EMULSION COMPOSITIONS CONTAINING A HYDROPHOBICALLY MODIFIED POLYSACCHARIDE COMPOUND AND AN AQUEOUS-PHASE FILM FORMING AGENT

Abstract

EMULSION COMPOSITIONS CONTAINING A HYDROPHOBICALLY MODIFIED POLYSACCHARIDE COMPOUND AND AN AQUEOUS-PHASE FILM-FORMING AGENT. The invention relates to oil-in-water (o / w) emulsion compositions, preferably for skin, comprising at least one hydrophobically modified polysaccharide compound and at least one aqueous-phase film-forming agent, as well as methods and equipment for incorporating such emulsion compositions in one or more containers or for application. Figure for abstract: none

Description

Title of the invention: EMULSION COMPOSITIONS CONTAINING A HYDRO-PHOBICALLY MODIFIED POLYSACCHARIDE COMPOUND AND A WATER-BASED FILM FORMER FIELD OF THE INVENTION

[0001] The present invention relates to oil-in-water (o / w) emulsions (compositions) comprising at least one hydrophobically modified polysaccharide compound and at least one film former in the aqueous phase, as well as methods and kits comprising such emulsion compositions in one or more containers or in application. The compositions have beneficial cosmetic properties, including, for example, as primer or fixative compositions for good or improved staying power, water and / or sebum resistance, and / or transfer resistance properties of separately applied compositions. DISCUSSION OF THE CONTEXT

[0002] Currently, on the market for the care and makeup of keratinous materials, many products claim persistence throughout the day, resistance to external factors such as water, sebum, mechanical friction, etc. (water-resistant mascara, meal-resistant lipsticks, long-lasting foundations). Long-lasting products for lips, eyelashes, eyebrows or the face, which can be used at home, are mainly based on synthetic coating polymers in the presence of organic solvents.For lip makeup and facial makeup compositions, compositions are known comprising an unmodified silicone resin as film-forming agent, such as the compound having the INCI name: Trimethylsiloxysilicate or a compound having the INCI name: Polypropylsilsesquioxane, or alternatively a silicone acrylate copolymer such as the product having the INCI name: Acrylates / polytrimethylsiloxymethacrylate copolymer). Long-lasting makeup products for eyelashes and / or eyebrows (mascaras, eyeliners) typically use waxes or particles of film-forming polymers in aqueous suspension of the latex type (i.e.: styrene / acrylate copolymers) as film-forming agents.

[0003] In addition to these long-lasting products, the current trend is towards semi-permanent makeup. Specifically, in recent years, classic makeup products have found themselves in competition with the semi-permanent makeup market in professional salons. It is found in the eye makeup sector (semi-permanent mascara, permanent eyelash makeup, eyelash extensions, etc.), eyebrows (semi-pigmentation known as blade pigmentation), complexion (freckles, moles or the entire face, healthy glow effect or radiant complexion) or lips (semi-permanent tattoo). This new trend is pushing consumers to seek increasingly long-lasting results for greater practicality (avoiding the need to apply and remove makeup daily, a healthy glow effect upon waking, etc.).

[0004] The aim of the present invention is to provide compositions which offer excellent persistence of the expected cosmetic effects, in particular of the color of the makeup on keratinous materials (skin, lips, nails, hair, eyelashes, eyebrows) which can prolong the duration of the cosmetic composition on the keratinous materials, as well as improve the hold of the cosmetic composition on the keratinous materials and its resistance to external forces such as one or more of mechanical friction, water, sweat and perspiration, sebum, oil, etc.

[0005] Potentially associated patent references include: • US 11,253,462 discloses low wax compositions containing silicone polymers among other ingredients; • US 2020 / 0022898 discloses film-forming compositions comprising a first random copolymer of anionic or non-ionic non-crosslinking polyacrylate and a second random copolymer of cationic non-crosslinking polyamide; • US 11,033,478 discloses a self-curling mascara composition containing at least about 7% by weight of a water-soluble or water-dispersible non-ionic copolymer that includes a cyclic amide monomer, a cyclic amine monomer, and an acrylamide monomer; • US 2003 / 0082221 discloses compositions containing pullulan; • US 2016 / 0113860 discloses compositions containing silicone-modified pullulan and silicone oils which it thickens; • JP-A H08-208989 is referred to in the previous application, and characterized by the disclosure of silicone-modified pullulan which thickens silicone oil components, but has an inadequate thickening effect; • CN 111801092 discloses compositions for impregnating a material, where the compositions contain PEG or polyether modified silicones as well as dendrimer type siloxanes; • FR 3 104 958 discloses compositions containing polyurethane dispersions among other ingredients; and • FR 3 110 849 discloses compositions containing dispersions of polyurethane and / or acrylic among other ingredients, with little or no fat.

[0006] There remains a need for improved compositions such as primer compositions or of fixative having improved properties with regard to the ease and / or comfort of application of the composition, and / or in particular with regard to improved properties linked to better hold of the cosmetic composition on keratinous materials and its resistance to external forces such as mechanical friction, water, sweat and perspiration, sebum and / or oil. Summary of the invention

[0007] The present invention relates to oil-in-water (o / w) emulsions (compositions) comprising at least one hydrophobically modified polysaccharide compound and at least one film-forming agent in the aqueous phase. Preferably, the composition is a composition for application to the skin. Most preferably, the composition is a fixative or a priming composition, and / or is in the form of a gel. Also preferably, the composition further comprises at least one gelling agent and / or at least one active agent.

[0008] In a particular embodiment, the composition further comprises at least one compound selected from the group consisting of at least one gelling agent, at least one colorant, at least one active agent and mixtures thereof. At least two of the gelling agents, colorants and active agents may be present in the composition.

[0009] In a particular embodiment, the at least one film-forming agent in the aqueous phase is chosen from polyvinylpyrrolidone, a vinylpyrrolidone / vinyl acetate copolymer, a vinylpyrrolidone / acrylic acid copolymer, a polyvinyl alcohol, a copolymer of N-vinylpyrrolidone, methacrylamide and N-vinylimidazole, polyurethanes, latexes, pectin, water-soluble cellulose compounds and mixtures thereof, and is preferably a copolymer of N-vinylpyrrolidone, methacrylamide, and N-vinylimidazole.

[0010] The present invention also relates to methods of fixing a color cosmetic composition (e.g., a composition containing a colorant such as a foundation) and / or of priming keratinous material for a color cosmetic composition by applying compositions of the present invention to the keratinous material (priming) and / or to a color cosmetic composition previously applied to the keratinous material (fixing) in an amount sufficient to prime the keratinous material for the color cosmetic composition and / or in an amount sufficient to achieve fixation of the color cosmetic composition previously applied to the keratinous material.

[0011] The present invention also relates to kits comprising, as separate compositions in one or more containers within the kits, (A) at least one composition of the present invention, in particular a fixative or primer composition for cosmetics, comprising at least one poly hydrophobically modified saccharide and at least one film-forming agent in aqueous phase; and (B) at least one cosmetic composition comprising at least one colorant.

[0012] The present invention also relates to assemblies, as applied to a keratinous material, comprising (A) at least one first layer of at least one cosmetic composition comprising at least one colorant; and (B) at least one second layer of at least one composition of the present invention, in particular a fixative or primer composition for cosmetic compositions comprising at least one colorant, comprising at least one hydrophobically modified polysaccharide compound and at least one aqueous-phase film former. Preferably, the at least one second layer is applied over the at least one first layer (in which case the second layer is a fixative layer formed by applying a fixative composition to the first layer).However, if the at least one first layer is applied over the at least one second layer, the at least one second layer is a primer layer formed by applying a primer composition to a keratinous material.

[0013] The present invention also relates to methods for making oil-in-water (o / w) emulsions (compositions) of the present invention comprising combining at least one hydrophobically modified polysaccharide compound and at least one film former in the aqueous phase during the formation of the emulsion composition. Preferably, the composition is a composition for application to the skin. Preferably, the composition is a fixative or a priming composition, and / or is in the form of a gel. Also preferably, the composition further comprises at least one gelling agent and / or at least one active agent.

[0014] It is to be understood that both the foregoing general description and the following detailed description are provided by way of example and explanation only, and do not limit the invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] In the following description of the invention and the claims appended thereto, it is to be understood that the terms used have their ordinary and customary meanings in the art, unless otherwise specified.

