HK1182041A - Method for improving color retention in artificially colored hair - Google Patents

Description

Method for improving color retention on artificially colored hair

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application serial No. US12/940,805, filed on 2/11/2010, which is incorporated herein by reference for all purposes.

Technical Field

The present invention relates generally to methods and compositions for hair. More particularly, the present invention relates to compositions for improving the color retention of artificially colored hair and/or for applying films to lightened and enhanced feel hair.

Background

Consumers have used a wide variety of cosmetic and personal care compositions to promote and/or modify the appearance of keratin fibers such as hair. One stylish change is the use of chemical dyes to impart artificial colors on hair. For example, hair may be treated with direct dyes or oxidative dyes, also known as "permanent" hair dyes, to achieve a desired color.

It is known in the art that artificial hair color, particularly red shades, obtained by treatment with chemical dyes can quickly fade due to repeated shampooing and washing. Chemical dyes used to impart color to hair tend to increase the porosity of the hair keratin fibers. The increased porosity provides increased surface area and allows increased flow of fluid (e.g., water) through the hair fibers, thereby increasing the rate at which chemical dye molecules are leached from the hair. Artificially colored hair can show significant fading after only a few washes. It was confirmed that more than 20% of the artificial color had disappeared in the first 5 washing processes.

Recent advances in facilitating color retention and/or reducing color fading of artificially colored hair include the use of color protection agents. These color protection agents may include mild surfactants, cationic conditioning agents, amino-functional silicones, uv absorbers, starch or sugar surfactants, and the like. Significant improvements over these conventional approaches are disclosed in U.S. patent publication No. US2009/0274640 to Avon Products, which relates to improving color retention on artificially colored hair using a combination of silicone polyurethane polymers, film-forming esters, and fluorosilicones.

Despite the advances made in color protection agents, there remains a need in the art for compositions and methods for reducing the fading of artificially colored hair. It is therefore an object of the present invention to provide compositions and methods for improving color retention on artificially colored hair.

Summary of The Invention

In accordance with the above objects and other objects, the present invention provides methods and compositions for improving color retention on artificially colored hair. The compositions of the present invention surprisingly provide protection against color fading that may persist through repeated hair washes. The compositions of the invention may be anhydrous or in the form of emulsions, in particular water-in-oil or water-in-silicone emulsions.

In one aspect of the present invention, there is provided a method for improving the color retention of artificially colored hair comprising applying to the artificially colored hair a composition having: (a) a hydrophobic particulate material of hydrophobic surface-modified alumina having a median particle size of from about 10nm to about 20 μm, the hydrophobic particulate material comprising from about 0.1% to about 2.0% by weight of the composition; (b) a silicone-based hydrophobic film former comprising from about 0.01% to about 20% by weight of said composition; and (C) a cosmetically acceptable vehicle comprising a silicone fluid having a vapor pressure above about 0.01mmHg at 20 ℃. The total weight percent of all non-volatile water-soluble or water-dispersible organic components in the composition is typically less than 5%, based on the total weight of the composition. The composition can form a substantially uniform coating on the shaft of the hair fibers. Preferably the hydrophobic particulate material is surface modified with alkylsilyl groups such as octanoylsilane. More preferably the hydrophobic particulate material comprises fumed alumina.

In a preferred embodiment, the silicone-based hydrophobic film former may be selected from dimethicone, amodimethicone, dimethiconol, silicone polyurethane, silicone acrylate, or combinations thereof. In particular, the film former may be a silicone acrylate copolymer, such as a copolymer comprising a poly (alkyl acrylate) backbone and a dimethicone polymer grafted with alkyl ester side chains.

The composition may be in the form of a liquid or an emulsion. The product may be a product intended to remain on the hair without rinsing and may be distributed in or sprayed on the hair with a brush, comb or fingers. The composition is typically applied to the hair daily, for example immediately after shampooing. The composition reduces color loss in artificially colored hair and sustains repeated shampooing.

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

Detailed Description

Unless otherwise stated, all amounts provided in weight percent are relative to the composition as a whole. Unless otherwise stated, the term "alkyl" is intended to include straight, branched or cyclic hydrocarbons, particularly those having from 1 to 20 carbon atoms and more particularly C_1-12Those of hydrocarbons.

As used herein, the term "keratin fibers" includes scalp hair, eyelashes, eyebrows, facial hair, body hair (e.g., arms, legs), and the like. Keratin fibers are not limited to humans, and also include any keratin fibers from mammals, such as pet hair and mammalian fur.

The cosmetic compositions of the present invention will generally be anhydrous, although aqueous formulations (e.g., water-in-oil emulsions) are within the scope of the present invention. As used herein, water-in-oil emulsions include water-in-silicone emulsions. When referring to the weight% of ingredients based on the weight of the total composition, the total weight of the composition will be understood to include the aqueous and oil phases of the emulsion. In the context of the present invention, water is considered to be a volatile solvent and will therefore be excluded from the limitations of the hydrophilic components and liquids described herein.

The cosmetic composition for reducing fading from artificially dyed keratin fibers (e.g. hair) of the present invention comprises a combination of a hydrophobic particulate material and a silicone-based hydrophobic film former for imparting a coating on the keratin fibers. This combination has been found to reduce the amount of colorant washed off the hair, as typically encountered during shampooing, swimming, and other activities in which the hair is exposed to water. Without wishing to be bound by any theory, it is believed that the composition may apply a water repellent coating to the surface of the keratin fibres, which reduces the penetration of water into the fibres and thereby slows the leaching of the colourant from the hair. It is believed that the water repellency is due to the micro-or nano-scale structure imposed by the hydrophobic particles on the hair surface, known as the "lotus effect", similar to the phenomenon of water droplets beading and rolling off the lotus leaves due to their surface structure. The hydrophobicity of a surface can be quantified in terms of the contact angle at which the liquid/water vapor interface contacts the solid surface. The contact angle of a drop of water with a glass slide coated with the composition film can suitably be measured using a contact angle goniometer. It is contemplated that the compositions of the present invention are capable of providing a film on a surface upon evaporation of a volatile solvent, and in some embodiments, the film is characterized by a contact angle with a water droplet of greater than about 70 °, greater than about 80 °, greater than about 90 °, or greater than about 100 °, up to about 110 °, about 120 °, about 130 °, about 140 °, or about 150 °. Films having contact angles that produce greater than about 150 ° are referred to as "superhydrophobic.

The method of the present invention provides protection and retention of hair color on color treated hair. The method comprises applying to the hair a composition having (a) a hydrophobic particulate material, such as a hydrophobic surface modified alumina, having a median particle size of from about 10nm to about 20 μm, from about 0.1% to about 2.0% by weight of the composition of the hydrophobic particulate material; (b) a hydrophobic film former, such as a silicone-based hydrophobic film former, present in an amount of from about 0.01% to about 20% by weight of the composition; and (C) a cosmetically acceptable vehicle comprising a volatile hydrophobic solvent, such as a silicone fluid, having a vapor pressure above about 0.01mmHg at 20 ℃. Preferably, the hydrophobic particulate material is surface modified with alkylsilyl groups, such as octanoylsilane. More preferably the hydrophobic particulate material comprises fumed alumina. The total weight percent of all non-volatile water-soluble or water-dispersible organic ingredients in the composition is preferably less than 5%, based on the total weight of the composition. The composition can form a substantially uniform coating on the hair fiber shaft to prevent the colorant from draining from the hair.

The first ingredient of the cosmetic composition of the present invention comprises one or more particulate materials which are hydrophobic in nature or hydrophobically modified by surface treatment or the like. While not wishing to be bound by theory, it is believed that the particulate material provides a nano-scale (1nm to about 1000nm) or micro-scale (1 μm to about 200 μm) surface roughness or structure on the surface that substantially reduces water contact with the surface and reduces surface adhesion by providing protrusions on which water beads may be located, thereby repelling moisture from the surrounding air.

In one embodiment, the particulate material may comprise at least one hydrophobic particulate material having a dynamic (kinetic) coefficient of friction (μ;)_k) Is greater than 0.5. The particulate material may have a chalky or gritty feel and may have a substantially non-spherical shape. Without wishing to be bound by any theory, it is believed that the high μ_k(i.e., greater than 0.5) the substantially non-spherical shape of the particles provides the particles with a nanoscale roughness for repelling moisture. High mu_kThe high drag of the particles also increases the affinity of the particles for hair.

The surface roughness can be observed or measured by AFM, SEM, and the like. The dynamic friction coefficient can be suitably measured using, for example, a friction tester (KES-SE) (manufactured by Kato Tech co., LTD), in which a specific amount (e.g., 0.01g) of a sample uniformly dispersed on a base quartz plate is measured at 2mm/sec with a load of 50g using a silicone rubber friction probe.

A preferred particulate material according to the invention is hydrophobically modified alumina (Al)₂O₃) (also known as alumina), particularly fumed (or fumed) alumina. Hydrophobically modified silicon dioxide (SiO)₂) Including fumed (or fumed) silica (e.g., having a particle size range of about 7nm to about 40nm and a collective particle size of about 100 to about 400nm) are also contemplated to be particularly useful. Other noteworthy particulate materials are hydrophobically modified metal oxides, which include but are not limited to: titanium dioxide (TiO)₂) Iron oxide (FeO, Fe)₂O₃Or Fe₃O₄) Zirconium dioxide (ZrO)₂) Tin dioxide (SnO)₂) Zinc oxide (ZnO) and combinations thereof.

