HK1168285A - Methods and compositions for preventing or reducing frizzy appearance of hair - Google Patents

Description

Methods and compositions for preventing or reducing frizzy appearance of hair

Technical Field

The present invention relates to methods and compositions for preventing or reducing frizzy appearance of keratin fibers, particularly hair of the head, and for reducing the amount of hair fly-away strands, particularly under wet conditions. More particularly, the present invention relates to methods and compositions for forming a coating on hair that is resistant to moisture and water vapor from the air or surrounding environment.

Background

Many cosmetic and personal care compositions are utilized by consumers to enhance the look and feel of keratin fibers, such as hair. Exposure to humid conditions can cause hair to "pop out," which has an excessively swollen volume (i.e., "frizzy volume") or exhibits frizzy. This frizzy condition of hair often occurs uncontrollably and is often characterized by a number of hair fly-locks. Frizzy hair is unsightly and makes it difficult for the consumer to control and maintain the hairstyle. This frizzy condition is particularly pronounced in dry, damaged or curly hair.

A conventional way to reduce the frizzy appearance of hair is by applying silicone to the hair. However, these conventional compositions are generally impractical because the large amounts required to effectively reduce the frizzy appearance of hair can also cause the hair to feel greasy and sticky, thereby attracting dirt, and appearing dull and dirty. Conventional compositions may also flake off or leave an unsightly residue.

It is therefore an object of the present invention to provide an aesthetically pleasing composition for application to keratin fibers (e.g., hair) that prevents or reduces frizzy appearance and reduces the amount of hair fly-away when the hair is exposed to humid conditions. It is also an object of the present invention to provide a method for preventing or reducing frizzy appearance of hair without adversely affecting other aesthetic characteristics of the hair (e.g., look, feel, volume, shine, softness).

Summary of The Invention

In accordance with the foregoing and other objects, the present invention provides methods and compositions for preventing or reducing frizzy appearance of hair. The compositions of the present invention surprisingly provide protection against humid conditions and prevent or reduce frizzy appearance of hair over an extended period of time, such as 24 hours, 48 hours or days, or semi-permanent, which can last 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 invention, a method for preventing or reducing frizzy appearance of hair is provided. The method comprises applying to the hair a composition having: (a) a hydrophobic particulate material comprising hydrophobically surface-modified alumina having a median particle size of from about 10nm to about 20 μm, the hydrophobic particulate material constituting from about 0.1% to about 2.0% by weight of the composition, (b) a silicone-based hydrophobic film former constituting from about 0.01% to about 20% by weight of the composition, and (C) a cosmetically acceptable vehicle comprising a silicone oil having a vapor pressure above about 0.01mmHg at 20 ℃. The total weight percent of all non-volatile water-soluble or water-dispersible organic constituents in the composition is 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 alkylsilane groups (e.g. 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 bonded to an alkyl ester side chain.

The composition may be in the form of a liquid or an emulsion. In particular, the product is intended to be left on the hair without rinsing and may be distributed throughout the hair with a brush, comb or fingers or sprayed onto the hair. The composition may be applied to the hair when the ambient relative humidity is 85% or more. Alternatively, the composition may be applied to the hair daily. Furthermore, when the combination is applied to the hair, it may reduce or prevent the frizzy appearance of the hair after at least one shampooing or even after at least two shampooings.

In certain embodiments, the composition can provide a contact angle with a water droplet of 100 ° to 150 ° when applied as a thin film to a glass slide.

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

Detailed Description

All in weight percentThe amounts provided are relative to the total composition, unless otherwise stated. Unless otherwise provided, the term "alkyl" is intended to encompass straight, branched, or cyclic hydrocarbons, particularly those having from 1 to 20 carbon atoms, more particularly C_1-12A hydrocarbon.

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, such as water-in-oil emulsions, are within the scope of the present invention. As used herein, a water-in-oil emulsion includes a water-in-silicone emulsion. When referring to weight% of components 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 compositions of the present invention for reducing or preventing frizzy appearance of keratin fibers (e.g., hair) comprise a combination of a hydrophobic particulate material and a silicone-based hydrophobic film former for imparting a coating on the keratin fibers. This novel combination has been found to reduce and/or prevent the frizzy appearance of hair and to reduce the amount of fly-strands, particularly when the hair is exposed to humid conditions. Humid conditions refer to the humidity in the ambient air being at a level that can cause a frizzy appearance or fly-away locks of hair. In certain embodiments, the composition is effective to prevent or reduce frizz and reduce fly at the following ambient Relative Humidities (RH): greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 85%, greater than about 95% and then about 100% RH. It was observed that hair treated with the combination of the present invention was more resistant to frizzy appearance than hair treated with an equivalent amount of silicone alone. Without wishing to be bound by any theory, it is believed that reducing or preventing the frizzy appearance of hair or reducing the amount of fly-away strands of hair is achieved by resisting water vapor from the surrounding air, which is more abundant in humid conditions. It is also believed that the combination of the present invention provides a synergistic effect in reducing or preventing the frizzy appearance of keratin fibres and/or in reducing the amount of hair fly-strands. In particular, it is believed that the synergistic effect is observed in hair exposed to humid conditions. In one embodiment, the synergistic effect is observed in dry, damaged or curly hair.