[0016] “Approximately” as used herein means within 10% of the number indicated (e.g., “about 10%” means 9% to 11% and “about 2%” means 1.8% to 2.2%.

[0017] “A” or “an” as used herein means “at least one”

[0018] “At least one” means one or more and thus includes components in individual as well as mixtures / combinations.

[0019] As used herein, all proposed ranges are intended to include each specific range within the given ranges, and combinations of sub-ranges therebetween. medians. Thus, a range of 1 to 5 specifically includes 1, 2, 3, 4, and 5, as well as subranges such as 2 to 5, 3 to 5, 2 to 3, 2 to 4, 1 to 4, etc.

[0020] “Film former”, “film-forming polymer” or “film-forming agent” as used herein means a polymer or resin that leaves a film on the substrate to which it is applied, for example, after a solvent accompanying the film former has evaporated, been absorbed into, and / or dissipated on the substrate.

[0021] “Wax” as used herein is a lipophilic fatty compound that is solid at room temperature room temperature (25°C) and changes from solid to liquid state reversibly, having a melting temperature above 30°C and, for example, above 45°C, and a hardness above 0.5 MPa at room temperature.

[0022] “Surfactant” and “emulsifier” are used interchangeably throughout throughout this memorandum.

[0023] “Substituted” as used herein means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted.

[0024] "Volatile" as used herein means having a flash point less than about 115°C.

[0025] “Non-volatile,” as used herein, means having a flash point greater than about 115°C.

[0026] “Polymer” as used herein means a compound that is made up of at least two monomers.

[0027] “Mat” in compositions as used herein refers to compositions having little or no light reflection. For example, matte compositions may have average gloss properties, measured at 60°, of less than or equal to 10, e.g., 9, preferably less than or equal to 8, 6, 5, 4, or 1, including all intermediate ranges and sub-ranges such as 1 to 10, 1 to 5, 2 to 10, 3 to 8, less than 1, less than 3, less than 5, etc. Such measurements may be made by depositing films to be tested onto a substrate (e.g., a P121-10N black exfoliating panel or a BYK No. 2810 opacity card) using a pinch bar (e.g., 1 mil, 3 mil, or 6 mil thick) and an automatic pinching machine. The films can then be dried at room temperature and analyzed using a glossometer (BYK: micro-TRLgloss) at a 60° angle.

[0028] “Exempt” or “substantially free” or “devoid of” as used herein means that although it is preferable that no amount of the specific component be present in the composition, it is possible for there to be very small amounts thereof in the compositions of the invention provided that such amounts do not materially affect at least one, preferably most, of the beneficial properties of the conditioning compositions of the invention. Thus, for example, "dye-free" means that an effective amount (i.e., greater than trace amounts) of dye is omitted from the composition (i.e., about 0% by weight), "substantially dye-free" means that a dye is present in amounts not greater than 0.1% by weight, and "dye-free" means that a dye is present in amounts not greater than 0.25% by weight, based on the total weight of the composition.The same nomenclature applies to all other ingredients identified throughout the application and in this paragraph, such as, for example, silicone oils (compositions of the invention that are “free of silicone oils,” “substantially free of silicone oils,” and “oil-free” have meanings consistent with the discussion within this paragraph), even if not specifically discussed for each identified ingredient.Thus, for example, "free of phenylated silicone oil" means that an effective amount (i.e., a dullness-inhibiting effective amount) of phenylated silicone oil is omitted from the composition (i.e., about 0% by weight), "substantially free of phenylated silicone oil" means that the phenylated silicone oil is present in amounts no greater than 0.25% by weight, and "free of phenylated silicone oil" means that the phenylated silicone oil is present in amounts no greater than 0.5% by weight, based on the total weight of the composition.The same nomenclature applies to all other ingredients identified throughout the application and in this paragraph, such as, for example, (1) matting fillers (compositions of the invention that are “free of matting fillers,” “substantially free of matting fillers,” and “lacking matting fillers”) and (2) additional film formers other than the hydrophobically modified polysaccharide compound and the aqueous-phase film former (compositions of the invention that are “free of additional film formers,” “substantially free of additional film formers,” and “lacking additional film formers”) have meanings consistent with the discussion in this paragraph, even if not specifically discussed for each identified ingredient. The discussed examples of the use of such language as those in this paragraph are intended to be provided by way of example, not limitation.

[0029] “Makeup result” as used herein refers to compositions where the color remains the same or substantially the same as at the time of application, as seen by the naked eye, after an extended period of time. “Makeup result” may be evaluated by assessing long-lasting properties by any method known in the art for assessing such properties. For example, long-lasting properties may be assessed by a test involving the application of a composition to keratinous materials such as the lips and assessing the color of the composition after an extended period of time. For example, the color of a composition may be assessed immediately after application to keratinous materials such as the lips and these characteristics may then be re-assessed and compared after a period of time. Further, these characteristics may be assessed relative to other compositions, such as commercially available compositions.

[0030] “Keratinous material” or “keratin material” means natural nails, lips, skin such as that of the face, body, hands and the area around the eyes, and keratin fibers such as human hair, eyelashes, eyebrows, hair, as well as synthetic additions, such as false eyelashes, false eyebrows, false nails, etc.

[0031] “Physiologically acceptable” means compatible with keratinous material and having a pleasant color, odor, and feel, and which does not cause unacceptable discomfort (tingling or tightness) that would discourage a consumer from using the composition. The compositions of the present invention may be in the form of a gel composition.

[0032] "Gel composition" means a composition that does not flow like a liquid when applied to a substrate, a composition that has a three-dimensional network that prevents the composition from spreading on, or flowing from, a substrate after application due to gravity over a short period of time (e.g., in less than 10 seconds). G' (storage modulus) is greater than G” (loss modulus) in all strain ranges up to 300% strain. Preferably, G' (storage modulus) is greater than G” (loss modulus) at low strain, but with G' decreasing and G” increasing, and the gel has the crossover point at > 0.1% strain, preferably > 1% strain, and preferably less than 200% strain, preferably less than 150% strain.

[0033] The term "gel crossover point" (Sol / Gel point) means the point at which G" (loss modulus) intersects G' (storage modulus), reported as % strain. This is the point at which a composition changes from a fairly solid to a fairly liquid state. An example of a method for determining a gel crossover point is as follows: G” (loss modulus) and G' (storage modulus) using a TA Instruments Discovery HR-3 rheometer, having a 40 mm parallel plate geometry on a flat stainless steel peltier plate. The test can be run at 25°C with a test parameter of angular frequency of 1.0 rad / s and a logarithmic sweep: % strain from 0.01 to 1000.0%. 5 points per decade. Results reported as % strain constraint.

[0034] “Natural compound” means any compound derived directly from a natural substance such as a plant without having undergone any chemical modification.

[0035] “Naturally occurring compound” means any compound derived from a natural compound which has undergone one or more chemical modifications, for example by organic synthesis reaction, without the properties of the natural compound having been modified.

[0036] “Synthetic compound” means any compound that is not a compound natural nor a naturally occurring compound.

[0037] “Room temperature” means 25°C.

[0038] “Atmospheric pressure” means 760 mmHg, that is, 105 pascals.

[0039] The compositions and methods of the present invention may comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful. For example, the aqueous phase solvent system may "consist essentially of" water and a C2-C5 monohydric alcohol, and / or the film-forming system of the composition may consist essentially of the hydrophobically modified polysaccharide compound and the aqueous phase film-forming agent; likewise, the oil-phase film-forming system may consist essentially of the hydrophobically modified polysaccharide compound.

[0040] For the purposes of the present invention, the “fundamental and novel property” associated with compositions, components and methods which “consist essentially of” identified ingredients or actions is transfer resistance.

[0041] Reference is made herein to trade names of materials including, but not limited to, polymers and optional components. The inventors herein do not intend to be limited to the materials described and referenced by a certain trade name. Equivalent materials (e.g., those obtained from a different source under a different catalog name or (reference) number) to those referenced by a trade name may be substituted and used in the methods described and claimed herein.

[0042] All percentages and ratios are calculated by weight unless otherwise indicated. All percentages are calculated based on the total weight of a composition unless otherwise indicated. All levels of component or composition refer to the active level of that component or composition, and are exclusive of impurities, e.g., residual solvents or by-products, which may be present in commercially available sources.