Advantageously, the particulate material may be one that provides other functionality to the composition, including, for example, Ultraviolet (UV) light absorption or scattering (in the case of titanium dioxide and zinc oxide particles, for example), 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 lake pigments, particularly aluminum lakes, strontium lakes, barium lakes, and the like. Examples of inorganic particulate pigments are iron oxides (in particular 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 EP1640419, the disclosure of EP1640419 being 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 described, for example, in U.S. Pat. No. 3,393,155 (Schutte et al), U.S. Pat. No.2,705,206 (Wagner et al), U.S. Pat. No. 5,500,216 (Wagner et al), U.S. Pat. No. 6,683,126 (Keller et al), and U.S. Pat. No. 7,083,828 (muller et al), U.S. Pat. publication No. 2006/0110541 (Russell et al), and U.S. Pat. publication No. 2006/0110542 (Dietz et al), the disclosures of which are incorporated herein by reference. As used herein, a hydrophobically modified particle is a particle that is rendered less hydrophilic or more hydrophobic by surface modification than a particle without surface modification.

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 attached to) non-polar radicals such as alkyl, silicone, siloxane, alkylsiloxane, organosiloxane, fluorinated siloxane, perfluorosiloxane, organosilane, alkylsilane, fluorinated silane, perfluorinated silane, disilazane, and/or the like. The surface treatment may be any treatment that renders the particles more hydrophobic. The surface of the particles may, for example, be covalently or ionically bound to or adsorbed onto organic molecules or elemental silicon-based molecules, or the particles may be physically coated with a layer of hydrophobic material. There are essentially no restrictions on the nature of the hydrophobic treatment and mention may be made of alkyl, aryl or allyl silanes, siloxanes, dimethylpolysiloxanes, fatty acids (e.g. stearates), polymeric silanes, and their fluoro and perfluoro derivatives. The hydrophobic compound can be attached to the oxide particles by any suitable coupling agent, linking group, or functional group (e.g., silane, ester, ether, etc.). The hydrophobic compound comprises a hydrophobic moiety which may be selected from, for example, alkyl, aryl, allyl, vinyl, alkyl-aryl, aryl-alkyl, organosilicones, and fluoro or per-substituted versions thereofA fluorine derivative. Hydrophobic polymeric coatings (including polyurethanes, epoxies, etc.) are also expected to be useful. U.S. patent No. US6,315,990 (Farer et al), the disclosure of which is incorporated herein by reference, describes suitable fluorosilane-coated particles formed by reacting particles having nucleophilic groups (e.g., oxygen or hydroxyl groups) with a silicon-containing compound having a hydrocarbyl group substituted with at least one fluorine atom and a reactive hydrocarbyloxy group capable of being displaced by a nucleophile. An example of such a compound is tridecafluorooctyltriethoxysilane available from Sivento, Piscataway, N.J., under the trade name DYNASILANE^TMF8261. Preferred hydrophobic coatings according to the invention are prepared by treating an oxide, for example alumina, with trimethoxyoctanoylsilane.

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

In a particularly preferred embodiment, the particulate material is fumed (or fumed) alumina or fumed (or fumed) silica, which is surface functionalized (i.e., surface treated with alkylsilyl groups) with alkylsilyl, fluoro-alkylsilyl, or perfluoro-alkylsilyl groups (preferably with alkylsilyl groups). Typically, the alkylsilyl group will contain C_1-20Hydrocarbon (more typically C)_1-8Hydrocarbons) which are optionally fluorinated or perfluorinated. Such groups may be formed by reaction of the surface of the particles with a silane (e.g., C)_1-12Alkyl-trialkoxysilanes (e.g. C)_1-12-alkyl-trimethoxy siliconAlkane or C_1-12-alkyl-triethoxysilane)) are introduced. Preferably, the particle surface is functionalized with alkylsilyl groups (i.e., accomplished via an alkylsilane surface treatment). More preferably, the particle surface is functionalized and surface modified with octylsilyl groups (also known as octanoylsilyl groups) introduced by reacting the particle with octylsilane (or octanoylsilane), such as trimethoxyoctanoylsilane or triethoxycaprylsilane. Such particles are commonly referred to as being octyl silane treated. In another embodiment, the oxide particles are perfluoroalkylsilanes (particularly perfluoroalkylsilanes, e.g., C)_1-20Perfluoroalkylsilanes, or more typically C_1–12Perfluoroalkylsilane), including exemplary embodiments wherein the oxide particles are C₈And (3) performing surface treatment on the perfluoroalkyl silane. The pigment may be prepared by treating oxide particles with a trialkoxyfluoroalkylsilane, such as perfluorooctyltriethoxysilane (INCI). Because the particles are preferably calcined (or fumed), the primary particle size (primary particle size) is typically very small, i.e., on the order of 5nm to about 30 nm. The Specific Surface Area (SSA) of these particulate materials will typically, but not necessarily, be in the range of about 50 to about 300m²In the range of/g, more typically, from about 75 to about 250m²Per gram, and preferably from about 100 to about 200m²/g。

Suitable hydrophobically modified alumina particles include fumed alumina (obtained by reacting trimethoxyoctylsilane with fumed alumina) treated with octylsilane, such as from Evonik IndustriesAlu and AEROXIDE^TMALU C805. This product is believed to have an average primary particle size of about 13nm (nanometers) and about 100 + -15 m²Specific surface area per gram (SSA). Typically, the alumina or hydrophobically modified alumina is not calcined, meaning that the alumina is not heated to high temperatures (e.g., above 1000 ℃) to drive off volatility from the crude metal oxideImpurities. Preferably, the particulate material is substantially free of calcined alumina, meaning that calcined alumina is not intentionally added to the particulate material and is present in such a low level that it has no measurable effect on the performance, appearance or feel of the composition. More preferably, the particulate material is free of calcined alumina.

In other embodiments, the composition is substantially free of alumina or hydrophobically modified alumina. By substantially free of alumina or hydrophobically modified alumina, it is meant that these constituents 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.

Additional particles, such as hydrophobically modified fumed silica, may be included. When present, suitable hydrophobically modified fumed silica particles include, but are not limited to, AEROSIL from Evonik/Degussa Corporation of Parsippany, N.J^TMR202、AEROSIL^TMR805、AEROSIL^TMR812、AEROSIL^TMR812S、AEROSIL^TMR972、AEROSIL^TMR974、AEROSIL^TMR8200、AEROXIDE^TMLE-1、AEROXIDE^TMLE-2 and AEROXIDE^TMLE-3, which are considered to be hydrophobic fumed silicas, the surface of which is hydrophobically functionalized with alkylsilyl groups and the Specific Surface Area (SSA) is about 100. + -.30 m²A/g of about 220. + -.30 m²(ii) in terms of/g. Hydrophobically modified silica materials described in U.S. patent publication No. US2006/0110542 to Dietz et al, the disclosure of which is hereby incorporated by reference, are also contemplated to be suitable.

Although in some embodiments silicon dioxide (SiO)₂) And hydrophobically modified silicas are contemplated to be useful, but in other embodiments, the composition is substantially free of silica or hydrophobically modified silica. By substantially free of silica or hydrophobically modified silica, it is meant that these ingredients 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. In other embodiments, the composition will be substantially free of silica or hydrophobically modified silica. "By "free" is meant that no intentional additions are made and the amount present will be so low as to have no effect on the look, feel or performance of the composition.

The one or more particulate materials may also comprise particulate organic polymers, such as polytetrafluoroethylene, polyethylene, polypropylene, nylon, polyvinyl chloride, and the like, formulated as a fine powder. Alternatively, the particulate material may be a microcapsule comprising any of the shell materials described in U.S. patent publication 2005/0000531, the disclosure of which is incorporated herein by reference. Other optional particles are included under the trade name Tegotop^TM105(Degussa/Goldschmidt chemical corporation) and under the trade name Mincor^TMGranular vinyl polymer sold under 300 (BASF).

The one or more particulate materials will typically be in the form of a powder having a median particle size of from about 1nm (nanometers) to about 1mm (millimeters), more typically from about 5nm to about 500 μm (micrometers), preferably from about 7nm to about 100 μm, more preferably from about 10nm to about 5 μm, about 20 μm, about 50 μm, or about 75 μm. When more than one particulate material is employed (e.g., modified TiO)₂And/or modified SiO₂) The median particle size of each powder is preferably within the aforementioned range.

Particulate materials having a median particle size above about 1mm may be too large unless the particles themselves contain a surface roughness in the appropriate 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 can be characterized by: the size of the primary particles, the size of the aggregated particles in the aggregate, or by the distribution of particle sizes.

Typically, the one or more particulate materials will typically comprise from about 0.01% to about 10% (by weight) of the total composition, more typically from about 0.1% to about 5%, preferably from about 0.1% to about 2.5%, more preferably from about 0.25% to about 2.0% (by weight) of the composition, and most preferably from about 0.4% to about 1.5%. In some embodiments, the one or more particulate materials may comprise about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1.0%, about 1.25%, and about 1.5% (by weight) of the composition.