In addition, it is believed that the compositions of the present invention may also prevent or reduce the frizzy appearance of hair by imparting hydrophobic characteristics to the hair. It is contemplated that the present invention may impart hydrophilic properties. The contact angle is a measure of the hydrophobicity of a surface and is the angle at which the liquid/vapor interface contacts a solid surface. One method for measuring the contact angle is by applying the composition as a film onto a glass slide and allowing the volatile material to evaporate. The contact angle between the film and the drop of water on the slide 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 the volatile solvent, which in some embodiments is characterized by a contact angle with a water droplet of greater than about 70 °, about 80 °, about 90 °, or about 100 ° up to about 110 °, about 120 °, about 130 °, about 140 °, or about 150 °.

The first component 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 film that substantially reduces water contact with the surface (i.e., reduces surface adhesion) by providing protrusions on which water droplets 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 shapeThe shape of (2). 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 sample of a specific amount (e.g., 0.01g) evenly spread on a base quartz plate is measured at a load of 50g and at 2mm/sec 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 high heat) alumina. Hydrophobically modified silicon dioxide (SiO)₂) Including fumed (or pyrogenic) silica (e.g., having a particle size in the range of about 7nm to about 40nm and an aggregate 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, for example, titanium dioxide and zinc oxide particles), or providing 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(K₄Fe(CN)₆) Potassium ferrocyanide trihydrate (K)₄Fe(CN)₆·3H₂O), and mixtures thereof. The particulate material may also be based on inorganic fillers such as talc, mica, silica, and mixtures thereof, or any of the clays disclosed in EP 1640419, the disclosure of EP 1640419 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, organosilicon, siloxane, alkylsiloxane, organosiloxane, fluorinated siloxane, perfluorosiloxane, organosilane, alkylsilane, fluorinated silane, perfluorinated silane, and/or disilazane and the like. The surface treatment may be any treatment that renders the particles more hydrophobic. The surface of the particle may, for example, be covalently or ionically bound to or adsorbed onto an organic or silicone-based molecule, or the particle 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, silicones, dimethicones, fatty acids (for example stearic acid),polymeric silanes, and their fluoro and perfluoro derivatives. The hydrophobic compound can be attached to the oxide particles by any suitable coupling agent, linker 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, silicone, and fluoro or perfluoro derivatives thereof. Hydrophobic polymeric coatings (including polyurethanes, epoxies, etc.) are also expected to be useful. U.S. patent No. 6,315,990 (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 contemplated 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 high heat) alumina or fumed (or high heat) silica which is surface functionalized with alkylsilyl, fluoro-alkylsilyl or perfluoro-alkylsilyl groups (preferably with alkylsilyl groups)(i.e., surface treatment with alkylsilanes). Typically, the alkylsilyl group will contain C_1-20Hydrocarbons (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)_1-12Alkyl-trimethoxysilanes or C_1-12-alkyl-triethoxysilane)) are introduced. Preferably, the particle surface is functionalized with alkylsilyl groups (i.e., surface treated with alkylsilanes). 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 generally 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 fumed (or highly heated), the primary particle size (primary particle size) will generally be very small, i.e., on the order of 5nm to about 30 nm. The specific surface area 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 g, and preferably from about 100 to about 200m²(ii) in terms of/g. Suitable hydrophobically modified alumina particles include fumed alumina treated with octylsilane (obtained by reacting trimethoxyoctylsilane with fumed alumina), 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., at temperatures above 1000 ℃) to drive off volatile impurities in the crude metal oxide. 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.

Other particles may be included, such as hydrophobically modified fumed silica. When present, suitable hydrophobically modified fumed silica particles include, but are not limited to, AEROSIL^TMR202，AEROSIL^TM R805，AEROSIL^TM R812，AEROSIL^TM R812S，AEROSIL^TM R972，AEROSIL^TM R974，AEROSIL^TM R8200，AEROXIDE^TM LE-1，AEROXIDE^TMLE-2, and AEROXIDE^TMLE-3 from Evonik/Degussa Corporation of Parsippany, N.J., said particles being considered hydrophobic fumed silica, surface functionalized with alkylsilyl groups for hydrophobicity and having Specific Surface Areas (SSA) of about 160. + -. 30m each²G, about 220. + -.30 m²The sum of the amounts of the components is 100 +/-30 m²(ii) in terms of/g. Hydrophobically modified silica materials described in U.S. patent publication 2006/0110542 (Dietz et al), which is incorporated herein by reference, are also expected to be particularly suitable. Other optional particles include: particulate silicone wax under the trade name Tegotop^TM105(Degussa/Goldschmidt chemical Corporation); and particulate vinyl polymers, which are known under the name Mincor^TMSold under 300 (BASF). Although silicon dioxide (SiO)₂) And hydrophobically modified silicas are contemplated to be useful in some embodiments, in other embodiments, the compositions will be substantially free of silica or hydrophobically modified silica. By substantially free of silica or hydrophobically modified silica, it is meant that these components constitute less than about 2%, preferably less than about 1%, more preferably less than about 0.5% (by weight)) Of one or more particulate materials. In other embodiments, the composition will be free of silica or hydrophobically modified silica. By "free" is meant that no intentional addition is made and that 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.