[0043] Film-forming agent in aqueous phase

[0044] According to the present invention, compositions including one or more aqueous phase film-forming polymers ("first film-forming polymers" or "first film formers") that are a water-soluble or water-dispersible non-ionic polymer are provided. For clarity, by "water-soluble or water-dispersible non-ionic" is meant that the polymer is non-ionic. The polymer is also water-soluble or water-dispersible, particularly to the extent that it can be readily stabilized in a vehicle (e.g., water) present in the composition.

[0045] The one or more of these first film-forming polymers are part of an aqueous phase film-forming system. The aqueous phase film-forming system may comprise, consist essentially of, or consist of an aqueous phase film-former.

[0046] Examples of aqueous film-forming polymer include, but are not limited to, homopolymers and copolymers containing at least one (meth)acrylic acid (meth)acrylate monomer and / or at least one vinylpyrrolidone monomer such as polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / acrylic acid copolymers, vinylpyrrolidone / acrylate copolymers, alkyl (e.g., butyl) acrylate and hydroxyalkyl (e.g., propyl) dimethicone acrylate copolymers, styrene / acrylates / ammonium methacrylate copolymers, acrylamide / sodium acryloyldimethyltaurate copolymer, etc.; water-soluble polysaccharides such as pectin, unmodified pullulan, or cellulose compounds; polyurethanes; latex; and their mixtures.

[0047] According to preferred embodiments, the at least one aqueous-phase film-forming polymer is at least one cyclic amide-containing polymer. Preferably, the at least one cyclic amide-containing polymer also has at least one cyclic amine and / or acrylamide functionality, preferably both, although it is possible for the at least one polymer to contain neither cyclic amine functionality nor acrylamide functionality.

[0048] Cyclic amide and cyclic amine monomers useful in the preferred first film-forming polymers include those having one or more aromatic or aliphatic ring structures. These rings may have sizes ranging from about, for example, 5 to 8 ring members.

[0049] In some embodiments, the monomers useful for forming these first film-forming polymers are polymerizable, ethylenically unsaturated monomers having a cyclic amine residue or a cyclic amide residue. Accordingly, the cyclic amide monomers of these first film-forming polymers may include cyclic amide residues that are or include heterocyclic ring structures. such as lactams and the like. These may be α-lactam, β-lactam, γ-lactam, δ-lactam and ε-lactam. In a preferred embodiment, the cyclic amide is a pyrrolidone (a γ-lactam), especially vinylpyrrolidone.

[0050] Useful cyclic amine residues may include any of various heterocyclic amines such as azoles, pyrroles, pyrrolidines, carbamates, and the like. In a preferred embodiment, the cyclic amine residue is an imidazole.

[0051] In some embodiments, acrylamide monomers useful in these first film-forming polymers include those having -C3H5NO functional groups. Examples include (meth)acrylamides.

[0052] As noted above, at least one cyclic amide-containing polymer preferably has at least one cyclic amine and acrylamide functionality as well, preferably both, although it is possible for the polymer to contain no functionality. For example, the polymer(s) containing one or more cyclic amide residues but no cyclic amine or acrylamide functionality include, but are not limited to, vinylpyrrolidone homopolymers (polyvinylpyrrolidone) and vinylpyrrolidone copolymers containing at least one monomer other than vinylpyrrolidone such as, for example, substituted or unsubstituted C2 (acrylic acid) or C3 (allyl) groups, optionally in the form of esters (acrylates or methacrylates) or ethers.

[0053] In some embodiments, the at least one aqueous-phase film-forming polymer has a weight average molecular weight in a range of about 10,000 daltons to about 1,000,000 daltons, including all intermediate ranges and sub-ranges such as, for example, 50,000 daltons to 500,000 daltons, 75,000 daltons to 300,000 daltons, and 100,000 daltons to 250,000 daltons.

[0054] In some embodiments, the at least one cyclic amide-containing polymer is a copolymer of N-vinyl pyrrolidone, methacrylamide, and N-vinylimidazole.

[0055] In some embodiments, the at least one cyclic amide-containing polymer may be a commercially available variety, such as LUVISET CLEAR AT3, commercially available from BASF of Ludwigshafen, Germany.

[0056] According to preferred embodiments, the compositions of the present invention are free, free or substantially free of polyurethanes.

[0057] Preferably, the at least one aqueous phase film-forming polymer is present in the compositions of the present invention in an amount ranging from about 0.5% to about 25% by weight, preferably from about 0.75% to about 20% by weight, preferably from about 1% to about 10%, and preferably from about 1% to about 5% by weight relative to the weight of the composition, including all intermediate ranges and sub-ranges such as, for example, 4% to 15%, 1% to 3%, 3% to 25%, etc. Preferably, the at least one aqueous-phase film-forming polymer is present in the compositions of the present invention in an amount greater than 1% by weight of the total weight of the composition.

[0058] Hydrophobically modified polysaccharide compound

[0059] According to the present invention, compositions including one or more hydrophobically modified polysaccharide compounds ("second film-forming polymers" or "second film formers") are provided. The one or more of these second film-forming polymers are part of a composition film-forming system along with the at least one aqueous phase film former. Optionally, other film-forming agents may be present in the composition film-forming system in the composition, if desired. Preferably, the at least one hydrophobically modified polysaccharide is at least one hydrophobically modified pullulan compound.

[0060] Pullulan is a natural polysaccharide produced from starch by the fungus Aureobasidium pullulons. Pullulan is an alpha-glucan consisting primarily of maltotriose repeating units linearly linked by alpha 1,6-glycoid bonds. Natural pullulan is readily soluble in cold or hot water, forming clear, viscous solutions.

[0061] Pullulan can be produced, for example, from the fermentation of partially hydrolyzed starch or by using sucrose, sugarcane, milk, potato and other sources for carbohydrate raw materials.

[0062] Suitable pullulan compounds include those described in US patent application 2018 / 0133144.

[0063] Preferably, the pullulan compounds of the present invention are oil soluble. For example, preferred pullulan compounds of the present invention have been modified with a hydrophobic group such as a silicone group or a hydrocarbon group that imparts oil solubility to the compound. Such modifications may include, for example, a silicone group such as a siloxysilyl group (-[-SiRR'-SiOR"R"'-]-), where R, R', R" and R'" are alkyl groups preferably containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms and most preferably 1 to 3 carbon atoms), or may include C8 or higher hydrocarbon groups (e.g., hydrocarbon groups containing 8 to 24 carbon atoms, including intermediate ranges and sub-ranges such as 12 to 22 carbon atoms and 12 to 18 carbon atoms).

[0064] Preferably, the pullulan may be modified with a silicone group which imparts oil solubility to the compound ("silicone-modified pullulan compound.") A preferred silicone-modified pullulan compound has a structure corresponding to: • a pullulan-linker-silicone group; • where the silicone group is preferably a C1-C6 alkyl-substituted siloxysilyl group, such as, for example, a monoalkyl-substituted siloxysilyl group, a diacyl-substituted siloxysilyl group, or a trialkyl-substituted siloxysilyl group, where the C1-C6 alkyl group is linear, cyclic or branched, substituted or unsubstituted; and • when the linker does not adversely affect either the film-forming or oil-solubility properties of the compound. Preferably, the linker is an alkyl (-C-), an ester or ether (-O-), an amide or amine (-N-) or a combination thereof such as a carbamoyl group. Preferably, the linker is a carbamoyl group.

[0065] Preferably, the pullulan compound is a trialkylsiloxysilylcarbamoyl pullulan, a particularly preferred compound being trimethylsiloxysilylcarbamoyl pullulan.

[0066] Preferably, the pullulan compound(s) in the compositions of the present invention have a molecular weight of 50,000 to 10,000,000 daltons, preferably 100,000 to 5,000,000 daltons, preferably 250,000 to 1,000,000 daltons, including all intermediate ranges and sub-ranges including, for example, 200,000 to 7,600,000 daltons, 350,000 to 8,750,000 daltons, 225,000 to 700,000 daltons, etc.