In some embodiments, the octylsilyl-functionalized fumed alumina can comprise greater than about 5%, greater than about 10%, greater than about 15%, greater than about 20%, greater than about 25%, about 30%, greater than about 35%, about 40%, greater than about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, greater than about 75%, greater than about 80%, greater than about 85%, greater than about 90%, or greater than about 95% by weight of the one or more hydrophobically modified particles.

The compositions of the present invention may comprise one or more film forming agents, preferably hydrophobic film forming agents. The hydrophobic film former may be any hydrophobic film former suitable for use in cosmetic compositions, including waxes and oils, but hydrophobic film-forming polymers are preferred. 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 will typically refer to a polymer having a solubility in water of less than about 1% by weight at 25 ℃, or a polymer in which the monomer units of the polymer individually have a solubility in water of less than about 1% by weight at 25 ℃. A "hydrophobic" film-forming polymer can be one that partitions primarily into the octanol phase when shaken with a mixture of equal volumes of water and octanol. By predominantly is meant that more than 50% by weight, but preferably more than 75% by weight, more preferably more than 95% by weight will partition into the octanol phase. The film former is preferably silicone-based. By "silicone-based" it is meant that the hydrophobic film former comprises at least one silicone moiety, such as dimethicone, amodimethicone, dimethiconol, silicone urethane, silicone acrylate or combinations thereof.

Polymeric film formers may be natural or synthetic, formed by addition or condensation reactions, homo-or hetero-chains, mono-or polydisperse, organic or inorganic, homopolymers or copolymers, linear or branched or crosslinked, charged or uncharged, thermoplastic or thermosetting, elastomeric, resinous, crystalline or amorphous or both, isotactic or syndiotactic or atactic.

Polymeric film formers include polyolefins, polyethylenes, polyacrylates, polyurethanes, silicones, silicone acrylates, polyamides, polyesters, fluoropolymers, polyethers, polyacetates, polycarbonates, polyimides, rubbers, epoxies, formaldehyde resins, and homopolymers and copolymers of the foregoing.

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

Copolymers comprising one or more blocks selected from styrene (S), Alkylstyrene (AS), ethylene/butylene (EB), ethylene/propylene (EP), butadiene (B), isoprene (I), acrylate (a) and Methacrylate (MA), or combinations thereof, are contemplated AS suitable hydrophobic film formers. Particular mention may be made of ethylene/propylene/styrene and butylene/ethylene/styrene copolymers, including those sold under the trade name Versagel MD1600 (gelling agent in Isododecane (IDD) from Penreco).

Particular mention may be made of polyolefins, and in particular C₂-C₂₀Olefin copolymers, such as polybutene; having linear or branched, saturated or unsaturated C₁-C₈Alkyl celluloses of alkyl radicals, such as ethyl cellulose and propyl cellulose; copolymers of Vinylpyrrolidone (VP), in particular vinylpyrrolidone and C₂To C₄₀(more preferably C)₃To C₂₀) Copolymers of olefins, comprising vinylpyrrolidone and dodecene orCopolymers of dodecane monomers sold under the trade names Ganex V220 and Ganex V216 polymers (ISP inc. wayne, NJ); polyanhydride resins (such as those available from Chevron under the trade name PA-18); derived from maleic anhydride and C₃To C₄₀Copolymers of olefins (e.g., octadecene-1); polyurethane polymers such as those described in Performa V825(New Phase Technologies) and U.S. patent No. 7,150,878 (Gonzalez et al), which are incorporated herein by reference; and polymers and copolymers made from esters of vinyl acid monomers, including, but not limited to, (meth) acrylates (also known as (meth) acrylates), such as alkyl (meth) acrylates, wherein the alkyl is selected from linear, branched, and cyclic (C)₁-C₃₀) Alkyl radicals, e.g. (C)₁-C₂₀) Alkyl (meth) acrylates, and (C)₆-C₁₀) Alkyl (meth) acrylates. Among the alkyl (meth) acrylates that may be mentioned are those chosen from the following: methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and the like. Among the aryl (meth) acrylates that may be mentioned are those chosen from the following: benzyl acrylate, phenyl acrylate, and the like. The alkyl groups of the aforementioned esters may be selected from, for example, fluorinated and perfluorinated alkyl groups, i.e., alkyl groups in which some or all of the hydrogen atoms have been replaced by 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 result from the homopolymerization or copolymerization of at least one monomer selected from: vinyl esters, olefins (including fluoroolefins), vinyl ethers, and styrene monomers. For example, these monomers may be copolymerized with at least one of acid monomers, esters thereof, and amides thereof (such as those mentioned above). Non-limiting examples of vinyl esters that may be mentioned are selected from: vinyl acetate, vinyl neodecanoate, vinyl pivalate, styreneEsters and vinyl tert-butylbenzoate. Among the olefins that may be mentioned are those chosen from the following: such as ethylene, propylene, butylene, isobutylene, octene, octadecene, and polyfluorinated olefins selected from, for example, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene 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 it is possible to use any monomer known to the person skilled in the art that falls within the category of acrylic and vinyl monomers, which gives rise to hydrophobic films. In this connection, mention may be made in particular of silicone acrylate copolymers, in particular copolymers comprising a poly (alkyl) acrylic backbone and a dimethicone polymer conjugated to alkyl ester side chains, such as the commercially available film former cyclopentasiloxane (and) acrylate/dimethicone copolymers (KP-545, Shin-Etsu Chemical co., Ltd) and methyltrimethylpolysiloxane (and) acrylate/dimethicone copolymers (KP-549, Shin-Etsu Chemical co., Ltd.).

Other film forming agents 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, amodimethicone, AMP/acrylate copolymers, behenyl alcohol/isostearyl alcohol, butylated PVP, PVM/MA copolymer butyl ester, PVM/MA copolymer calcium/sodium, dimethicone copolymer, dimethicone/mercaptopropyl methicone copolymer, dimethicone propyl ethylenediamine behenate, dimethiconol ethyl cellulose, ethylene/acrylic acid copolymers, ethylene/MA copolymers, ethylene/VA copolymers, fluoroc C_2-8Alkyl dimethyl polysiloxane, C_30-38Olefin/isopropyl maleate/MA copolymer, hydrogenated styrene/butadiene copolymer, hydroxyethylethylcellulose, isobutylene/MA copolymer, methyl methacrylate crosspolymer, methacryloyl ethyl betaine/acrylate copolymer, octadecene/MA copolymer, octadecene/maleic anhydride copolymer, octylacrylamide/acrylateButylaminoethyl methacrylate copolymer, oxidized polyethylene, perfluoropolymethyl isopropyl ether, polyethylene, polymethyl methacrylate, polypropylene, PVM/MA decadiene crosspolymer, PVM/MA copolymer, PVP, PVP/decene copolymer, PVP/eicosene copolymer, PVP/hexadecene copolymer, PVP/MA copolymer, PVP/VA copolymer, sodium acrylate/vinyl alcohol copolymer, stearyloxydimethylpolysiloxane, stearyloxytrimethylsilane, stearyl alcohol, octadecyl vinyl ether/MA copolymer, styrene/DVB copolymer, styrene/MA copolymer, triacontyl, trimethylsiloxy silicic acid, VA/crotonic acid copolymer, VA/crotonic acid/vinyl propionate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer, and vinyldimethylpolysiloxane.

Other non-limiting representatives of hydrophobic film formers include at least one polycondensate 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 polyurethanes, polyurea copolymers comprising at least one of the following: at least one aliphatic polyester source, cycloaliphatic polyester source and aromatic polyester source of at least one sequence; at least one branched or unbranched siloxane sequence, for example from polydimethylsiloxane and polymethylphenylsiloxane; and at least one sequence comprising a fluorinated group. Other non-limiting representatives of polycondensates may be selected from the group consisting of polyesters, polyesteramides, aliphatic polyesters, polyamide resins, epoxy ester resins, arylsulfonamide-ethoxy resins, and resins resulting from the condensation of formaldehyde with arylsulfonamides.

Hydrophobic films may also be formed in situ by the use of resins that harden (cures) after application to the skin, nails, or hair, including, for example, polydimethylsiloxane films formed by in situ hydrosilation of hydrosilanes and olefin-substituted siloxanes, or by in situ polycondensation of alkoxy-functional siloxanes.

Preferred polymeric film formers include silicone polymers, acrylates, alkyl acrylates, polyurethanes, fluoropolymers such as fluoomer (polyperfluoroperhydrophenanthrene) or Flutec PP3, available from F2chemicals, and silicone acrylates such as acrylate/dimethicone copolymers sold under the trade name KP-545 or KP550 (Shin-Etsu). Suitable film formers include, but are not limited to, aminodipropyldimethicone, aminopropyldimethicone, aminodimethicone hydroxystearate, behenoxy dimethicone, C_30-45Alkyl dimethyl polysiloxane, C_24-28Alkyl dimethyl polysiloxane, C_30-45Alkyl methyl polysiloxane, cetearyl alcohol methyl polysiloxane, cetyl dimethicone, dimethoxy silyl ethylene diaminopropyl dimethicone, hexyl methyl polysiloxane, hydroxypropyl dimethicone, stearamidopropyl dimethicone, stearyloxydimethicone, stearyl methyl polysiloxane, stearyl dimethicone and vinyl dimethicone. Particularly preferred are silicone polymers, including methylpolysiloxanes (as described in CTFA publication No.1581, which is incorporated herein by reference), dimethylpolysiloxanes (as described in CTFA publication No.840, which is incorporated herein by reference) and amino-terminated polydimethylsiloxanes (as described in CTFA publication No.189, which is incorporated herein by reference). All CTFA specialty provided herein are found in International Cosmetic ingredient dictionary and Handbook, 12 th edition (2008), which is incorporated herein by reference.

