candelilla wax	2.5
Acrylate/stearate acrylate/polydimethylsiloxane methacrylate copolymer1	9.5
		Isododecane and acrylate/polydimethylsiloxane copolymers2	5
Stearic acid glyceride	1
		D&C Black No.23	1
Hydrophobic fumed silica4	11
		Iron oxide and triethoxyoctylsilane5	3
PEG/PPG-19/19 polydimethylsiloxane and hydrogenated polyisobutene6	2.5
		Butanediol	0.5
Sodium chloride	0.5
		Water (W)	11
Total of	100

¹KP 561 from Shin-Etsu;²KP550 from Shin Etsu;³carbonbblack from LCW;⁴aeroxide LE3 from Degussa;⁵iron Oxide Black NF 11S2 from Kobo;⁶Dow Corning BY 25-337。

the film was prepared by depositing the emulsion on a glass slide and allowing the volatiles to evaporate. The contact angle with the water drop was measured to be 142.7 ± 1.97.

Example 3

This example provides an emulsion-based foundation for imparting a superhydrophobic film on facial skin. Emulsions were prepared according to the formulations provided in table 3.

TABLE 3

¹Covalenine AS from Sensient;²aeroxide Alu C805 from Degussa;³KP550 from Shin-Etsu;⁴versagel MD1600 from Penreco;⁵Dow Corning5200flormulation aid；⁶PMMA spherial from Kobo;⁷orgasolnylon powder from Lipo;⁸cellulobead from Kobo;⁹tayca MT100SAS TiO from Tayca₂AS treated；¹⁰TiO from Cardre₂AS treated；¹¹Black Iron oxideNF 11S2 from Kobo;¹²red Iron Oxide from Ciba;¹³yellow Iron Oxide from Ciba;¹⁴sebustop from Barnet.

The film was prepared by depositing the emulsion on a glass slide and allowing the volatiles to evaporate. The contact angle with a drop of water was measured to be 146.8.

Example 4

This embodiment provides an emulsion-based sunscreen for imparting a superhydrophobic film on the skin. Emulsions were prepared according to the formulation in table 4. Organic sunscreens (including those listed herein) or insect repellents (e.g., DEET, IR3535 or Picaridin) may also be added to this formulation.

TABLE 4

INCI name/description	By weight%
		Cyclopentasiloxane	15
Titanium dioxide and trimethoxyoctylsilane1	6
		Alumina and trimethoxyoctylsilane2	6
Isododecane (IDD)	15
		Isododecane and acrylate/polydimethylsiloxane copolymers3	8
PEG/PPG-18/18 Dimethicone and Cyclopentasiloxane4	7.5
		Polydimethylsiloxane and dimethiconol5	2.5
Water (W)	40
		Total of	100

¹Tegosun T805G from Degussa;²aeroxide Alu C805 from Degussa;³KP550 from Shin-Etsu;⁴Dow Corning 5225C；⁵Dow Corning 1403fluid。

the contact angle with water was measured as above and found to be 144.9.

Example 5

This embodiment provides a skin care emulsion that imparts a superhydrophobic film on skin. Emulsions were prepared according to the formulations provided in table 5.

TABLE 5

INCI name/description	5A5	5B
			Hydrophobic fumed silica1	5.0	5.0
Disiloxanes2	41.0	58.0
			PEG/PPG-19/19 polydimethylsiloxane and hydrogenated polyisobutene3	2.0	2.0
Dihydroxypropyl dimethicone/SMDI copolymer and isododecane4	-	5.0
			Water (W)	52.0	30.0
Total of	100	100

¹Aeroxide LE3 from Degussa;²silicone Fluid 65cs from Dow Corning;³ts50-IP emulsifier from Dow Corning;⁴silmer UR-5050 from Siltech;⁵all amounts given are in weight percent.

The contact angle with water was 140.6 for formulation 5A and 143.7 for 5B, measured as above.

When the above composition is applied to skin or hair, it makes the skin and hair non-wettable and has a favorable aesthetic feeling.