[0067] Preferably, the at least one hydrophobically modified polysaccharide compound is present in the compositions of the present invention in an amount ranging from about 0.5% to about 25% by weight, preferably from about 0.75% to about 20% by weight, preferably from about 1% to about 10%, and preferably from about 1% to about 5% by weight based on the weight of the composition, including all intermediate ranges and sub-ranges such as, for example, 4% to 14%, 1% to 5%, 1.5% to 8%, etc. Preferably, the at least one hydrophobically modified polysaccharide compound is present in the compositions of the present invention in an amount greater than 1.5% by weight of the total weight of the composition.

[0068] According to preferred embodiments, the total combined amount of aqueous phase film former and hydrophobically modified polysaccharide compound present in the compositions of the present invention is from about 0.5% to about 25% by weight, preferably from about 0.75% to about 20% by weight, and most preferably from about 1% to about 10% by weight, all weights being based on the total weight of the composition, including all intermediate ranges and sub-ranges such as, for example, 1% to 10%, 2% to 8%, 2.5% to 6%; 2.75% to 8%, 1.5% to 4%, 1.25% to 5%, etc.

[0069] According to preferred embodiments, the at least one aqueous phase film former and the at least one hydrophobically modified polysaccharide compound are present in the compositions of the present invention in a weight ratio of about 5:1 to about 1:5, preferably from about 3:1 to about 1:3, and preferably from about 2.5:1 to about 1:2.5, including all intermediate ranges and sub-ranges of these ranges, and in particular the ranges and sub-ranges obtained by using the endpoints of the compositions in the examples below such as, for example, 3.75 / 1.5 (Example 3-G) to 3 / 1.25 (Example 3-1), etc.

[0070] Aqueous phase

[0071] According to preferred embodiments of the present invention, compositions comprising an aqueous phase solvent system comprising (i) water in an amount of at least about 10% by weight based on the total weight of the composition; and (ii) optionally, at least one C2-C5 monohydric alcohol are provided. Preferably, the composition is in the form of an emulsion with a continuous external phase which is aqueous, preferably an oil-in-water (o / w) emulsion.

[0072] According to preferred embodiments, the compositions of the present invention comprise water. Preferably, the compositions comprise at least about 10% water by weight, preferably greater than 20% water by weight, preferably greater than 25% water by weight, and preferably greater than 30% water by weight, preferably in amounts of about 10% to about 80%, preferably greater than 20% to about 75%, preferably about 25% to about 60%, and preferably about 30% to about 50%, by weight, based on the total weight of the composition, including all intermediate ranges and sub-ranges, such as, for example, about 30% to about 60%.

[0073] Suitable C2-C5 monohydric alcohols, where applicable, include ethanol, propanol, butanol, pentanol, isopropanol, isobutanol and isopentanol. Ethanol is particularly preferred.

[0074] Preferably, the C2-C5 monoalcohol(s), where appropriate, are present in the compositions of the present invention in an amount ranging from about 1% to about 50%, preferably from about 2.5% to about 40%, preferably from about 2.5% to about 30%, and preferably from about 2.5% to about 25%, by weight, relative to the total weight of the composition, including all intermediate ranges and sub-ranges such as, for example, from about 1 to about 25%.

[0075] Preferably, the aqueous phase solvent system of the compositions of the present invention consists essentially of, or consists of, water and, optionally, C2-C5 monohydric alcohols. Preferably, the aqueous phase solvent system is "free", "lacking" or "substantially free" of solvents other than water and, optionally, C2-C5 monohydric alcohols.

[0076] Oily phase

[0077] According to the present invention, compositions comprising at least one oil are provided. The compositions of the present invention preferably comprise suf of oil to form an oil-in-water emulsion, preferably from about 1% to about 80% oil, more preferably from about 2% to about 60% oil, preferably from about 5% to about 50% oil, preferably from about 10% to about 45% oil, and preferably from about 20% to about 40% oil by weight based on the total weight of the composition, including all intermediate ranges and sub-ranges such as, for example, 5% to 15%, 10% to 25%, etc. However, compositions "free", "substantially free" or "devoid" (as defined above) of oils may also be prepared.

[0078] Suitable oils include volatile and / or non-volatile oils. These oils may be any acceptable oil, including, but not limited to, silicone oils and / or hydrocarbon oils.

[0079] In some embodiments, the oil carrier comprises one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having a room temperature viscosity of 6 cSt or less and having 2 to 7 silicon atoms, such silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that may be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that may be used include KF 96A with a viscosity of 6 cSt, a commercial product from Shin Etsu having a flash point of 94°C. Preferably, volatile silicone oils have a flash point of at least 40°C.

[0080] Non-limiting examples of volatile silicone oils are listed in Table 1 below.

[0081] [Tables 1] Compound Flash point (°C) Viscosity (cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5) 55 2.5 Octamethylcyclotetrasiloxane 93 7 (cyclotetramethylsiloxane or D4) 63 1.7 Dodecamethylcyclohexasiloxane (D6) 94 6 Decamethyltetrasiloxane (L4) 56 1.5 Shin Etsu KF-96 A PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) Dow Corning PDMS DC 200 (2 cSt) Dow Corning 87 2

[0082] Furthermore, a volatile linear silicone oil may be employed in the present invention. Suitable volatile linear silicone oils include those described in U.S. Patent No. 6,338,839 and WO03 / 042221. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, the decamethyltetrasiloxane is further combined with another solvent more volatile than the decamethyltetrasiloxane.

[0083] According to certain embodiments, the oil carrier comprises one or more non-silicone volatile oils and may be selected from volatile hydrocarbon oils, volatile esters and volatile ethers. Examples of these volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof and in particular, branched C8 to C16 alkanes such as C8 to C16 isoalkanes (also known as isoparaffins), isododecane, isodecane, and for example, oils sold under the trade names Isopar or Permethyl. Preferably, the volatile non-silicone oils have a flash point of at least 40°C.

[0084] Non-limiting examples of volatile non-silicone oils are given in Table 2 below.

[0085] [Tables2] Compound Flash point (°C) Isododecane 43 Propylene glycol n-Butyl ether 60 Ethyl 3-Ethoxypropionate 58 Propylene glycol methyl ether acetate 46 Isopar L (Cn-Cu isoparaffin) 62 Isopar H (Cn-Ci2 isoparaffin) 56 Undecane 62 Tridecane 94 Isohexadecane 96

[0086] The volatility of solvents / oils can be determined using the evaporation rate presented in U.S. Patent No. 6,338,839.

[0087] According to other embodiments of the present invention, the oil carrier comprises at least one non-volatile oil. Examples of non-volatile oils that can be used in the present invention include, in particular, polar oils such as: • vegetable oils based on hydrocarbons with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have varying chain lengths, these chains being possibly linear or branched and saturated or unsaturated; these oils include wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy seed oil, pumpkin oil, sesame seed oil, cucurbit oil, avocado oil, hazelnut oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil or rosehip oil;or caprylic / capric acid triglycerides, for example those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; • synthetic oils or esters of formula R5COOR6 in which R5 represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R6 represents a branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms, such as, for example e.g., Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate and octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, e.g., isostearyl lactate or isostearyl malate; and pentaerythritol esters; • synthetic ethers containing 10 to 40 carbon atoms; • C8 to C26 fatty alcohols, for example oleyl alcohol, cetyl alcohol, stearyl alcohol and cetearyl alcohol; and • their mixtures.

[0088] Furthermore, examples of non-volatile oils that may be used in the present invention include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons and hydrocarbon waxes including polyolefins, particularly petrolatum (vaseline), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydro squalene and mixtures thereof.

[0089] According to preferred embodiments, the compositions of the present invention are free, free of, or substantially free of silicone oils.

[0090] According to preferred embodiments, the compositions of the present invention are free, free of, or substantially free of non-volatile oils.

[0091] According to preferred embodiments, the compositions of the present invention are free, free or substantially free of waxes.

[0092] High HLB surfactant

[0093] According to preferred embodiments of the present invention, compositions further comprising at least one high HLB surfactant are provided. "HLB" refers to the "hydrophilic-lipophilic balance" associated with the emulsifiers / surfactants. In particular, the "HLB" value relates to the ratio of hydrophilic groups to lipophilic groups in the emulsifiers, and also relates to the solubility of the emulsifiers. Emulsifiers with lower HLB are more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (W / O) emulsifiers. Emulsifiers with higher HLB are more soluble in water (hydrophilic material) and are more suitable for oil-in-water (O / W) emulsions. In the context of the present invention, a "high HLB surfactant" refers to a surfactant having an HLB value greater than 8.Also, in the context of the present invention, a "high HLB value" means a surfactant having an HLB value greater than or equal to 8, preferably greater than or equal to 9, preferably greater than or equal to 10, preferably greater than or equal to 12, and preferably greater than or equal to 13.