In one embodiment of the invention, the composition comprises a silicone rubber. Suitable silicone rubbers will typically have a molecular weight of from about 200,000 to about 600,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly (dimethylsiloxane) (diphenyl) (methylvinylsiloxane) copolymer, dimethiconol, fluorosilicone, dimethicone, or mixtures thereof. In a preferred embodiment, the film-forming silicone rubber is a high molecular weight dimethicone. The high molecular weight dimethicone has high tack and is commonly referred to as a dimethicone gum. The viscosity of the silicone rubber may range from (without limitation) about 500,000 centistokes to about one hundred million centistokes (measured at 25 ℃). High molecular weight dimethicone is commercially available in combination with lower molecular weight silicones or with volatile silicones, which makes high molecular weight dimethicone easier to handle. A suitable mixture containing high molecular weight dimethicone (MW about 500,000) is commercially available from Momentive under the trade name SF 1214.

In another preferred embodiment, the film-forming polymer is a silicone acrylate, such as that having the CTFA specialty No.10082 and INCI designation acrylate/dimethicone. This polymer is commercially available from Shin-Etsu Chemical co., ltd. under the trade name KP-544 and comprises a graft copolymer comprising an acrylic polymer backbone and dimethylpolysiloxane side chains. The same polymers are commercially available in a variety of different solvents, including isopropanol (KP-541), butyl acetate (KP-543), cyclopentasiloxane (KP-545), methyltrimethylpolysiloxane (KP-549), and isododecane (KP-550).

In another embodiment, the film former may be a silicone polyurethane, such as one having the INCI designation dihydroxypropyldimethicone/SMDI copolymer and INCI journal No. 22006. Such polymers are commercially available from Siltech corp, under the trade name SILMER UR-5050, which comprises the polymer in isododecane.

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 plant origin, including, but not limited to, carnauba wax, candelilla wax, bay fruit wax, sugarcane wax, and the like. Mineral waxes contemplated to be useful include, but are not limited toParaffin wax, ozokerite, montan wax, paraffin wax (paraffin), microcrystalline wax, petroleum wax, and petrolatum waxes. Synthetic waxes include, for example, Fischer Tropsch (FT) waxes and polyolefin waxes; for example ethylene homopolymers, ethylene-propylene copolymers and ethylene-hexene copolymers. Representative ethylene homopolymer waxes are commercially available under the trade namePolyethylene (BakerHughes Incorporated). Commercially available ethylene-alpha-olefin copolymer waxes are included under the trade nameThose sold under the Baker Hughes Incorporated. Another suitable wax is dimethiconol beeswax available from Noveon as ULTRABEE^TMPolydimethylsiloxane alcohol ester.

High molecular weight hydrophobic esters may also be useful, which can form a water-resistant hydrophobic film on hair. The hydrophobic ester may be saturated or unsaturated and may include, but is not limited to, a fatty acid monoester, a dibasic acid diester, a tribasic acid diester, or a tribasic acid triester. Monoesters comprising a straight, branched or cyclic C₄-C₂₄Preferably C₈-C₂₄And more preferably C₁₂-C₂₂Monocarboxylic acids and straight, branched or cyclic C₄-C₃₆Preferably C₈-C₂₄And more preferably C₁₂-C₁₈Esterification products of alcohols. Diesters including straight, branched or cyclic C₄-C₄₈Dicarboxylic acids, typically C₈-C₄₄Dicarboxylic acids and more preferably C₁₂-C₃₆Dicarboxylic acids with straight, branched or cyclic C₄-C₃₆Preferably C₈-C₂₄And more preferably C₁₂-C₂₈Esterification products of alcohols. The dicarboxylic acid may be, for example, a dimer formed by dimerizing an unsaturated fatty alcohol, such as linoleic acid. Diesters and triesters of tribasic acids including C₆-C₇₂Tricarboxylic acids, typically C₁₂-C₆₆Tricarboxylic acids with C₄-C₃₆Preferably C₈-C₂₄And more preferably C₁₂-C₁₈Esterification products of alcohols. The tricarboxylic acid may be, for example, a trimer formed by trimerization of an unsaturated fatty alcohol, such as linoleic acid. The ester is preferably a high molecular weight ester, by which is meant a molecular weight of at least 500. In some embodiments, the ester has a molecular weight of at least 750, at least 1000, or at least 1200. The ester is preferably hydrophobic and may optionally be dispersible, but insoluble in the excipient. One suitable hydrophobic ester is triisostearoyl trilinoleate (INCI) (CAS registry number 103213-22-5), available from Lubrizol Advanced Materials, Inc., under the trade name SCHERCEMOL^TMTIST ester.

In some embodiments, it may be desirable to add hydrophilic or water-soluble film forming agents (e.g., cellulosic materials, polysaccharides, polyquaterniums (e.g., polyquaternium-37 (INCI), etc.)) to the compositions to improve spreading, emulsion stability, aesthetic appearance and feel, and the like. Although less preferred, such hydrophilic or water-soluble film forming agents are included within the scope of the present invention. There is no limitation on the amount of hydrophilic or water-soluble film former in the broadest sense, although at high levels (e.g., greater than 20% by weight based on the total weight of the film former) it may be desirable to increase the ratio of hydrophobic particles to film former to counter the decrease in surface hydrophobicity. In some embodiments, the total weight percent of hydrophilic or water-soluble film forming agents will be less than about 20%, preferably less than about 15%, more preferably less than about 10%, and more preferably less than about 5% (by weight), based on the total weight of all film forming agents. In a preferred embodiment, the hydrophilic film former will comprise less than about 2% (by weight) of the total weight of film formers in the composition. In other embodiments, the composition is substantially free of water soluble film forming agents, by which is meant that the composition comprises less than 2% (by weight), preferably less than 1% (by weight), more preferably less than 0.5% (by weight) of the one or more film forming agents. In one embodiment, the composition does not contain a hydrophilic film former.

Combinations of any of the foregoing film formers are also contemplated as being suitable, including combinations of polymeric or non-polymeric film formers.

The film former will constitute from about 0.01% to about 20% (by weight) of the composition, and more typically will constitute from about 0.25% to about 15%, and preferably from about 1 to 12%, more preferably from 1.5% to about 10%, and more preferably from about 3% to about 8% (by weight) of the composition. Generally, the weight ratio of the one or more hydrophobic particulate materials to the one or more film forming agents will be from about 1:1 to about 1:100, from about 1:1.25 to about 1:75, from about 1:1.5 to about 1:50, from about 1:1.75 to about 1:25, or from about 1:2 to about 1: 10. In various embodiments, the ratio of the one or more hydrophobic particulate materials to the one or more film forming agents is about 1:20, about 1:15, about 1:10, about 1:9, about 1:8, about 1:7, about 1:6, about 1:5, about 1:4, about 1:3, about 1:2, about 1:1.5, and about 1:1.

In some embodiments, the composition will comprise a silicone acrylate film former, a silicone rubber film former. The silicone acrylate film former and silicone rubber film former each independently comprise from about 0.01% to about 20% (by weight) of the composition, and more typically will comprise from about 0.25% to about 15%, preferably from about 1.0% to about 10%, more preferably from 1.5% to about 8%, and more preferably from about 3% to about 5% (by weight) of the composition.

The compositions of the present invention will typically comprise a cosmetically acceptable vehicle. By "cosmetically acceptable" is meant that the vehicle is safe for contact with human skin. The excipient may comprise a liquid comprising a single phase, a biphasic system or an emulsion. Emulsions include oil-in-water, silicone-in-water, water-in-oil, water-in-silicone, and the like. When the product is intended as a spray, it may be desirable to employ a single phase vehicle, or a dual phase vehicle comprising a water phase and an oil phase, the oil phase comprising a silicone oil. When formulated as an emulsion, an emulsifier is typically included. In other embodiments, the composition is free or substantially free of an emulsifier. By substantially free of emulsifier is meant that no emulsifier is intentionally added to the composition and is present in such low amounts (if any) that there is no measurable effect on the stability of the emulsion.

In one embodiment, the vehicle may comprise a cosmetically suitable volatile solvent. Typically, the volatile solvent may have a vapor pressure above about 0.01mmHg at 20 ℃ and evaporate at ambient temperature. The volatile solvent may include volatile C_5-12Hydrocarbons (e.g., isododecane), aromatic hydrocarbons (e.g., xylene, toluene, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g., diethyl ether, methyl ethyl ether, etc.), perfluorocarbons, hydrofluoroethers, freons, volatile siloxanes (e.g., cyclopentasiloxane), lower alcohols (e.g., ethanol, isopropanol, etc.), esters of acetic acid (e.g., ethyl acetate, butyl acetate, etc.), and the like.

In the volatile C_5-12Particular mention may be made, among the hydrocarbons, of isododecane commercially available under the trade name Permethyl-99A (PresperseEnc). Suitable fluorinated solvents include, but are not limited to, for example, perfluoroethyl ether, perfluorodecalin, perfluoromethyldecalin, perfluorohexane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane, perfluoroheptane, perfluorooctane, perfluorononane, or perfluoromethylcyclopentane.