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

Claims (16)

1. A composition for imparting a hydrophobic film on a surface comprising:

a water-in-oil emulsion comprising:

(i) a continuous oil phase;

(ii) a discontinuous aqueous phase; and

(iii) 0.001 to 10 wt%, based on the total weight of the composition, of an emulsifier having an HLB value of less than 10 selected from: sorbitan esters, polyglyceryl-3-diisostearate, sorbitan monostearate, sorbitan tristearate, sorbitan sesquioleate, sorbitan monooleate, glycerol esters, polyoxyethylene phenols, polyoxyethylene ethers, polyoxyethylene glycol esters, polyoxyethylene sorbitan esters, dimethicone copolyols and polyglyceryl esters;

(iv) one or more hydrophobic film-forming agents,

(v) one or more hydrophobic particulate materials having a median particle size of from 5nm to 1 mm; the weight ratio of the one or more hydrophobic film formers to the one or more hydrophobic particulate materials is from 1: 5 to 5: 1; and said one or more hydrophobic film formers and said one or more hydrophobic particulate materials together comprise at least 5% by weight of said water-in-oil emulsion; and

wherein the total weight percent of all non-volatile water-soluble or water-dispersible organic components in the water-in-oil emulsion is less than 15 percent, based on the total weight of the emulsion; the composition is capable of providing a film on a surface upon evaporation of the volatile component, characterized by a contact angle with water of greater than 140 °.

2. A composition according to claim 1, wherein the emulsifier has an HLB value of less than 8.5.

3. A composition for imparting a superhydrophobic film on a surface comprising:

a water-in-silicone emulsion comprising:

(i) a continuous silicone oil phase;

(ii) a discontinuous aqueous phase; and

(iii) emulsifier comprising an organosiloxane polymer having side chains comprising- (EO)_m-and/or- (PO)_n-a group wherein the sum of n and m is 50 or less, the side chain being terminated by hydrogen or lower alkyl;

(iv) one or more hydrophobic film-forming agents,

(v) one or more hydrophobic particulate materials having a median particle size of from 5nm to 1 mm; the weight ratio of the one or more hydrophobic film formers to the one or more hydrophobic particulate materials is from 1: 5 to 5: 1; and said one or more hydrophobic film formers and said one or more hydrophobic particulate materials together comprise at least 2% by weight of said water-in-oil emulsion; and

wherein the total weight percent of non-volatile water-soluble or water-dispersible organic components in the water-in-silicone emulsion is less than 15 percent, based on the total weight of the emulsion; the composition is capable of providing a film on a surface upon evaporation of the volatile component, characterized by a contact angle with water of greater than 140 °.

4. The composition according to any one of the preceding claims, wherein the one or more hydrophobic particulate materials comprise oxide particles selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, zirconium dioxide, tin dioxide, zinc oxide, iron oxide, and combinations thereof, the oxide particles having hydrophobic moieties covalently bonded to their surfaces.

5. A composition according to claim 4, wherein the oxide particles comprise silica.

6. Composition according to claim 5, in which the silica is a fumed silica.

7. The composition of claim 4, wherein the oxide particles comprise alumina.

8. The composition according to claim 7, wherein the alumina is fumed alumina.

9. The composition according to claim 4, wherein the hydrophobic moiety comprises one or more of an alkyl, fluoroalkyl, perfluoroalkyl, siloxane, alkylsiloxane, fluoroalkyl siloxane, or perfluoroalkyl siloxane.

10. A composition according to any one of the preceding claims 1 to 4, wherein the weight ratio of the one or more hydrophobic film formers to the one or more hydrophobic particulate materials is from 1: 5 to 2: 1.

11. A composition according to any one of the preceding claims 1 to 4, wherein the weight ratio of the one or more hydrophobic film formers to the one or more hydrophobic particulate materials is 1: 1.

12. The composition according to any of the preceding claims 1-4, wherein at least one of said one or more hydrophobic particulate materials has a median particle size of from 7nm to 40 nm.

13. The composition according to any of the preceding claims 1 to 4 wherein the total weight percentage of all non-volatile water-soluble or water-dispersible organic components in said water-in-oil emulsion is less than 5% and wherein the weight percentage of all polyols is less than 1%.

14. The composition according to any of the preceding claims 1-4, wherein said one or more hydrophobic film formers are selected from the group consisting of (alkyl) acrylates, polyurethanes, fluoropolymers, silicones and copolymers thereof.

15. A method of providing a hydrophobic film on skin or hair comprising depositing the composition of claim 1 or 3 on skin or hair and allowing the volatile components to evaporate thereby forming a hydrophobic film characterized by a contact angle with a water droplet of at least 140 °.

16. The method according to claim 15, wherein the composition is applied to the animal's hair to impart water repellency thereto.