[0094] Examples of surfactants include, but are not limited to, the following: • Polyethylene glycol (PEG) and / or glycerolated esters or ethers, such as branched or linear C8-C24 polyethylene glycol and / or glycerolated compounds, for example, Oleth-50, Oleth-20, Oleth-10, Ceteth-10, Steareth-20, Laureth-23, PEG-8 stearate, PEG-8 isostearate, PEG-20 stearate, PEG-40 stearate, etc.; • sorbitan esters or ethers, such as oxyethylenated or non-oxyethylenated mono- or polyalkyl sorbitan esters or ethers, such as polysorbate 21, polysorbate 40, polysorbate 80, polysorbate 60, polysorbate 61, sorbitan isostearate, glyceryl sorbitan isostearate, sorbitan sesquioleate, sorbitan laurate, sorbitan monopalmitate, sorbitan oleate, sorbitan trioleate and sorbitan triostearate, etc.; • Monoalkyl or polyalkyl sugar esters or ethers, such as monoalkyl or polyalkyl sugar esters or ethers as described in US patent 6,689,371. Examples include methyl glucose isostearate, sucrose distearate, sucrose stearate, etc.; • Alkoxylated alkenyl succinates; and • Silicone derivatives, such as dimethicone copolyols, for example mixture of cyclomethicone and dimethicone copolyol sold under the name "DC 5225 C" by Dow Corning, and alkyl dimethicone copolyols, such as lauryl methicone copolyol, sold under the name "Dow Corning 5200 Formulation Aid" by Dow Corning, and cetyl dimethicone polyol, sold under the name "Abil EM 90" by Goldschmidt, or the mixture of polyglyceryl-4 isostearate / cetyl dimethicone copolyol / hexyl laurate sold under the name "Abil WE 90" by Goldschmidt.

[0095] The at least one high HLB surfactant is preferably present in the compositions of the present invention at a level of about 0.1% to about 5%, preferably about 0.1% to about 4%, and preferably about 0.1% to about 3% by weight relative to the total weight of the composition, including all intermediate ranges and sub-ranges. Gelling agent / Coloring agent / Active agent

[0096] Gelling agent

[0097] According to preferred embodiments of the present invention, compositions further comprising at least one gelling agent are provided. Suitable gelling agents include any gelling agent, such as, for example, gums, clays and acrylic acid (co)polymers, such as high molecular weight homo- or copolymers comprising acrylic acid, optionally crosslinked with a polyalkenyl polyether, including certain polymers identified as "carbomer" as well as amphiphilic polymers. Preferably, the gelling agent is a gum, an amphiphilic polymer or a clay, or a combination of any of these.

[0098] According to preferred embodiments, the at least one gelling agent is preferably at least one gum. Suitable examples of thickening gums include, but are not limited to, suitable gums include xanthan, sclerotium, pectin, karaya, arabic, gelatin, agar, guar, carrageenan, alginate and combinations thereof.

[0099] According to preferred embodiments, the at least one gelling agent is preferably at least one amphiphilic polymer, comprising at least one ethylenically unsaturated monomer, preferably containing a sulfonic group, in free or partially or totally neutralized form.

[0100] The amphiphilic polymers may comprise at least one hydrophobic portion. The hydrophobic portion present in these "polymers" preferably contains from 6 to 50 carbon atoms, preferably from 6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms and preferably from 12 to 18 carbon atoms, including all intermediate ranges and sub-ranges.

[0101] The amphiphilic polymers may have a molar mass ranging from 50,000 g / mol to 10,000,000 g / mol, preferably from 80,000 g / mol to 8,000,000 g / mol, and preferably from 100,000 g / mol to 7,000,000 g / mol.

[0102] The amphiphilic polymers may be based on at least one ethylenically unsaturated hydrophilic monomer A and at least one hydrophobic monomer B. Preferably, the monomer A comprises a strong acid function, in particular a sulfonic acid or phosphonic acid function. The hydrophobic monomer B comprises at least one hydrophobic radical, chosen from: saturated or unsaturated C6-C18 linear alkyl radicals (for example, n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl or oleyl); branched alkyl radicals (for example, isostearic) or cyclic alkyl radicals (for example, cyclododecane or adamantane); C6-C18 fluoro or alkylfluoro radicals (for example, the group of formula —(CH2)2—(CF2)9—CF3); a cholesteryl radical or radicals derived from cholesterol (e.g., cholesteryl hexanoate); aromatic polycyclic groups, e.g., naphthalene or pyrene; and silicone or alkyl-silicone or alkylfluorosilicone radicals.Among these radicals, linear and branched alkyl radicals are preferred.

[0103] Amphiphilic polymers may be water-soluble or water-dispersible in neutralized form.

[0104] The amphiphilic polymers can be crosslinked. The crosslinking agents can be chosen, for example, from polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by free radical polymerization. According to a preferred embodiment of the invention, the crosslinking agent crosslinking is selected from methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA). The degree of crosslinking preferably ranges from 0.01 mol% to 10 mol%, and preferably from 0.2 mol% to 2 mol%, relative to the polymer, including all intermediate ranges and sub-ranges.

[0105] The amphiphilic polymers can be homopolymers or copolymers.

[0106] Amphiphilic polymers can be partially or completely neutralized with an inorganic base (e.g., sodium hydroxide, potassium hydroxide, or liquid ammonia) or an organic base such as monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, N-methylglucamine, or basic amino acids, e.g., arginine and lysine, and mixtures thereof.

[0107] The amphiphilic polymers may be water-soluble or water-dispersible homopolymers such as, for example, optionally crosslinked polymers of sodium 2-acrylamido-2-methylpropanesulfonate acid such as that used in the commercial product SIMULGEL 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of ammonium 2-acrylamido-2-methyl propanesulfonate acid (INCI name: AMMONIUM POLYACRYLDIMEHYLTAURAMIDE) such as the product marketed under the trade name HOSTACERIN AMPS@ by Clariant.

[0108] The amphiphilic polymers may be chosen from crosslinked or non-crosslinked amphiphilic polymers of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and at least one ethylenically unsaturated monomer comprising at least one hydrophobic portion containing from 6 to 30 carbon atoms, preferably from 6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms and preferably from 12 to 18 carbon atoms, including all intermediate ranges and sub-ranges.

[0109] Suitable examples of amphiphilic polymers include, but are not limited to, hydrophobically modified sulfonic acid copolymers such as ammonium acryloyldimethyltaurate / VP copolymer (Clariant's Aristoflex AVC), ammonium acryloyldimethyltaurate / beheneth-25 methacrylate crosslinked polymer (Clariant's Aristoflex HMB) (crosslinked and ethoxylated AMPS / behenyl methacrylate), ammonium acryloyldimethyltaurate / steareth-25 methacrylate crosslinked polymer (Aristoflex HMS) (ethoxylated AMPS / stearyl methacrylate copolymer crosslinked with trimethylol triacrylate), Aristoflex SNC (crosslinked and ethoxylated AMPS / C16-C18), Aristoflex LNC (non-AMPS / C12-C14 crosslinked), acrylamide / sodium acryloyldimethyl taurate / isohexadecane / polysorbate 80 copolymer (Simulgel 600) and mixtures thereof.

[0110] According to preferred embodiments, the gelling agent(s) may be at least one clay. Among the clays, mention may be made of clays from the smectite family, such as laponite, from the kaolinite family, such as kaolinite, dickite or nacrite, the facultatively modified clays of the family of halloysites, dombassites, antigorites, berthierines, pyrophyllites, montmorillonites, beidellites, vermiculites, talcs, stevensites, hectorites, saponites, chlorites, sepiolites and illites.

[0111] Clays are products already well known in themselves, which are described, for example, in the publication “Minéralogie des argiles”, S. Caillère, S. Hénin, M. Rautureau, 2nd edition 1982, Masson, the teaching of which is included here for reference.

[0112] Natural clay is a sedimentary rock composed largely of specific minerals, generally aluminum silicates. Kaolin is therefore a natural clay.

[0113] Clays can also be synthetic. Thus, Sumecton mentioned below is a synthetic saponite.