Volatile silicones are preferred volatile solvents. Volatile silicones are understood to mean oils which readily evaporate at ambient temperature. Typically, volatile silicone oils will exhibit a vapor pressure in the range of from about 1Pa to about 2kPa at 25 ℃; will preferably have a viscosity of from about 0.1 to about 10 centistokes, preferably about 5 centistokes or less, more preferably about 2 centistokes or less, at 25 ℃; and will boil at about 35 c to about 250 c at atmospheric pressure. Volatile silicones include cyclic and linear volatile dimethylsiloxane silicones, including 0.5cst dimethicone, 0.65cst dimethicone, 1cst dimethicone, and 1.5cst dimethicone. In one embodiment, the volatile silicone may comprise a cyclomethicone comprising tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicone, or mixtures thereof. Suitable dimethicone is available from Dow Corning under the name Dow CorningA Fluid, andand has a viscosity ranging from 0.65 to 5 centistokes. Suitable non-polar, volatile liquid silicone oils are disclosed in U.S. Pat. No. 4,781,917, which is incorporated herein by reference in its entirety. Other Volatile Silicone materials are described in Todd et al, "Volatile Silicone Fluids for Cosmetics," Cosmetics and Toiletries,91:27-32(1976), which is incorporated herein by reference in its entirety. Linear volatile silicones typically have a viscosity of less than about 5 centistokes at 25 ℃, while cyclic silicones have a viscosity of less than about 10 centistokes at 25 ℃. Examples of volatile silicones of various viscosities include Dow Corning200, Dow Corning244, Dow Corning245, Dow Corning344 and Dow Corning345(Dow Corning Corp.); SF-1204 and SF-1202 siloxane fluids (g.e. silicones), GE7207 and 7158(General Electric Co.); and SWS-03314(SWS Silicones Corp.). The linear, volatile siloxanes include low molecular weight polydimethylsiloxane compounds such as methyltrimethylsiloxane, trisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane, among others. In particular, preferred volatile silicones for the present invention include cyclomethicone tetramers, cyclomethicone pentamers, cyclomethicone hexamers, trisiloxanes, methyltrimethylpolysiloxanes, or combinations thereof.

Lower alcohol solvents, including methanol, ethanol, propanol, and isopropanol, are also expected to be useful. Ethanol is particularly preferred due to its high volatility and low toxicity. Preferably, the ethanol is anhydrous ethanol, such as SD ethanol 40 from Exxon. In other embodiments, the composition comprises less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, or less than about 5% (by weight) ethanol. In some embodiments, the composition comprises less than about 2.5%, less than about 1%, or less than about 0.5% (by weight) ethanol. In other embodiments, the composition is substantially free of ethanol, meaning that no ethanol is intentionally added and is present in such low amounts (if any) as to have no measurable effect on the look, feel, or performance of the product. In another embodiment, the composition is free of ethanol.

In another embodiment, the composition of the present invention comprises ethanol, preferably anhydrous ethanol, and one or more solvents having a vapor pressure lower than the vapor pressure of ethanol at 25 ℃. In another embodiment, the composition of the invention comprises ethanol, preferably anhydrous ethanol, and one or more solvents having a vapor pressure higher than the vapor pressure of ethanol at 25 ℃.

In a preferred embodiment, the solvent will comprise a combination of volatile siloxane (preferably cyclomethicone pentamer) and ethanol (optionally anhydrous ethanol). Preferably, the volatile siloxane (cyclomethicone pentamer) will comprise from about 1% to about 99% by weight of the solvent system, provided that the total amount of volatile siloxane and ethanol does not exceed 100%. More particularly, the volatile siloxane (cyclomethicone pentamer) will constitute from about 50% to about 99% and the ethanol will constitute from about 1% to about 50% (by weight) of the solvent system. In a preferred embodiment, the volatile siloxane (cyclomethicone pentamer) will comprise from about 70% to about 90% and the ethanol will comprise from about 10% to about 30% (by weight) of the solvent system.

Anhydrous formulations

The compositions of the present invention may be provided as anhydrous or substantially anhydrous formulations. By "substantially anhydrous" is meant that the weight percent of water in the composition is less than about 0.5%, preferably less than 0.25%, and most preferably less than about 0.1% (by weight). Typically, the anhydrous composition is substantially anhydrous, meaning that no water is intentionally added to the composition and the level of water does not exceed the level expected based on water absorbed from the air. The anhydrous compositions will typically comprise volatile hydrophobic solvents such as volatile hydrocarbons, volatile silicones, anhydrous alcohols, and the like, including combinations of such solvents.

Water-in-oil emulsion

The compositions of the present invention may be formulated as water-in-oil emulsions. These emulsions comprise a continuous phase comprising oil and a discontinuous phase comprising water.

The oil-containing phase will typically comprise from about 10% to about 99%, from about 20% to about 85%, or from about 30% to about 75% (by weight), based on the total weight of the composition; while the aqueous phase will typically comprise from about 1% to about 90%, from about 5% to about 80%, from about 10% to about 70%, or from about 15% to about 60% (by weight) of the composition. In one embodiment, the oil-containing phase and the aqueous phase may comprise about equal percentages of the total weight of the emulsion.

The oleaginous phase may be composed of a single oil or a mixture of different oils. It is contemplated that essentially any oil will 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 dioctyl ether; fatty alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol; isoparaffins, such as isooctane, isododecane and isohexadecane; silicone oils such as dimethylpolysiloxane, cyclosiloxane, and polysiloxane; hydrocarbon oils such as mineral oil, petrolatum, isoeicosane and polyisobutylene; natural or synthetic waxes, and the like.

Suitable hydrophobic hydrocarbon oils may be saturated or unsaturated, aliphatic in character, and may be straight or branched chain, or contain alicyclic or aromatic rings. Hydrocarbon oils include those having from 6 to 20 carbon atoms, more preferably from 10 to 16 carbon atoms. Representative hydrocarbons include decane, dodecane, tetradecane, tridecane and C_8-20Isoparaffins. Paraffinic hydrocarbons are available from Exxon under the ISOPARS trademark, and from Permethyl Corporation. Furthermore, C_8-20Paraffinic hydrocarbons, such as Permethyl99A, manufactured by Permethyl Corporation, under the trade name Permethyl99^TMC of (A)₁₂Isoparaffins (isododecanes) are also expected to be suitable. Various commercially available C₁₆Isoparaffinic hydrocarbons, e.g. isohexadecane (Permethyl R, trade name)^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 (available from Exxon Chemicals). A representative hydrocarbon solvent is isododecane.

The emulsion has no or few non-volatile hydrophilic components, including some conventional humectants. Ingredients such as glycerin and polyols (including propylene glycol, ethoxydiglycol, glycerol, butylene glycol, pentylene glycol and hexylene glycol) should be removed, or should be maintained at such levels that the non-volatile hydrophilic components, such as the non-volatile water-soluble or water-dispersible organic components, in the aggregates do not exceed 15% (by weight), and preferably will be less than 10%, less than 5%, less than 2% or less than 1% (by weight), based on the total weight of the composition. Glycerol was found to be particularly detrimental and therefore should be maintained at levels below 2% by weight, or below 1% by weight, or removed altogether.

The choice and amount of emulsifier was found to be important to obtain a film that provides water vapor resistance. Because the emulsifier itself may be detrimental to the formation of a water vapor resistant film or adversely affect the durability of performance over repeated hair rinses, the composition preferably has a minimum level of emulsifier capable of producing a stable emulsion. The amount of emulsifier will typically be from about 0.001 to about 10% by weight, but preferably will range from about 0.01 to about 5% by weight, more preferably from 0.1 to 3%, and most preferably from about 0.25 to about 1% by weight, based on the total weight of the composition. In other embodiments, the emulsifier may be absent. In compositions where the emulsifier is minimal or absent, the composition may be of the "shake-up" type, such that when the composition is vigorously mixed or shaken, it forms a transient emulsion, and when left undisturbed in a container for a period of time, it separates into two distinct phases.

For water-in-oil emulsions the emulsifier itself should be of low hydrophilic-lipophilic balance (HLB), preferably below 10, more preferably below 8.5. While combinations of more than one emulsifier are contemplated to be within the scope of the present invention, each such emulsifier (alone) should be of low HLB. Thus, the use of high and low HLB emulsifiers, the combination of which gives a low HLB (e.g. less than 8.5), is less desirable because even if the combined HLB of the system is below 8.5, the contribution of the higher HLB emulsifier will be detrimental to the formation of water vapour resistant films. 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 more preferably less than 0.2% (by weight).

When the emulsifier is a mixture containing- (CH)₂CH₂O)_nType of polyethoxylate of the chain of the form (for example, polyoxyethylene ethers or esters), preferably n is less than 20, more preferably less than 10, most preferably less than 5. Propoxylated emulsifiers are also expected to be suitable. The propoxylated emulsifier also preferably has 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: for example, sorbitan esters; polyglyceryl-3-diisostearate; sorbitan monostearate, sorbitan tristearate, sorbitan sesquioleate, sorbitan monooleate; glycerol esters 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; dimethicone copolyol; polyglyceryl esters, such as polyglyceryl-3-diisostearate; glyceryl laurate; steareth-2, steareth-10, steareth-20, and the like. Other 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 which is expected to be suitable according to the present invention is Span83, which is a double half ester of monooleate and dioleate in a 2:1 molar ratio, 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 other solvents, preferably volatile solvents, including lower alcohols, such as ethanol, isopropanol, and the like. When present in the aqueous phase, the volatile solvent will typically comprise 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 expected to enhance the formation of water vapor resistant films because as the solvent evaporates, the particles will tend to be pushed toward the surface of the film.