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 1 μm, more preferably from about 10nm to about 5 μm, about 20 μm, about 50 μm, or about 100 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 of about 1mm or more 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.

Generally, 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 2.0%, 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 certain embodiments, the one or more particulate materials may comprise about 0.4%, about 0.5%, about 0.6%, about 0.67%, about 0.7%, about 0.75%, 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 particulate material may comprise more than about 5%, more than about 10%, more than about 15%, more than about 20%, more than about 25%, more than about 30%, more than about 35%, more than about 40%, more than about 45%, more than about 50%, more than about 55%, more than about 60%, more than about 65%, more than about 70%, more than about 75%, more than about 80%, more than about 85%, more than about 90%, or more than about 95% (by weight) fumed alumina functionalized with octyl silicon groups.

The second component of the composition of the present invention comprises one or more film formers. The film former preferably comprises a hydrophobic material. The hydrophobic film former may be any hydrophobic film former suitable for use in cosmetic compositions, including but not limited to hydrophobic film-forming polymers. The term film-forming polymer may be understood to mean a polymer capable of forming (by itself or in the presence of at least one auxiliary film-forming agent) a continuous film, which adheres to a surface and acts as a binder for the particulate material. The term "hydrophobic" film-forming polymer will generally 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 ℃. Alternatively, a "hydrophobic" film-forming polymer may 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), and 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 polyurethane, silicone acrylate, or combinations thereof. Without wishing to be bound by any theory, it is believed that the reduction or prevention of frizzy appearance of hair and the reduction of the amount of hair fly-strands is achieved by the hydrophobic film former binding the hydrophobic particulate material into an aggregate structure (similar to brick and mortar walls), thereby improving the water vapor resistance properties of hair treated with the composition of the present invention.

The film-forming agent may be natural or synthetic, polymeric or non-polymeric, a resin, a binder, having a low or high molar mass. The polymeric film former may be natural or synthetic, added or condensed, homo-or hetero-chain, mono-or polydisperse, organic or inorganic, homopolymer or copolymer, linear or branched or crosslinked, charged or uncharged, thermoplastic or thermosetting, elastomeric, 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, polyacetic acid, 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, those described in 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 building blocks (blocks) selected from styrene (S), Alkylstyrene (AS), ethylene/butylene (EB), ethylene/propylene (EP), butadiene (B), isoprene (I), acrylates (a) and Methacrylates (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 MD 1600 (gelling agent (IDD) in isododecane from Penreco).

Particular mention may be made of polyolefins, and in particular C₂-C₂₀Olefin copolymers, e.g. polybutene, having linear or branched, saturated or unsaturated C₁-C₈Alkylcelluloses of alkyl radicals, e.g. ethylcellulose and propylcellulose, copolymers of Vinylpyrrolidone (VP), especially vinylpyrrolidone and C₂To C₄₀(more preferably C)₃To C₂₀) Copolymers of olefins, including copolymers of vinylpyrrolidone with dodecene or dodecane monomers sold under the trade names GanexV 220 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. Pat. No. 7,150,878 (Gonzalez et al), 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 group 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. Vinyl polymers for hydrophobic film-forming polymers can also be producedHomopolymerization 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, vinyl benzoate and vinyl t-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 copolySubstance, ethylene/VA copolymer, fluorine C_2-8Alkyl dimethyl polysiloxane, C_30-38Olefin/isopropyl maleate/MA copolymer, hydrogenated styrene/butadiene copolymer, hydroxyethyl ethyl cellulose, isobutylene/MA copolymer, methyl methacrylate crosspolymer, methacryloyl ethyl betaine/acrylate copolymer, octadecene/MA copolymer, octadecene/maleic anhydride copolymer, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, oxidized polyethylene, perfluoropolymethyl isopropyl ether, polyethylene, polymethyl methacrylate, polypropylene, PVM/MA decadiene crosspolymer, PVM/MA copolymer, PVP, PVP/decene copolymer, PVP/eicosene copolymer, PVP/hexadecene copolymer, PVP/MA copolymer, PVP/VA copolymer, sodium acrylate/vinyl alcohol copolymer, stearyloxydimethicone, stearyloxytrimethylsilane, stearyl alcohol, octadecyl vinyl ether/MA copolymer, styrene/DVB copolymer, styrene/MA copolymer, triacontyl PVP, trimethylsiloxysilicacid, VA/crotonic acid copolymer, VA/crotonic acid/vinyl propionate copolymer, VA/butyl maleate/isobornyl acrylate copolymer, vinylcaprolactam/PVP/dimethylaminoethyl methacrylate copolymer, and vinyldimethicone.