[0114] Preferably, in the context of the present invention, clays are used which are cosmetically compatible and acceptable with keratinous materials. Clays which may be mentioned in particular include kaolinite, montmorillonites, saponites, laponites, hectorites and illites. Mixtures of clays and natural clays may also be used.

[0115] Natural clays that may be mentioned include green clays, particularly rich in illite; clays rich in montmorillonite, known as Fuller's earth, or such as bentonite or white clays rich in kaolinite. As bentonites, mention may be made in particular of those sold under the names Bentone 38 VCG®, Bentone Gel CAO V®, Bentone 27 V® and Bentone Gel MIO V® by the company Elementis.

[0116] As a montmorillonite-rich clay, we can cite hydrated aluminum silicate sold under the name Gel White H® by the Rockwood company.

[0117] As saponite, which belongs to the montmorillonite family, we can cite synthetic saponite, in particular the product sold by the company Kunimine under the name Sumecton®.

[0118] As talc, we can cite those sold under the names Rose Talc® and Talc SG-2000® sold by the company Nippon Talc, Luzenac Pharma M® sold by the company Luzenac, J-68BC® from US Corporation and Micro ACE-P-3® sold by the company Nippon Talc.

[0119] Preferably, where applicable, the gelling agent(s) are present in the compositions of the present invention in amounts ranging from about 0.1 to about 30% by weight, preferably from 0.5 to 25% by weight, preferably from 1 to 20% and most preferably from 2.5 to 15% by weight, all weights being based on the weight of the composition as a whole, including all intermediate ranges and sub-ranges such as, for example, 0.1 to 1.5%, 2 to 20%, 10 to 20%, etc.

[0120] Dye (Coloring agent)

[0121] According to embodiments of the present invention, compositions optionally further comprising at least one coloring agent are provided. According to preferred embodiments, the at least one coloring agent, if any, is at least one surface-treated pigment. "Surface-treated pigment" means pigments which have undergone, totally or partially, a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with a surface treatment agent. Preferably, the pigments are selected from inorganic pigments or mixed inorganic / organic pigments.

[0122] The surface treatment agents may be selected from the group consisting of alkyl silanes, organotitanates, halogenated phosphonates and halogenated organosilanes. According to preferred embodiments, the pigments have been surface-treated with a surface-treating agent selected from the group consisting of alkoxylated alkyl silanes such as, for example, ethoxylated and / or propoxylated C2-C8 alkyl silanes, and salts thereof, organotitanates such as, for example, titanium salts of fatty acids such as, for example, C2-C8 alkylated titanium salts of C9-C24 fatty acids such as stearic acid, isostearic acid, oleic acid, cetearic acid, cetyl acid, etc., halogenated organophosphonates such as, for example, per-fluoroalkyl phosphonates, and salts thereof, and halogenated organosilanes such as, for example, C2-C8 perfluoro alkyl silanes (optionally ethoxylated and / or propoxylated), and their salts.Specific examples of suitable surface treatment agents include (1) triethoxy caprylylsilane, (2) perfluorooctyltriethoxysilane, (3) sodium perfluorohexylethylphosphonate, and (4) isopropyl titanium triisosteate.

[0123] Preferred surface treatment agents are selected from the group consisting of alkyl silanes and halogenated organosilanes. In preferred embodiments, the pigments have been surface treated with a surface treatment agent selected from the group consisting of alkoxylated alkyl silanes such as, for example, ethoxylated and / or propoxylated C2-C8 alkyl silanes, and salts thereof, and halogenated organosilanes such as, for example, perfluoro (optionally ethoxylated and / or propoxylated) C2-C8 alkyl silanes, and salts thereof. Specific examples of suitable surface treatment agents include (1) triethoxy caprylylsilane and (2) perfluorooctyltriethoxysilane.

[0124] The surface-treated pigments of the present invention may be prepared according to surface treatment techniques well known to one of ordinary skill in the art or may be commercially available.

[0125] For example, the surface treatment agent with which the pigments are treated may be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surface treatment agent, or creation of a covalent bond between the surface treatment agent and the pigments. The surface treatment may thus be achieved, for example, by chemically reacting a surface treatment agent with the surface of the pigments and creating a covalent bond between the surface treatment agent and the pigments. An exemplary method is described, for example, in U.S. Patent No. 4,578,266.

[0126] The at least one surface-treated pigment, if any, is preferably present in the compositions of the present invention at an active solids content ranging from about 1% to about 30%, preferably from about 3% to about 25%, and preferably from about 5% to about 20%, by weight relative to the total weight of the composition, including all intermediate ranges and sub-ranges.

[0127] According to preferred embodiments of the present invention, compositions further comprising at least one non-surface-treated coloring agent are provided. Such coloring agents, if desired, may be in addition to or replace the surface-treated pigment discussed above.

[0128] According to this embodiment, the coloring agent is preferably chosen from pigments, dyes, such as fat-soluble dyes, pearlescent pigments and pearlescent agents.

[0129] Representative fat-soluble dyes that may be used in accordance with the present invention include Sudan Red, DC Red 17, DC Green 6, [3-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, annatto, and quinoline yellow. Fat-soluble dyes, if any, generally have a concentration of up to 40% by weight of the total weight of the composition, such as from 0.0001% to 30%, including all intermediate ranges and sub-ranges.

[0130] The pearlescent pigments that can be used according to the present invention can be chosen from colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and pearlescent pigments based on bismuth oxychloride. The pearlescent pigments, if any, are present in the composition at a concentration of up to 50% by weight of the total weight of the composition, such as from 0.0001% to 40%, preferably from 0.001% to 30%, including all intermediate ranges and sub-ranges.

[0131] The non-surface-treated pigments, which may be used according to the present invention, may be selected from white, colored, inorganic, organic, polymeric, and non-polymeric pigments. Representative examples of inorganic pigments include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, and ferric blue. Representative examples of organic pigments include carbon black, D & C type pigments, and lakes based on cochineal carmine, barium, strontium, calcium, and of aluminum.

[0132] Optionally, the coloring agents may be present in the composition at a concentration of up to 50% by weight of the total weight of the composition, such as from 0.0001% to 40%, and further such as from 0.001% to 30%, including all intermediate ranges and sub-ranges.

[0133] According to preferred embodiments, the compositions of the present invention are free, free or substantially free of coloring agents.

[0134] Active agent

[0135] According to preferred embodiments of the present invention, compositions further comprising at least one active agent are provided. Preferably, the active agent is in the aqueous phase (hydrophilic active agent), although active agents may be present in the oily phase (hydrophobic active agent).