Water-in-silicone emulsions

One water-in-oil emulsion that has been found useful is a water-in-silicone emulsion having a continuous phase containing silicone oil and a discontinuous phase containing water. Typically, water is incorporated into the composition to form a water-in-silicone emulsion, in order to solubilize water-soluble ingredients into the composition. The water-soluble ingredients may include, inter alia, water-soluble polymers that impart additional aesthetic benefits, such as the appearance and/or feel of hair. Preferably, the amount of water added to the composition will be the minimum amount required or necessary to dissolve the desired water-soluble ingredients. Alternatively, water is incorporated into the composition in order to form a water-in-silicone emulsion and to increase the viscosity of the composition. Preferably, the amount of water introduced is the minimum amount necessary to achieve the desired viscosity.

The silicone containing phase will typically comprise from about 10% to about 99%, from about 20% to about 85%, or from about 30% to about 75% (by weight), based on the total weight of the composition, while the aqueous phase will typically comprise from about 1% to about 90%, from about 5% to about 80%, from about 10% to about 70%, or from about 15% to about 60% (by weight) of the weight of the composition. In one embodiment, the silicone containing phase and the aqueous phase may comprise about equal percentages of the total weight of the emulsion.

Preferably, only the minimum amount of water necessary to achieve the desired function (e.g., dissolving the water-soluble ingredients or increasing the viscosity of the composition) should be introduced. For example, if hair styling consistency is desired and the composition includes a small amount of water-soluble polymer, about 10% to about 25% by weight of water will generally be sufficient. In another example, if cream consistency is desired for the composition, or a large amount of water soluble ingredients (e.g., actives/polymers/etc.) are desired, about 25% to about 50% water may be necessary. The silicone-containing or oil-containing phase may vary depending on the amount of aqueous phase present in the composition.

The silicone oil phase may include volatile silicone oils, non-volatile silicone oils, and combinations thereof. Volatile silicone oil means that the oil evaporates readily at ambient temperature (e.g. about 25 ℃). Typically, a volatile silicone oil will exhibit a vapor pressure in the range of from about 1Pa to about 2kPa at 25 ℃; will preferably have a viscosity of from about 0.1 to about 10 centistokes, preferably about 5 centistokes or less, more preferably about 2 centistokes or less, at 25 ℃; and will boil at about 35 c to about 250 c at atmospheric pressure.

Volatile silicones useful in the silicone phase of the water-in-silicone emulsion include silicones of the cyclic and linear volatile dimethylsiloxanes. In one embodiment, the volatile silicone may comprise a cyclomethicone comprising tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicone, or mixtures thereof. Mention may be made in particular of volatile cyclomethicone-hexamethylcyclotrisiloxane, octamethyl-cyclotetrasiloxane and decamethyl-cyclopentasiloxane. Suitable volatile dimethicone is available from Dow Corning under the name Dow CorningA fluid and has a viscosity ranging from about 0.65 to about 5 centistokes. Suitable non-polar, volatile liquid silicone oils are disclosed in U.S. Pat. No. 4,781,917, which is incorporated herein by reference in its entirety. Other Volatile Silicone materials are described in Todd et al, "Volatile Silicone Fluids for Cosmetics," Cosmetics and oils, 91:27-32(1976), which is incorporated herein by reference in its entirety. Linear volatile silicones typically have a viscosity of less than about 5 centistokes at 25℃, while cyclic siliconesThe siloxane has a viscosity of less than about 10 centistokes at 25 ℃. Examples of volatile silicones of various viscosities include Dow Corning200, Dow Corning244, Dow Corning245, Dow Corning344, and Dow Corning345, (Dow Corning Corp.); SF-1204 and SF-1202Silicone Fluids (G.E. Silicones), GE7207 and 7158(general electric Co.); and SWS-03314(SWS Silicones Corp.). Linear, volatile siloxanes include low molecular weight polydimethylsiloxane compounds such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like.

The non-volatile silicone oil will typically comprise a polyalkylsiloxane, a polyarylsiloxane, a polyalkylarylsiloxane, or mixtures thereof. Polydimethylsiloxane is a preferred non-volatile silicone oil. The non-volatile silicone oil will typically have a viscosity of from about 10 to about 60,000 centistokes, preferably from about 10 to about 10,000 centistokes, more preferably from about 10 to about 500 centistokes, at 25 ℃; and a boiling point at atmospheric pressure of greater than 250 ℃. Non-limiting examples include dimethylpolysiloxane (dimethylpolysiloxane), phenyltrimethylpolysiloxane, and diphenyldimethylpolysiloxane.

The volatile and nonvolatile silicone oils may optionally be substituted with various functional groups such as alkyl, aryl, amine, vinyl, hydroxyl, haloalkyl, alkylaryl, and acrylate groups, and the like.

The water-in-silicone emulsion is emulsified with a nonionic surfactant (emulsifier). Suitable emulsifiers 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 generally comprise a polydiorganosiloxane backbone (typically polydimethylsiloxane) having an inclusion- (EO)_m-and/or- (PO)_nSide chains of groups in which EO is ethyleneoxy and PO is 1, 2-propyleneoxy, typically with hydrogen or lower alkyl (e.g. C)_1-6Typically C_1-3) Capping or end-capping. The side chains will preferably comprise 50 EO and/or PO units or less (e.g.,m+n=<50) preferably 20 or less, more preferably 10 or less. In addition to the alkoxylated side chains, the silicone emulsifier may also comprise alkyl chain pendant groups 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 those available from Dow Corning under the trade designations 3225C and 5225 cformulant AID; siloxane SF-1528, available from General Electric; ABIL EM90 and EM97, available from Goldschmidt Chemical Corporation (Hopewell, Va.); and SILWET^TMEmulsifier series, sold by OSI Specialties (Danbury, CT).

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 Abil EM-90, Goldschmidt Chemical Corporation), PEG-12 dimethicone (trade name SF1288, General Electric), lauryl PEG/PPG-18/18 methylpolysiloxane (trade name 5200FORMULATION AID, Dow Corning), PEG-12 dimethicone crosspolymer (trade name 9010 and 9011 silicone elastomer blend, Dow Corning), PEG-10 dimethicone crosspolymer (trade name KSG-20, Shin-Etsu), and dimethicone PEG-10/15 crosspolymer (trade name KSG-210, Shin-Etsu).

It was found that the choice and amount of emulsifier is important to obtain a film that provides water vapor resistance. Because the emulsifier itself may be detrimental to the formation of a water vapor resistant film or adversely affect the persistence of the appearance over repeated hair rinses, the composition preferably has a minimum level of emulsifier capable of producing a stable emulsion. Water-in-silicone emulsifiers will typically be present in the composition in the following amounts: about 0.001% to about 10% by weight, particularly in an amount of about 0.01% to about 5% by weight, more preferably in an amount of less than 1% by weight. In other embodiments, the emulsifier may be completely absent. In compositions where the emulsifier is present at very low levels or is absent, the composition may be of the "shake-up" type, such that when the composition is vigorously mixed or shaken, it forms a transient emulsion, and when left undisturbed for a period of time, it separates into two distinct phases.

In one embodiment of the invention, the one or more hydrophobic particulate materials and the film-forming agent are first dispersed or dissolved into the oil or silicone phase of a water-in-oil or water-in-silicone emulsion. The oil or silicone is then mixed with water to form an emulsion. The hydrophobic film former and any hydrophobic pigment in the emulsion will typically be dispersed or dissolved primarily in the oil or silicone phase.

In some embodiments, it has been found desirable to include one or more agents that enhance the shine of hair treated with the compositions of the present invention. The hydrophobic particulate material, particularly hydrophobically modified fumed oxides such as alumina and silica, impart a matte effect to the hair, which may be undesirable from a consumer perspective. It has been found that by including one or more agents that modify the shine of hair, the shine of hair can be restored without sacrificing water resistance. The shine enhancing agent is preferably hydrophobic and also preferably solid at room temperature such that the particulate material is not covered when the composition is applied to the hair. For example, lens-shaped particles (e.g., hemispheric PMMA) have been found suitable for imparting gloss. One such commercially available material is a hemispherical cross-linked polymer of methyl methacrylate, sold under the trade name 3D Tech PW (Plain) xp (kobo). Other suitable gloss enhancers include phenylpropyl dimethylsiloxy silicate, polybutene, polyisobutylene, and hydrogenated polyisobutylene.