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 sequence of at least one aliphatic polyester origin, cycloaliphatic polyester origin and aromatic polyester origin; at least one silicone sequence, branched or unbranched, 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 Fluomer (polyperfluorophenanthane) or Flutec PP3, available from F2 chemicals, and silicone acrylates such as acrylate/dimethicone copolymers sold under the trade names KP-545 or KP 550 (Shin-Etsu). Suitable film formers include, but are not limited to, aminodipropyldimethicone, aminopropyldimethicone, aminodimethicone hydroxystearate, behenyloxydimethicone, 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 aminoterminated polydimethylsiloxanes (as described in CTFA publication No.189, which is incorporated herein by reference). All CTFA books provided herein are found in the 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 generally 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 be, without limitation, from about 500,000 centistokes to about one hundred million centistokes (measured at 25 ℃). High molecular weight dimethicone is commercially available in combination with a lower molecular weight silicone or with a volatile silicone, which makes the high molecular weight dimethicone easier to handle. Suitable mixtures containing high molecular weight dimethylpolysiloxanes (MW about 500,000) are 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 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 conjugated 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 publication 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 that are contemplated to be useful include, but are not limited to, paraffin wax, ozokerite wax, 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 (Baker hughes 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.

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 forming agent, although at high levels (e.g., greater than 20% by weight based on the total weight of the film forming agent) it may be desirable to increase the ratio of hydrophobic particles to film forming agent 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 one embodiment, 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. Typically, 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. Mention may be made of the following proportions of hydrophobic particulate material(s) and film-forming agent(s): 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 certain embodiments, the composition will comprise a silicone acrylate film former in addition to a silicone rubber film former. The silicone acrylate film former and silicone rubber film former may 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 generally comprise a cosmetically acceptable vehicle. By "cosmetically acceptable" it is meant that the vehicle is safe for contact with human skin. The medium may comprise a liquid, including 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 an aqueous 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 substantially free or free of emulsifiers. 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 volatile solvent. Typically, the volatile solvent can have a vapor pressure above about 0.01mmHg at 20 ℃. 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 silicones (e.g., cyclopentasiloxane), lower alcohols (e.g., ethanol, isopropanol, etc.), esters of acetic acid (e.g., ethyl acetate, butyl acetate, etc.), and the like. Preferred volatile solvents will be cosmetically acceptable.

Volatile silicones are preferred volatile solvents. Volatile silicones refer to oils that readily evaporate at ambient temperature. 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 ℃ to about 250 ℃ 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 include a cyclomethicone, which includes tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicone, or mixtures thereof. Suitable dimethicone is available from Dow Corning under the nameKnown as Dow CorningA liquid, and 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, "volateSilicone Fluids for Cosmetics," Cosmetics and Toiletries,91:27-32(1976), which is incorporated herein by reference in its entirety. Linear volatile silicones generally 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 Corning 200, Dow Corning 244, Dow Corning 245, Dow Corning 344, and Dow Corning 345, (Dow Corning Corp.); SF-1204 and SF-1202 silicone oils (G.E. Silicones), GE 7207 and 7158(General Electric Co.); and SWS-03314(SWS Silicones Corp.). Linear, volatile silicones include low molecular weight polydimethylsiloxane compounds such as methyltrimethylsiloxane, trisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane. 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 (also known as 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, by which is meant 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 the volatile C_5-12Among the hydrocarbons, mention may be made in particular of the isododecanes, which are available under the trade name Permethyl-99A (Presperse Inc.). Suitable fluorinated solvents include, but are not limited to, for example, perfluoroether, perfluorodecalin, perfluoro (methyldecalin), perfluorohexane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane, perfluoroheptane, perfluorooctane, perfluorononane, and perfluoromethylcyclopentane.

In a preferred embodiment, the solvent will comprise a combination of volatile silicone (preferably cyclomethicone pentamer) and anhydrous ethanol. Preferably, the volatile silicone (cyclomethicone pentamer) will comprise from about 1% to about 99% of the solvent system, and ethanol will comprise from about 1% to about 99% (by weight) of the solvent system. More particularly, volatile silicones (cyclomethicone pentamers) will constitute from about 50% to about 99% and ethanol will constitute from about 1% to about 50% (by weight) of the solvent system. In a preferred embodiment, the volatile silicone (cyclomethicone pentamer) will constitute from about 70% to about 90% and the ethanol will constitute from about 10% to about 30% (by weight) of the solvent system.

In other embodiments, the composition according to the invention will comprise ethanol (preferably anhydrous) in combination with one or more solvents having a vapor pressure less than that of ethanol at 25 ℃. In another embodiment, the composition according to the invention will comprise ethanol (preferably anhydrous) in combination with one or more solvents having a vapour pressure at 25 ℃ that is greater than the vapour pressure of ethanol.

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 composition will typically comprise a volatile hydrophobic solvent, such as a volatile hydrocarbon, a volatile silicone, and the like.

Water-in-oil emulsion

The composition according to the invention may be formulated as a water-in-oil emulsion. 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 oily 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, cyclosilicones, and polysiloxanes; 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 having10-16 carbon atoms. Representative hydrocarbons include decane, dodecane, n-tetradecane, n-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 Permethyl 99A, manufactured by Permethyl Corporation, under the trade name Permethyl 99A^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.

Critically, the emulsions have little or no non-volatile hydrophilic components, including some conventional humectants. Components 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 constituents, such as the non-volatile water-soluble or water-dispersible organic constituents, 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.