[0136] In some embodiments, the active agent may be: • a moisturizing agent, such as a polyol such as, for example, glycerin and sugars, urea and its derivatives, such as in particular a hydroxyalkyl urea, in particular a hydroxyalkylurea, and mixtures thereof; • a desquamating agent, which may be a compound capable either of acting directly on desquamation by promoting exfoliation, such as [3-hydroxy acids, in particular salicylic acid and its derivatives (including 5-n-octanoylsalicylic acid); α-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; an extract of Saphora japonica; resveratrol and certain jasmonic acid derivatives; or of acting on the enzymes involved in desquamation or the degradation of corneodesmosomes, glycosidases, the stratum corneum chymotryptic enzyme (SCCE), or even other proteases (trypsin, chymotrypsin type). Examples of mineral salt chelating agents include: EDTA; N-acyl-N.N' acid.N'-Ethylenediaminctriacetic acid; aminosulfonic compounds and in particular (N-2-hydroxyethylpiperazine-N-2-ethane)sulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid derivatives (procysteine); α-amino acid derivatives of the glycine type (as described in EP-0 852 949 and sodium methylglycinediacetate sold by BASF under the trade name Trilon M); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine; . • a humectant; • an anti-aging agent, which may include, for example, one or more of C-beta-D-xylopyranoside-2-hydroxypropane (Pro-Xylane), retinol, peptides, caffeine and other skin texture enhancing components, any other suitable soluble / dispersible targeted active ingredient, and combinations thereof, a matting agent, which may include, but is not limited to, matting fillers such as, for example, talc, silica, silicone elastomers and polyamides, and waxes such as, for example, beeswax and co-pemicia cerifera (carnauba) wax. an antimicrobial agent, non-limiting examples of which include 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorobanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and its salts, micronazole and its salts, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clo-trimazole, butoconazole, oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox, ciclopiroxolamine, undecylenic acid and its salts, benzoyl peroxide, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, acid N-acetyl-L-cysteine, lipoic acid, azelaic acid and its salts, arachidonic acid, resorcinol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanalide, octopirox, octoxyglycerin, octanoylglycine, caprylyl glycol, 10-hydroxy-2-decanoic acid, dichlorophenylimidazole dioxolane and its derivatives described in WO 93 / 18743, famesol and phytosphingosines,and their mixtures; , a pigment modifying agent and / or skin lightening agents, such as double-stranded RNA oligonucleotides, are useful in decreasing tyrosinase expression. Other examples include ceramides, vitamin C and its derivatives, in particular vitamin CG, CP and 3-O ethyl vitamin C, alpha- and beta-arbutin, ferulic acid, kojic acid, resorcinol and its derivatives, calcium D-pantetheine sulfonate, lipoic acid, ellagic acid, vitamin B3, phenylethyl resorcinol, for example Symwhite 377® from Symrise, a kiwi juice (Actinidia chinensis) sold by Gattefosse, a Paeonia suffructicosa root extract, such as the product sold by Ichimaru Pharcos under the name Botanpi Liquid B®, a brown sugar extract (Saccharum officinarum), such as the molasses extract sold by Taiyo Kagaku under the name Molasses Liquid, a mixture of undecylenic acid and undecylenoyl phenyl alanine, such as Sepiwhite MSH® from Seppic; a vitamin such as a vitamin A compound such as retinol or retinoic acid, a vitamin B compound such as vitamin B1, B3 or B6, a vitamin C compound such as an ascorbyl phosphate salt (e.g., magnesium or sodium, and / or their derivatives; • an ultraviolet (UV) filter such as, for example, an aminobenzoic acid derivative, a dibenzoylmethane derivative, a salicylic acid derivative, a cinnamic derivative, a [3,[3] diphenylacrylate derivative, a benzophenone derivative, a benzylidene camphor derivative and mixtures thereof. Examples include ethylhexyl methoxycinnamate sold under the trade name UVINUL MC 80® by BASF, ethylhexyl salicylate sold under the trade name NEO HELIOPAN OS® by SYMRISE and octocrylene sold under the trade name NEO HELIOPAN 303® by SYMRISE; and / or • one of their combinations.

[0137] Additional additives

[0138] The composition of the invention may also include any additive commonly used in the art. For example, additional film-forming agents (in addition to the hydrophobically modified polysaccharide compound and the aqueous-phase film-forming agent), waxes, dispersants such as poly(12-hydroxystearic acid), preservatives, fragrances, fillers, antioxidants, neutralizing agents, silicone elastomers, and mixtures thereof may be added. A non-exhaustive list of such ingredients may be found in U.S. Patent Application Publication No. 2004 / 0170586. Other examples of suitable additional components may be found in the other U.S. references that have been cited previously in this application. Still other examples of such additional ingredients may be found in the International Cosmetic Ingredient Dictionary and Handbook (9th ed. 2002).However, it should be understood that preferred embodiments of the present invention include compositions that are "free", "substantially free" or "devoid of" the ingredients discussed in this paragraph such as additional film-forming agents and waxes.

[0139] According to preferred embodiments, the compositions of the present invention contain a total solids content (excluding film formers) of 10% by weight or less, preferably 5% by weight or less, or preferably 3% by weight or less relative to the weight of the composition. Preferably, the compositions of the present invention are free, free or substantially free of solids (excluding film formers).

[0140] A person skilled in the art will take care to select the optional additional additives and / or their quantity so that the advantageous properties of the composition according to the invention are not, or not substantially, compromised by the envisaged addition.

[0141] These substances can be selected in various ways by the person of the craft in order to prepare a composition that has the desired properties, for example, consistency or texture.

[0142] It goes without saying that the composition of the invention must be cosmetically or dermatologically acceptable, that is to say that it must contain a physiologically acceptable non-toxic support and must be able to be applied to the keratinous material of human beings.

[0143] According to preferred embodiments of the present invention, methods of caring for, and / or making up, keratinous material by applying compositions of the present invention to the keratinous material in an amount sufficient to care for, and / or make up, the keratinous material are provided. Similarly, preferred embodiments of the present invention include methods of priming the keratinous material for a cosmetic composition and / or fixing a cosmetic composition that has been previously applied to the keratinous material by applying compositions of the present invention over the keratinous material before applying a cosmetic composition (priming) and / or by applying compositions of the present invention over a cosmetic composition previously applied to the keratinous material (fixing).Preferably, the cosmetic composition used in conjunction with the compositions of the present invention is a color cosmetic composition.

[0144] Preferably, "making up" the keratinous material includes applying at least one coloring agent to the keratinous material (either in the composition itself or in a color layer composition applied either over or under the composition as described above) in an amount sufficient to impart color to the keratinous material.

[0145] According to particularly preferred embodiments of the present invention, methods of making up keratinous material such as skin comprising (1) applying a color cosmetic composition such as a foundation to the keratinous material (e.g., skin), (2) allowing the color cosmetic composition to dry on the keratinous material (e.g., skin), preferably allowing it to dry for about 1 minute to about 15 minutes, preferably for about 5 minutes to 10 minutes, and (3) applying a composition of the present invention over the dried color cosmetic composition that has been applied to the keratinous material (e.g., skin) are provided.Preferably, compositions of the present invention are applied over the dried color cosmetic composition in an amount sufficient to improve the transfer resistance of the color cosmetic composition relative to the transfer resistance provided by the color cosmetic composition when applied alone to a keratinous material.

[0146] According to preferred embodiments of the present invention, kits comprising, as separate compositions in one or more containers within the kits, (A) at least one composition of the present invention, in particular a fixative or primer composition for cosmetics, comprising at least one hydrophobically modified polysaccharide compound and at least one film former in aqueous phase; and (B) at least one other composition such as a cosmetic composition comprising at least one colorant are provided.

[0147] Compositions (A) and (B) may be contained in different portions or sections of the same container within the kit. However, compositions (A) and (B) may also be in different containers within the kit.

[0148] According to preferred embodiments of the present invention, assemblies, as applied to a keratinous material, comprising (A) at least one first layer of at least one composition comprising at least one colorant; and (B) at least one second layer of at least one composition of the present invention, in particular a fixative or primer composition for cosmetics, comprising at least one hydrophobically modified polysaccharide compound and at least one aqueous film former are provided. Preferably, the at least one second layer is applied over the at least one first layer (in which case the second layer is a fixative layer formed by applying a fixative composition to the first layer).However, if the at least one first layer is applied over the at least one second layer, the at least one second layer is a primer layer formed by applying a primer composition to a keratinous material.

[0149] According to a preferred embodiment of the present invention, compositions having improved cosmetic properties such as, for example, increased water resistance, sebum resistance and / or transfer resistance are provided. Preferably, the composition is a skin composition. Preferably, the composition is a fixative or primer composition. Also preferably, the composition further comprises at least one gelling agent and / or at least one active agent.

[0150] According to a preferred embodiment of the present invention, methods for manufacturing oil-in-water (o / w) emulsions (compositions) of the present invention comprising combining at least one hydrophobically modified polysaccharide compound and at least one aqueous film former in the amounts and / or ratios discussed above during formation of the emulsion composition are provided. Preferably, the composition is a composition for application to the skin. Preferably, the composition is a fixative or primer composition, and / or is in the form of a gel. Also preferably, the composition comprises furthermore at least one gelling agent and / or at least one active agent.

[0151] Unless otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations which may vary depending on the desired properties sought to be achieved by the present invention.

[0152] Although the numerical ranges and parameters presenting the broad scope of the invention are approximations, the numerical values ​​presented in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without limiting its scope accordingly. Percentages are given on a weight basis. EXAMPLES

[0153] Example 1 - Samples of inventive compositions

[0154] [Tables3] Total % 100.00 - General Total 100% - Preferred Chemical Name / Function % W / W % W / W Surfactants 0.1-10% 0.1-3% Waterborne Film Former 0.5-20% 1-10% Compound Modified Pullulan 0.5-20% 1-10% Oils 1-30% 2-20% Colorant / Fragrance / Active Optional Optional Water QS QS Monoalcohol 0-30% 2.5-25% Gelling Agent 0.1-10% 0.1-3% Example 2 - Test Protocols

[0155] The transfer resistance can be determined as follows.