Silicone fluids, such as aryl substituted silicones having a high refractive index, can also be used as gloss enhancers. Mention may in particular be made of phenyltrimethicones, which are available under the trade names SCI-TEC PTM100(ISP) and PDM20(Wacker-Belsil), and trimethylsiloxyphenyldimethicones (INCI name), which are available under the trade name PDM1000 (Wacker-Belsil). The PDM20 material has a refractive index of 1.437 at 25 ℃. The PDM1000 material has a refractive index of 1.461 at 25 ℃. Another suitable silicone fluid is trimethylsiloxyphenyldimethicone. In general, any aryl-substituted silicone that is expected to have a refractive index greater than 1.4 at 25 ℃ is suitable for restoring shine to hair treated with the compositions of the present invention. Phenyl siloxanes, such as pentaphenyl trimethyl trisiloxane or tetraphenyl tetramethyl trisiloxane, may also be used to improve gloss, which is commercially available as an HRI fluid from Dow corning HRI. Some organic compounds, such as octyl methoxycinnamate, may also be used to enhance gloss.

Gloss enhancers are typically present in about 0.01% to about 5% (by weight) of the total composition. More typically, the gloss enhancer component will comprise from about 0.05% to about 2.5% (by weight) of the composition. Preferably, the gloss enhancer will comprise from about 0.1% to about 1.5% (by weight) of the composition.

A third ingredient of some embodiments of compositions according to the present invention is fluorosilicone, which can impart excellent spreading characteristics. The fluorosilicone is preferably hydrophobic and oleophobic and also preferably insoluble, but dispersible in the vehicle. There is essentially no restriction on the nature of the fluorosilicone. In one embodiment, the fluorosilicone comprises a fluorine substituted polysiloxane. Fluorosilicones typically comprise the form- [ Si (R)₂)(R₃)–O]A repeating unit of (A) wherein R₂And/or R₃Independently is alkyl, aryl or alkylaryl (e.g. benzyl), wherein at least one R is₂And R₃Substituted by one or more fluorine atoms. Preferably, at least one R₂Or R₃Is C_1-30Alkyl, which contains one or more fluorine atoms and preferably a perfluorinated segment, has the meaning of the form- (CF)₂)_x-wherein x is an integer from 1 to 29; and/or trifluoromethyl.

Fluorosilicones may be included as a diffusion aid. A suitable fluorineThe siloxane is perfluorononyl dimethicone, available from Phoenix Chemical, Inc., under the trade name Perfluorononyl dimethiconeFSL-150, FSL-300, FSH-150, FSH-300, FSU-150 and FSU-300, all of which have the chemical Abstract number CAS 259725-95-6.

In addition to the foregoing, the compositions according to the invention may contain other pigments, pearlescers and/or colorants to counter the white appearance of fumed alumina or fumed silica, or to impart a desired color to the hair, provided that such ingredients do not adversely detract from the performance of the product. Inorganic pigments include, but are not limited to, titanium dioxide, zinc oxide, iron oxide, chromium oxide, ferric blue, mica (mica), bismuth oxychloride, and mica (tinated mica); organic pigments include barium, strontium, calcium or aluminum lakes, ultramarine and carbon black; colorants include, but are not limited to, D & C Green #3, D & C Yellow #5, and D & C Blue # 1. The pigments and/or colorants may be coated or surface treated with one or more compatibilizers to aid dispersion in the solvent. Preferred pigments and/or colorants are those that have been surface treated to render them hydrophobic.

Preferred colorants include ferric oxide, black iron oxide, red iron oxide, CI77489, CI77491, CI77492, CI77499, Red iron oxide 10-34-PC-2045, pigment Black 11, pigment Brown 6, pigment Brown 7, pigment Red 101, pigment Red 102, pigment yellow 42, pigment yellow 43, ferric oxide, synthetic ferric oxide, and yellow iron oxide.

Various fillers and additional ingredients may be added. Suitable fillers include, but are not limited to, silica, treated silica, talc, zinc stearate, mica, kaolin, nylon powders such as Orgasol^TMPolyethylene powder, Teflon^TMBoron nitride, copolymer microspheres such as Expancel^TM(Nobel Industries)、Polytrap^TM(Dow Corning) and Silicone resin Microbeads (Tospearl from Toshiba)^TM) And the like.

Other pigment/powder fillers include, for example, but are not limited to, inorganic powders such as gums, chalk, fuller's earth, kaolin, sericite, muscovite, phlogopite, synthetic mica, paragonite, 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, octenyl aluminum starch succinate, barium 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 powder, metal soaps (zinc stearate, magnesium stearate, zinc myristate, calcium palmitate, and aluminum stearate), colloidal siloxane dioxide, and boron nitride; organic powders such as polyamide resin powder (nylon powder), cyclodextrin, polymethyl methacrylate Powder (PMMA), 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 such as bentonite gel and rheoparrl TT 2. Other useful powders are disclosed in U.S. patent No. 5,688,831, the disclosure of which is incorporated herein by reference.

The total amount of all such additional pigments, colorants and fillers is not particularly limited, provided that the water resistance of the treated hair is not compromised. Typically, all additional pigments, colorants, fillers, etc., if present, will collectively comprise from about 0.1% to about 5% of the total composition, but more typically will comprise from about 0.1% to about 2% (by weight) of the composition.

The compositions of the present invention may optionally comprise other active and inactive ingredients typically associated with hair care products. The nature of these other ingredients and their amounts should preferably be suitable for formulating stable hair care products which form a hydrophobic film on keratin fibres. Preferably, these additional ingredients include at least one bioactive ingredient for improving the keratin fibers. The selection of other active and/or inactive ingredients for hair care products is within the skill of the art. Suitable additional ingredients include, but are not limited to, amino acids, antioxidants, conditioning agents, chelating agents, colorants, emollients, emulsifiers, excipients, fillers, fragrances, gelling agents, humectants, minerals, humectants, photostabilizers (e.g., UV absorbers), sunscreen agents, preservatives, stabilizers, colorants, surfactants, viscosity and/or rheology modifiers, vitamins, waxes, and mixtures thereof. It is contemplated that the hair care products of the present invention may also include anti-dandruff and/or sunscreen ingredients. The level of such other ingredients, if present, should be judiciously selected so as not to adversely affect the ability of the composition to form a hydrophobic film on the hair. Collectively, all such other ingredients will suitably comprise less than 5% (by weight) of the composition, but will typically comprise less than about 2% (by weight), and preferably will comprise less than 1% (by weight), more preferably less than 0.5% (by weight), and ideally less than 0.1% (by weight) of the total composition.

In one embodiment, the composition is free or substantially free of cationic hair conditioning agents. By substantially free of cationic hair conditioning agents is meant that the composition comprises less than 0.5% by weight, preferably less than 0.25% by weight and more preferably less than 0.1% by weight of cationic conditioning agents. In other embodiments, the composition may comprise an amount of cationic (quaternary ammonium) ingredient that is anhydrous or has a very low level of water, for example less than 1% by weight. Suitable quaternary ammonium compounds include, but are not limited to, polyquaternium-37 (INCI), cyclopentasiloxane, and siloxane quaternium-18 (INCI), PEG-2 disuccinimidyl oil amide ethylmethylammonium methyl sulfate and hexylene glycol (INCI), and hexadecyl trimethyl ammonium chloride (INCI). Such quaternary ammonium salt compounds, if present, will typically comprise from about 0.05% to about 1.5% (by weight) of the total composition, and more typically from about 0.1% to about 1% (by weight).

The compositions of the present invention may be formulated in any suitable form, including various rinse-off and leave-on formulations, such as, but not limited to, shampoos, conditioners, serums, creams, sprays, emulsions, gels, ointments, liquids, and the like.

In one embodiment, the composition may be formulated for pumping or aerosol delivery to the hair. When formulated for aerosol delivery, a propellant will be included which is suitable for delivering the composition onto the hair. Suitable propellants include, but are not limited to, n-butane, isobutane, and isobutane/propane, nitrogen, carbon dioxide, compressed air, nitrous oxide, 1, 2-difluoroethane, 1,1,1, 2-tetrafluoroethane, dimethyl ether, and mixtures thereof. When referring to the total weight of the compositions of the invention herein, such weight will be understood to exclude the weight of propellant.

In one embodiment, the provided product comprises an aerosol device comprising a container adapted with a dispenser (e.g., a dispensing valve) for dispensing an aerosol composition from the container. The container is filled with a composition according to the invention (e.g. comprising one or more particulate materials, one or more film forming agents, and a volatile solvent). Suitable propellants may be included in the container containing the composition of the present invention or may be included in a second container in a dual chamber type aerosol device. When the propellant is included in a container containing other ingredients, it will typically be present at about 20% to about 50%, by weight of the composition in which the propellant is included. The vessel may be pressurized or unpressurized.

Particularly detrimental to the practice of the present invention are nonvolatile water-soluble or water-dispersible ingredients, such as propylene glycol or glycerin, that can coat or mask particles on the hair surface or can attract or bind water. Preferably, the total amount of such non-volatile water-soluble or water-dispersible ingredients in the composition will be less than about 15%, less than about 10%, less than about 5%, less than about 2.5%, less than about 1%, less than about 0.5%, less than about 0.25%, less than about 0.1%, or less than about 0.05%, based on the total weight of the composition. In some embodiments, the composition is free of non-volatile water-soluble or water-dispersible ingredients, and in particular free of liquid water-soluble or water-dispersible ingredients.