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 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 generally 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, polyglycerol-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 ester, dimethicone copolyol; polyglycerol esters such as polyglycerol-3-diisostearate, glycerol laurate, steareth-2, steareth-10 and steareth-20. Other emulsifiers are provided in INCI ingredient dictionaries and manuals, 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 comprise 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.

Aqueous silicone-in-water emulsion

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 dissolve the water-soluble ingredients into the composition. Water-solubility 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 the 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 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 lotion consistency is desired and the composition includes a small amount of water soluble polymer in its formulation, 10% to 25% 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 easily at ambient temperature. Generally, 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 from about 35 ℃ to about 250 ℃ at atmospheric pressure.

Volatile silicones that can be used in the silicone oil phase of the water-in-silicone emulsion include cyclic and linear volatile dimethylsiloxane silicones. In one embodiment, the volatile silicone may include a cyclomethicone, which includes tetramer (D4), pentamer (D5), and hexamer (D6) cyclomethicone, or mixtures thereof. Mention may in particular be made of volatile cyclomethylpolysiloxanes-hexamethylcyclotrisiloxane, octamethyl-cyclotetrasiloxane, and decamethyl-cyclotetrasiloxanePentasiloxane. Suitable volatile dimethicone is available from Dow Corning under the name Dow CorningA liquid, 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 generally 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 Corning 200, Dow Corning 244, Dow Corning 245, Dow Corning 344, and Dow Corning 345, (Dow Corning Corp.); SF-1204 and SF-1202 silicone oils (G.E. Silicones), GE 7207 and 7158(general electric Co.); and SWS-03314(SWS Silicones Corp.). Linear, volatile silicones include low molecular weight polydimethylsiloxane compounds such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane.

The non-volatile silicone oil will typically comprise a polyalkylsiloxane, a polyarylsiloxane, a polyalkylarylsiloxane, or mixtures thereof. Polydimethylsiloxane is the 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 greater than 250 ℃ at atmospheric pressure. Non-limiting examples include dimethylpolysiloxane (dimethylpolysiloxane), phenyltrimethylpolysiloxane, and diphenyldimethylpolysiloxane.

The volatile and non-volatile silicone oils may optionally be substituted with various functional groups, such as alkyl, aryl, amino, vinyl, hydroxy, haloalkyl, alkylaryl, and acrylate groups.

The water-in-silicone emulsion is emulsified with a nonionic surfactant (emulsifier). Suitable emulsifiers include polydiorganosiloxane-polyoxyalkylene building block copolymers, including those described in U.S. Pat. No. 4,122,029, the disclosure of which is incorporated herein by reference. These emulsifiers usually comprise a polydiorganosiloxane backbone (usually polydimethylsiloxane) with an inclusion of- (EO)_m-and/or- (PO)_nSide chains of radicals in which EO is ethyleneoxy and PO is 1, 2-propyleneoxy, usually with hydrogen or lower alkyl (e.g. C)_1-6Usually C_1-3) Capping or end-capping. The side chain will preferably comprise 50 EO and/or PO units or less (e.g., m + n = g =)<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 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 5225CFORMULATION AID, Silicone SF-1528 available from General Electric, ABIL EM 90 and EM 97 available from Goldschmidt Chemical Corporation (Hopewell, Va.), and SILWET^TMEmulsifier series, sold by OSI Specialties (Danbury, CT).

Examples of silicone water-in-emulsifier 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 SF 1288, 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 durability of performance over repeated hair rinses, the composition preferably has a minimum level of emulsifier capable of producing a stable emulsion. The silicone-in-water emulsifier will generally 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 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.

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 the water-in-oil or water-in-silicone emulsion. The oil or silicone is then mixed with the aqueous phase to form an emulsion. The hydrophobic film former and any hydrophobic pigments 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 silicic acid, polybutene, polyisobutylene, hydrogenated polyisobutylene.

Silicone oils, such as aryl-substituted siloxanes 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 PTM 100(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 oil 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 silicones, such as pentaphenyl trimethyl trisiloxane or tetraphenyl tetramethyl trisiloxane, may also be used to improve gloss, which is commercially available as an HRI liquid from Dow corning HRI. Certain organic compounds, such as octyl methoxycinnamic acid, may also be used to enhance gloss.

Gloss enhancers are generally 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, including embodiments wherein the gloss enhancer is present at about 0.1%, 0.3%, 0.5%, 0.75%, 1%, 1.25%, or 1.5% (by weight) of the composition.

In addition to the foregoing, the compositions according to the invention may contain other pigments, pearlescent and/or coloring agents to counter the white appearance of fumed alumina or fumed silica, or to impart a desired color to the hair, provided that such components 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, and mica, organic pigments include barium, strontium, calcium, or aluminum lakes, ultramarine, and carbon black, and 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 with one or more compatibilizing agents or surface treated to aid dispersion in a solvent. Preferred pigments and/or colorants are those that have been surface treated to render them hydrophobic.

Preferred colorants include iron oxide, black iron oxide, brown iron oxide, CI77489, CI 77491, CI 77492, CI 77499, 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, Red iron oxide, synthetic iron oxide and yellow iron oxide.