[0156] A color cosmetic composition (e.g., a foundation such as L'Oréal Paris Makeup True Match Liquid Foundation) is applied to a keratinous material (e.g., skin) in a controlled amount (e.g., 0.020 grams) in a controlled area (e.g., 3 cm x 3 cm square). Wait 5 to 15 minutes until the solution has dried.

[0157] Apply a test composition (fixer) in a controlled amount (e.g., the same amount as the applied color cosmetic composition, such as 0.020 grams) over the applied color cosmetic composition, and allow it to dry. If a test composition (fixer) is not applied over the color cosmetic, the transfer resistance of the color cosmetic alone (without a fixative composition) can be compared to the transfer resistance when a fixative composition is used in conjunction with the color cosmetic composition.

[0158] A white cotton pad / ball is then used to rub over the area an identified number of times (e.g., 5 or more times) to assess the transfer resistance of the color cosmetic composition onto the pad / ball after such rubbing. Transfer resistance may be assessed by determining the difference in the amount of color cosmetic composition transferred onto the cotton pad / ball, with or without the fixing composition applied.Transfer resistance is rated on a scale of 1 to 5, with 1 = minimal improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball; 3 = moderate improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball; and 5 = significant improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball, with little or no transfer of the color cosmetic composition to the cotton pad / ball. Example 3 - Transfer resistance test

[0159] The following compositions A to J were prepared and tested as setting compositions for L'Oréal Paris Makeup True Match liquid foundation according to the protocol of Example 2.

[0160] Examples 3A-3D were comparative examples, containing little or no hydrophobically modified pullulan compound and / or little aqueous film former.

[0161] Examples 3E to 3J were representative of the inventive compositions containing the indicated amounts and / or ratios of hydrophobically modified pullulan compound and aqueous film former.

[0162] The transfer resistance of the commercial foundation + prepared fixer compositions was determined according to the protocol of Example 2: Example 3-A Example 3-B Example 3-C Example 3-DT Trimethylsiloxysilylcarbamoyl pullulan 0.15 0.30 0.60 0.00 Isododecane 4.85 4.70 4.40 5.00 Isohexadecane 0.32 0.32 0.32 0.32 Sorbitan oleate 0.04 0.04 0.04 0.04 Polysorbate 80 0.10 0.10 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 0.60 0.60 Vinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer 0.10 0.20 0.40 2.50 Ethanol 0 to 25 0 to 25 0 to 25 0 to 25 water QS QS QS QS Film-forming in oil phase 0.15 0.30 0.60 0.00 Film-forming in aqueous phase 0.10 0.20 0.40 2.50 Total film-forming 0.25 0.50 1.00 2.50 Transfer test - Transfer resistance 1 1 2 2 Example 3-E Example 3-F Example 3-G Example 3-H Example 3-1 Example 3-JT rimethylsiloxysilyl-carbamoyl pullulan 1.50 1.50 1.50 3.00 3.00 3.00 Isododecane 3.50 3.50 3.50 7.00 7.00 7.00 Isohexadecane 0.32 0.32 0.32 0.32 0.32 0.32 Sorbitan oleate 0.04 0.04 0.04 0.04 0.04 0.04 Polysorbate 80 0.10 0.10 0.10 0.10 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 0.60 0.60 0.60 0.60 Vinyl pyrrolidone / methacrylamide / viny 1 imidazole copolymer 1.25 2.50 3.75 0.00 1.25 2.50 Ethanol 0 to 25 0 to 25 0 to 25 0 to 25 0 to 25 water QS QS QS QS QS QS Oil-phase film-forming agent 1.50 1.50 1.50 3.00 3.00 3.00 Aqueous-phase film-forming agent 1.25 2.50 3.75 0.00 1.25 2.50 Total film-forming agent 2.75 4.00 5.25 3.00 4.25 5.50 Transfer test - Transfer resistance 3 5 5 5 5 5

[0165] As can be seen, the fixative compositions of the present invention resulted in superior transfer resistance when used in conjunction with the commercial foundation product compared to the com- comparative fixative positions containing no or too little hydrophobically modified pullulan compound and / or aqueous film former. Example 4

[0166] As in Example 3, the following inventive fixative compositions A to I were prepared and used as fixative compositions for L'Oréal Paris True Match Makeup liquid foundation according to the protocol of Example 2 to determine transfer resistance: Example 4-A Example 4-B Example 4-C Example 4-D Example 4-E Trimethylsiloxysilyl-carbamoy 1 pullulan 1.50 1.50 1.50 1.50 1.50 Isododecane 3.50 3.50 3.50 3.50 3.50 Isohexadecane 0.32 0.32 0.32 0.32 0.32 Sorbitan oleate 0.04 0.04 0.04 0.04 0.04 Polysorbate 80 0.10 0.10 0.10 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 0.60 0.60 0.60 Polyvinyl pyrrolidone 1.50 0 0 0 0 Polyvinyl alcohol 0 1.50 0 0 0 Vinyl pyrrolidone / vinyl acetate copolymer 0 0 1.50 0 0 Vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer 0 0 0 1.50 0 Vinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer 0 0 0 0 1.50 Ethanol 0 to 25 0 to 25 0 to 25 0 to 25 0 to 25 water QS QS QS to QS QS Transfer test - Transfer resistance 3 3 3 3 3 Example 4-F Example 4-G Example 4-H Example 4-1 Trimethylsiloxysilylcarbamoyl pullulan 1.50 1.50 1.50 1.50 Isododecane 3.50 3.50 3.50 3.50 Isohexadecane 0.32 0.32 0.32 0.32 Sorbitan oleate 0.04 0.04 0.04 0.04 Polysorbate 80 0.10 0.10 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 0.60 0.60 Butyl acrylate / hydroxypropyl dimethicone acrylate copolymer 1.50 0 0 0 Styrene / acrylates / ammonium methacrylate copolymer 0 1.50 0 0 Pectin 0 0 1.50 0 Pullulan 0 0 0 1.05 Ethanol 0 to 25 0 to 25 0 to 25 0 to 25 water QS QS QS QS Transfer test - Transfer resistance 3 3 3 3

[0169] As in Example 3, the inventive fixative compositions A-I demonstrated superior transfer resistance when used in conjunction with the commercial foundation product compared to comparative fixative compositions containing no or insufficient hydrophobically modified pullulan compound and / or aqueous film former.

Claims

Claims

1. An oil-in-water emulsion composition, preferably in the form of a gel, comprising (a) water, (b) at least one oil, (c) at least one hydrophobically modified polysaccharide compound; and (d) at least one aqueous-phase film former.

2. The composition of claim 1, wherein the composition further comprises (e) at least one compound selected from the group consisting of at least one gelling agent, at least one colorant, at least one active agent, and mixtures thereof.

3. A composition according to claim 2, wherein at least two of the gelling agents, coloring agents and active agents are present in the composition.

4. A composition according to any preceding claim, wherein the at least one hydrophobically modified polysaccharide compound is a silicone-modified pullulan compound, preferably trimethylsiloxysilylcarbamoyl pullulan.

5. Composition according to any one of the preceding claims, in which the at least one aqueous-phase film-forming agent is chosen from polyvinylpyrrolidone, a vinylpyrrolidone / vinyl acetate copolymer, a vinylpyrrolidone / acrylic acid copolymer, a polyvinyl alcohol, a copolymer of N-vinylpyrrolidone, methacrylamide and N-vinylimidazole, polyurethanes, latexes, pectin, water-soluble cellulose compounds and mixtures thereof, and is preferably a copolymer of N-vinylpyrrolidone, methacrylamide, and N-vinylimidazole.

6. A composition according to any preceding claim, wherein the weight ratio of aqueous phase film former to hydrophobically modified polysaccharide compound is from about 5:1 to about 1:5, preferably from about 3:1 to about 1:

3.

7. A composition according to any preceding claim, wherein the composition is free of colorant.

8. A method of making up the skin comprising applying the composition of any one of the preceding claims to a color cosmetic composition which has been previously applied to the skin.

9. A method of making up the skin comprising applying the composition of any one of the preceding claims to the skin, and applying a colored cosmetic composition over the composition that has been previously applied to the skin.