Other optional ingredients include, but are not limited to, silicone elastomers, which may be incorporated to provide conditioning properties to the hair or to improve the tactile properties of the film. Silicone elastomers are crosslinked elastomeric silicones that can undergo large reversible deformations. Such elastomers may be formed, for example, by a platinum group metal catalyzed reaction between an SiH containing diorganopolysiloxane and an organopolysiloxane having silicon-bonded vinyl groups. Suitable silicone elastomers include dimethicone/vinyl dimethicone crosspolymer, vinyl dimethicone/methyl silsesquioxane crosspolymer, and dimethicone/phenyl vinyl dimethicone crosspolymer. Examples include Dow Corning9040, 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 elastomer is preferably present at a concentration of 0.01% to 10%, more preferably at a concentration of 0.1% to 5%, most preferably at a concentration of 1% to 3%. The silicone elastomer did not form a good film and was not included in the calculation of the powder to film former ratio. Vinyl dimethicone/methyl silicone/silsesquioxane crosspolymers are one silicone elastomer found to be particularly useful. Other ingredients that may optionally be present include, but are not limited to, conditioning agents (e.g., polyquaternium-37/PG dicaprylate/tridecyl polyether blend), aesthetic modifiers (e.g., polymethyl methacrylate spherical powder having a diameter of 4-8 μm), silicone resins (e.g., trimethylsiloxy silicic acid), thickening agents (e.g., PEG-150/decanol/SMDI copolymer), sunscreens, preservatives, fragrances, and the like.

Other ingredients may be incorporated as fillers or for various functional purposes according to the convention in the cosmetic field. However, while other compositional ingredients may be included to formulate the above cosmetic compositions, the inclusion of other ingredients is limited to those that do not interfere with the formation of the water-resistant film.

The anhydrous compositions of the present invention may suitably be prepared by mixing a solvent (e.g. ethanol and cyclomethicone pentamer) with the particulate material and the film-forming agent, and, if present, the gloss enhancing agent and optional ingredients. There is essentially no restriction on the order of addition of the ingredients or the manner in which they are mixed. The composition may be mixed or homogenized at room temperature. It has been found useful (but not necessary) to mill the mixed ingredients, which milling can be carried out using any suitable technique in the art. For example, a Silversen L4RT mixer operating at 4000RPM for about 4 minutes was found to be suitable. Once completed, the composition may be packaged, for example as a pump spray or aerosol spray, and then filled with a propellant. In some embodiments, when the compositions are emulsions prepared from different phases, each prepared separately, the phases are combined and the emulsion may be formed by mixing or milling at room temperature or by any suitable means in the art.

The present invention provides a method for preventing or reducing the fading of artificially colored hair. The method comprises applying to the hair of keratin fibres, such as the scalp, a hair care composition having a combination of a hydrophobic particulate material and a silicone-based hydrophobic film former. By "artificially colored" is meant treating hair with synthetic or natural chemicals or materials to change or enhance the color or appearance of the hair.

The compositions of the present invention may be applied to dry or wet hair. The composition according to the invention is preferably applied to the hair (hair of the scalp, beard, etc.). More preferably, the composition of the invention can be distributed on the hair strands to form a substantially uniform coating on the stem of the hair fibers. The substantially uniform distribution may be achieved by spraying the composition onto the hair or working through the hair with a comb, brush, fingers, or the like. Typically the composition is left on the hair after application, i.e. is not rinsed off immediately after application. Alternatively, the hair treated with the composition may be rinsed with water after the composition is applied to the hair. The composition may be reapplied frequently, depending on the needs of the consumer. In one embodiment, the composition may be administered daily, every other day, weekly or biweekly, particularly after each shampoo.

Application of the present compositions to color-treated hair can reduce fading by at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or even at least about 100% after 1,2, 3, 4, 5,6, or 7 shampoos of the same color-treated hair, as compared to hair that has not been treated with the present compositions. The results can be tested using artificially colored hair samples, such as treated with or with the compositions of the present invention.

In other embodiments, the composition is applied to color treated, e.g., covered, synthetic fibers to prevent color fading in outdoor applications.

Example 1

This example provides compositions for reducing the fading of artificially colored hair. Representative hair lotion formulations are shown in table 1.

Table 1.

Example 2

By measuring L after repeated washing of chemically stained female hair^＊a^＊b^＊Color-space parameter change the ability of the hair lotions of the present invention of table 1 to retard the fading of artificially colored hair was evaluated. The female hairline used was an 3/4 inch x6 inch bleached Hair tress from International hairr treated with a two-part oxidative Hair coloring agent prior to use. The long hair was wetted and the hair styling liquid of table 1 was applied in an amount of 0.5g, working evenly through the hair. Repeatedly washing long hair with shampoo, and re-washing hair after each shampooLiquid application is used for wetting hair. The overall change in color (Δ E) was determined as Δ E²=(ΔL^＊)²+(Δa^＊)²+(Δb^＊)². Mixing the hair-beautifying liquid of the present invention with a standard preparation Avon Products' Advance TECHNIQES^TMColorprotection Lock-In Treatment was compared under otherwise identical conditions. The higher the Δ Ε value, the more dye remains in the hair bundle. The results are plotted in figure 1 and show that the hair lotions of table 1 are superior to the benchmark formulations in retarding fading after repeated washes, up to 18 shampoos.

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 the present 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 modifications are also intended to fall within the scope of the appended claims. All publications cited herein are incorporated by reference in their entirety.

Claims (23)

1. A method for improving color retention of artificially colored hair comprising applying to the artificially colored hair a composition comprising: :

(a) a hydrophobic particulate material having a median particle size of from about 10nm to about 20 μm, the hydrophobic particulate material comprising from about 0.1% to about 2.0% by weight of the composition;

(b) a silicone-based hydrophobic film former comprising from about 0.5% to about 20% by weight of said composition; and

(c) a cosmetically acceptable vehicle comprising a volatile hydrocarbon or silicone fluid having a vapor pressure above about 0.01mmHg at 20 ℃;

wherein the total weight percent of all non-volatile water-soluble or water-dispersible organic components in the composition is less than 5%, based on the total weight of the composition.

2. The method of claim 1, wherein the hydrophobic particulate material comprises a hydrophobically surface-modified oxide selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, tin dioxide, zinc oxide, iron oxide, and combinations thereof.

3. The method of claim 2, wherein the oxide is surface modified with alkylsilyl groups.

4. The method of claim 3, wherein the alkylsilane is octanoylsilane, and wherein the oxide is selected from the group consisting of alumina, silica, and mixtures thereof.

5. The method of claim 4, wherein the alumina is fumed alumina, and wherein the silica is fumed silica.

6. The method of claim 1, wherein the silicone-based hydrophobic film former comprises dimethicone, amodimethicone, dimethiconol, silicone polyurethane, silicone acrylate, or a combination thereof.

7. The method of claim 6, wherein the silicone-based hydrophobic film former comprises a poly (alkyl) acrylate backbone and a dimethicone polymer grafted with alkyl ester side chains.

8. The method of claim 1, wherein the composition is in the form of a liquid or an emulsion.

9. The method of claim 1, wherein the color loss of said hair is reduced or prevented after at least two shampooings as compared to untreated, otherwise identical hair.

10. The method of claim 1, wherein said artificially colored hair has been colored with a direct dye or an oxidative dye.

11. The method of claim 10, wherein the dye is an oxidative dye that applies a red color to the hair.

12. The method of claim 1, wherein the excipient comprises said volatile silicone fluid selected from the group consisting of cyclomethicone tetramers, cyclomethicone pentamers, cyclomethicone hexamers, trisiloxanes, methyltrimethylpolysiloxanes, or combinations thereof.

13. The method of claim 1, wherein the vehicle further comprises a solvent comprising ethanol or water.

14. The method of claim 1, wherein said composition is in the form of a water-in-silicone emulsion.

15. The method of claim 1, wherein the composition further comprises an emulsifier comprising an organosiloxane polymer having side chains comprising- (EO)_m-and/or- (PO)_nA group in which the sum of n and m is about 50 or less, the side chain being substituted by hydrogen or C_1-8And (4) alkyl end capping.

16. The method of claim 15 wherein the emulsifier comprises an emulsifier selected from the group consisting of peg10 dimethicone, peg/ppg-18/18 dimethicone, peg/ppg-19/19 dimethicone, and cetyl peg/ppg-10/1 dimethicone.

17. The method of claim 1, further comprising a water soluble quaternary or polyquaternium film former.

18. The method of claim 17, wherein the water soluble film forming agent is polyquaternium-37 (INCI).

19. The method of claim 1, wherein the silicone film former comprises silicone rubber.

20. The method of claim 1, wherein the composition is anhydrous.

21. The method of claim 1 wherein the composition is applied to color-treated hair and to wet hair after each shampooing for at least one week.

22. The method of claim 1 wherein the composition is applied to color-treated hair after each shampooing and to dry hair for at least one week.

23. A composition suitable for improving color retention on artificially colored hair comprising:

(a) a hydrophobic particulate material having a median particle size of from about 10nm to about 20 μm, the hydrophobic particulate material comprising from about 0.1% to about 2.0% by weight of the composition;

(b) a silicone-based hydrophobic film former comprising from about 0.5% to about 20% by weight of said composition; and

(c) a cosmetically acceptable vehicle comprising a volatile hydrocarbon or silicone fluid having a vapor pressure above about 0.01mmHg at 20 ℃;

wherein the total weight percent of all non-volatile water-soluble or water-dispersible organic components in the composition is less than 5%, based on the total weight of the composition.