Various fillers and other components 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, e.g. Expancel^TM(Nobel Industries)，Polytrap^TM(Dow Corning) and Silicone resin Microbeads (Tospearl)^TMFrom Toshiba), and the like.

Other pigment/powder fillers include, but are not limited to, inorganic powders such as gums, chalk, fuller's earth, kaolin, sericite, muscovite, phlogopite, synthetic mica, laponite, 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, starch aluminum octenyl succinate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstates, magnesium, silica alumina, zeolites, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powders, metal soaps (zinc stearate, magnesium stearate, zinc myristate, calcium palmitate, and aluminum stearate), colloidal silicone dioxides, and boron nitrides, 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; 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 vapor resistance and frizzy appearance of the treated hair are not compromised. Generally, all additional pigments, colorants, fillers, and the like (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 commonly 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 the keratin fibres. Preferably, these other ingredients include at least one bioactive ingredient for improving 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, chelating agents, colorants, emollients, emulsifiers, excipients, fillers, fragrances, gelling agents, humectants, minerals, humectants, photostabilizers (e.g., UV absorbers), 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, deodorant, sunscreen and/or antiperspirant ingredients. If present, the level of such other components should be judiciously selected so as not to adversely affect the ability of the composition to reduce or prevent the frizzy appearance of hair. Collectively, all such other components will suitably comprise less than 5% (by weight) of the composition, but will generally 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 will be free or substantially free of cationic hair conditioning agents. By substantially free of cationic hair conditioning agents, it is meant that the composition comprises less than 0.5% (by weight), preferably less than 0.25% (by weight), more preferably less than 0.1% (by weight) cationic conditioning agents.

In other embodiments, the composition may contain an amount of cationic (quaternary ammonium) component that is anhydrous or has a very low level of water, e.g., less than 1% (by weight). Suitable quaternary ammonium compounds include, but are not limited to, for example, polyquaternium-37 (INCI), cyclopentasiloxane and silicone quaternium-18 (INCI), PEG-2 Albizia oil amide ethylmethylammonium methylsulfate and hexylene glycol (INCI), and cetyl 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 composition of the invention, this 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 generally be present at about 20% to about 50%, by weight of the composition in which the propellant is included.

Particularly detrimental to preventing and reducing frizzy appearance in hair and reducing hair frizzy strands are non-volatile water-soluble or water-dispersible components (e.g., propylene glycol or glycerin) that can coat or mask particles on the surface of the hair, or that can attract or bind water. Preferably, the total amount of such non-volatile water-soluble or water-dispersible components 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 components, and in particular free of liquid water-soluble or water-dispersible components.

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, which 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 Corning 9040, 9041, and 9506, and Shin-Etsu KSG-15, 16, and 17, and Shin-Etsu KSP-100, 101, 102, 103, 104, 105, 200, and 300. The 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%. Silicone elastomers do not form good films and are not included in calculating the ratio of powder to film former. Vinyl dimethicone/methyl silicone/silsesquioxane crosspolymer is a silicone elastomer that has been 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), thickeners (e.g., PEG-150/decanol/SMDI copolymer), sunscreens, preservatives, fragrances, and the like.

Other components 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 reduction or prevention of frizzy appearance of hair and the formation of water vapor resistant films.

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 limitation on the order of addition of these components 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 certain 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 frizzy appearance and hair fly-away strands, particularly in dry, damaged or curly hair, comprising applying to keratin fibres a hair care composition having a combination of a hydrophobic particulate material and a silicone-based hydrophobic film former. As used herein, damaged hair is any type of hair fiber that suffers from a detrimental effect on hair appearance, feel, or intensity, including color-treated hair, as the dyeing process often causes damage to the feel and intensity of the hair fiber. However, the present invention is not limited to application to dry, damaged or curly hair. The methods and compositions may be applied to any hair, including fine hair, to reduce or prevent frizzy appearance and to impart a water-resistant film on keratin fibers.

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 (scalp hair, beard, etc.) to provide resistance to frizzy appearance. 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 and applying the composition throughout the hair. The substantially uniform distribution may also be achieved by applying the composition to the hair by hand and rubbing and spreading the composition on the hair with the fingers. A brush or comb may also be used to distribute the composition in a substantially uniform manner throughout the hair. The composition may be applied to the hair and allowed to remain on the hair. Alternatively, the hair treated with the composition may be rinsed with water after applying the composition to the hair. The composition can be reapplied at any time, depending on the needs of the consumer. In one embodiment, the composition may be applied daily, every other day, weekly, or biweekly.

It has been found that when the composition of the present invention is applied to hair (particularly scalp hair), the frizzy appearance of the hair can be reduced and/or prevented, the undesirable volume is reduced, the consumer's ability to control and maintain the hairstyle (e.g., to make the hair easier to manipulate or style), the amount of fly strands of the hair is reduced, the consumer's ability to obtain well-aligned hair (e.g., smooth and smooth out irregularities, frizzy hair or fly), impart a desired feel (e.g., soft or smooth) to the hair, or the consumer's ability to hold or extend the hairstyle, or change the volume of the hair when applied to hair (particularly scalp hair). In particular, the present invention imparts these properties to hair and protects hair against aesthetically undesirable changes, particularly in humid conditions.

The volume of hair refers to the structure of the hair strand and the space occupied in a defined area, and relates to the apparent hair thickness through vision and touch, which also relates to the body of the hair. The body may be defined by feel, weight and hair styling. Lack of a host causes the hair to feel weak, with less maneuverability. In some embodiments, the compositions of the present invention can reduce the volume of hair. For example, the compositions of the present invention may reduce the volume of hair by at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least 90%, or even at least about 100%. In other embodiments, the compositions of the present invention reduce the volume of hair by about 50% to about 100%, about 65% to about 95%, about 70% to about 90%, or about 75% to about 85%.

The benefits of the present invention can be imparted to hair immediately upon application of the composition to hair and can last for a period of time after application of the composition to hair. The benefit can last for a period of time of at least 6 hours, at least 8 hours, at least 12 hours, or at least 18 hours. Preferably, the benefit may last for an extended period of time. For example, in some embodiments, the benefit lasts at least 24 hours, at least 48 hours, at least 3 days, at least 5 days, or at least 1 week. In other embodiments, the benefit is semi-permanently sustained, meaning that the benefit is sustained for more than 1 week. In a preferred embodiment, hair treated with the combination of the invention retains some or all of the benefits identified above (particularly resistance to frizzy appearance) after shampooing the hair at least once, which is one cycle of wetting the hair, applying the shampoo thereto and rinsing the hair. In a more preferred embodiment, hair treated with the combination of the invention retains some or all of the benefits identified above, particularly resistance to frizzy appearance, after shampooing the hair at least two, three, or more times.

This can be tested by using a hair sample treated with a composition of the present invention. Similarly, the composition may be applied to the hair of pets (e.g., dogs) or fur materials (e.g., fur coats) to improve the aesthetics of the hair.

Changes in Hair volume can be determined on a bundle of Hair using a variety of techniques, including those described by c.r.robbins and r.j.crawford in the article "a Method to evaluation Hair Body," j.soc.cosmet.chem., 35, pp.369-377(1984), the disclosure of which is incorporated herein by reference, and modified versions thereof. Other means suitable for assessing hair volume changes involve taking a digital picture of the hair strand and analyzing the picture using an image analysis program, a commercially available test service known as image analysis methods from MarTech Personal Care. Another suitable means for assessing hair volume changes involves pulling a bundle of hair through loops of different radial dimensions and correlating the force required for the pull to a measure of volume or body. An exemplary method of such an alternative test is performed using the Dia-Stron MiniaureTensil Tester 175 and is available as a commercially available test service known as the radial compression/Ring method from MarTech Personal Care. Preferably, the change in hair volume can be detected using the test protocol described below.

Hair volume test method

The method consists of: fine raw european brown hair was prepared in the form of a sample suitable for attachment to a hair holder, and a 2cm ring. Each hair sample is configured to the appropriate weight and length for loop attachment and can be pre-treated by washing the hair strands 2 to 3 times. Each cleaned raw hair sample was combed 5 times with a large tip control comb (end control comb) before any measurements were taken.

To test the volume of the hair strand, a sample of hair was pulled through a 2cm loop at a constant rate. The force applied to the hair tress when the hair sample was pulled through a 2cm loop was measured using the Dia-Stron Miniature tension Tester 170. The amount of work used to pull each sample of hair through the loop was obtained by calculating the area under the curve of the measured force applied to the strand versus the length of the strand. All such measurements are obtained from dry hair.

5-6 measurements (curves) were made on the washed original hair tresses before analysis. The baseline value is determined using the average amount of work calculated from measurements taken of the original hair strand. The same tress may then be treated with the composition of the invention. The treated tresses were allowed to dry and then tested in the same manner. The percent increase in volume is determined by comparing the average amount of work measured from the treated hair strand to a baseline average work value obtained from the original hair strand. An increase in work indicates an increase in hair volume.

Examples

Example 1

This example provides a composition for preventing or reducing frizzy appearance of hair. Formulations 1A and 1B were prepared according to table 1.

TABLE 1

Formulation 1A is an exemplary embodiment of an anhydrous formulation, while formulation 1B provides an exemplary embodiment of a shake-up emulsion. Emulsifiers may be added to formulation 1B to provide a more durable emulsion or a stable emulsion. Suitable emulsifiers include ethoxylated silicone emulsifiers such as PEG-10 dimethicone, PEG/PPG-18/18 dimethicone, PEG/PPG-19/19 dimethicone, cetyl PEG/PPG-10/1 dimethicone, and the like.

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 (45)

1. A method for preventing or reducing frizzy appearance of hair, the method comprising applying to the hair a composition comprising:

(a) a hydrophobic particulate material comprising 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 0.5% to about 20% by weight of said composition, and

(c) a volatile hydrocarbon or silicone oil 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 constituents in the composition is less than 5%, based on the total weight of the composition.

2. The method according to claim 1, wherein the alumina is surface modified with alkylsilane groups.

3. The method of claim 2 wherein said alkylsilane is caprylylsilane.

4. The method of claim 2 wherein the alumina is fumed alumina.

5. The method of claim 4 wherein said alkylsilane is caprylylsilane.

6. The method according to claim 1, wherein said silicone-based hydrophobic film former comprises dimethicone, amodimethicone, dimethiconol, silicone urethane, silicone acrylate, or a combination thereof.

7. The method according to claim 6, wherein the silicone-based hydrophobic film former comprises a silicone acrylate copolymer.

8. The method according to claim 7, wherein the silicone acrylate copolymer is a copolymer comprising a poly (alkyl) acrylate backbone and a dimethicone polymer grafted to an alkyl ester side chain.

9. A method according to claim 1, wherein the composition forms a substantially uniform coating on the shaft of the hair fibre.

10. The method according to claim 9, wherein the composition is in the form of a liquid or an emulsion.

11. The method according to claim 9, wherein the composition applied to the hair is an emulsion comprising water.

12. A method according to claim 11, wherein the composition is distributed throughout the hair with a brush, comb or fingers.

13. The method according to claim 4, wherein the composition applied to the hair is an emulsion comprising water.

14. The method according to claim 13, wherein the silicone-based hydrophobic film former comprises a silicone acrylate copolymer.

15. The method according to claim 14, wherein the silicone acrylate copolymer is a copolymer comprising a poly (alkyl) acrylate backbone and a dimethicone polymer grafted to an alkyl ester side chain.

16. The method according to claim 14, wherein the composition further comprises ethanol.

17. The method according to claim 1, wherein the frizzy appearance of said hair is reduced or prevented after at least one shampooing.

18. The method according to claim 15, wherein the frizzy appearance of said hair is reduced or prevented after at least two shampooings.

19. The method according to claim 1, wherein frizzy volume of the hair is reduced.

20. The method according to claim 1, wherein the composition is applied to the hair daily.

21. A method according to claim 1, wherein the composition is applied to the hair when the ambient relative humidity is 85% or above.

22. The method according to claim 1, wherein said composition comprises said silicone oil having a vapor pressure above about 0.01mmHg at 20 ℃.

23. A composition for preventing or reducing frizzy appearance of hair comprising:

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

(b) a silicone acrylate film former comprising from about 0.1% to about 20% by weight of said composition, and

(c) a silicone film former comprising from about 0.1% to about 20% by weight of said composition, and

(d) a cosmetically acceptable vehicle comprising a silicone oil having a vapor pressure above 0.01mmHg at 20 ℃;

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

24. The composition according to claim 23, wherein said alumina is surface modified with alkylsilane groups.

25. The composition of claim 24 wherein said alkylsilane is caprylylsilane.

26. A composition according to claim 23 wherein the alumina is fumed alumina.

27. A composition according to claim 24 wherein the alumina is fumed alumina.

28. A composition according to claim 23, wherein said silicone film former is selected from the group consisting of: dimethicone, amodimethicone, dimethiconol, silicone polyurethane, and combinations thereof.

29. The composition according to claim 23, wherein the volatile silicone is selected from the group comprising: cyclomethicone tetramer, cyclomethicone pentamer, cyclomethicone hexamer, trisiloxane, methyltrimethylpolysiloxane, or a combination thereof.

30. The composition of claim 23, wherein the vehicle further comprises ethanol.

31. The composition of claim 23, wherein the vehicle further comprises water.

32. The composition according to claim 31, wherein the emulsion is a water-in-silicone emulsion further comprising an emulsifier.

33. The composition of claim 32, wherein the emulsifier comprises a polymer having an average molecular weight- (EO) of_m-and/or- (PO)_nOrganosiloxane polymers of side chains of groups in which the sum of n and m is about 50 or less, the side chains being hydrogen or C_1-8Alkyl-terminated.

34. The composition according to claim 32, wherein the emulsifier comprises an emulsifier selected from the group consisting of: peg-10 dimethicone, peg/ppg-18/18 dimethicone, peg/ppg-19/19 dimethicone, and cetyl peg/ppg-10/1 dimethicone.

35. The composition according to claim 23, further comprising a water soluble film forming agent.

36. A composition according to claim 35, wherein said water soluble film former is a quaternary ammonium salt or a polyquaternary ammonium salt.

37. The composition according to claim 36, wherein said water soluble film former is a polyquaternium which is polyquaternium-37 (INCI).

38. The composition according to claim 32, the silicone acrylate copolymer being a copolymer comprising a poly (alkyl) acrylate backbone and a dimethicone polymer grafted to an alkyl ester side chain.

39. The composition of claim 38, wherein the alumina is fumed alumina comprising an alkylsilane group surface modification.

40. A composition according to claim 39, wherein said silicone film former is selected from the group consisting of: dimethicone, amodimethicone, dimethiconol, silicone polyurethane, and combinations thereof.

41. The composition according to claim 40, wherein the volatile silicone is selected from the group comprising: cyclomethicone tetramer, cyclomethicone pentamer, cyclomethicone hexamer, trisiloxane, methyltrimethylpolysiloxane, or a combination thereof.

42. The composition of claim 40, wherein said vehicle further comprises ethanol.

43. A composition according to claim 23, wherein said silicone film former comprises dimethicone.

44. A composition according to claim 23, wherein said silicone film former comprises silicone rubber.

45. The composition according to claim 23, wherein the composition is anhydrous.