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

Abstract

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

Description

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

[0001] The present invention relates to water-in-oil (w / o) emulsions (compositions) comprising at least one hydrophobically modified pullulan compound and at least one film-forming agent in the aqueous phase, as well as to methods and kits comprising such emulsion compositions in one or more containers or in application. The compositions have beneficial cosmetic properties, including good or improved resistance to wear, water and / or sebum, and / or transfer resistance properties, in particular sebum resistance. 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 micropigmentation), 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 as soon as you wake up, 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 to 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] Furthermore, the aim of the present invention is to provide compositions which allow the expected cosmetic effects to persist, in particular the color of the makeup on keratinous materials, associated with a good level of comfort compared to conventional systems, in particular based on unmodified silicone resin.

[0006] 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 11,253,462 discloses compositions containing polymethyl methacrylate polymers among other ingredients; • US 2003 / 0082221 discloses compositions containing pullulan; • US 2016 / 0113860 discloses compositions containing modified pullulan by silicone 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.

[0007] There remains a need for improved compositions such as emulsion compositions having improved properties with respect to ease and / or comfort of application of the composition, and / or in particular with respect to improved properties related 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

[0008] The present invention relates to water-in-oil (w / o) emulsion compositions comprising at least one hydrophobically modified pullulan 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 foundation. Also preferably, the composition further comprises at least one thickening agent, at least one colorant and / or at least one active agent.

[0009] The present invention also relates to methods for treating, caring for and / or making up keratinous material such as the skin by applying compositions of the present invention to the keratinous material in an amount sufficient to treat, care for and / or make up the keratinous material. Preferably, the composition is a composition for application to the skin. Most preferably, the composition is a foundation.

[0010] The present invention also relates to methods of making a water-in-oil (w / o) emulsion composition comprising the combination of at least one hydrophobically modified pullulan 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. Most preferably, the composition is a foundation. Also preferably, the composition further comprises at least one thickening agent, at least one colorant and / or at least one active agent. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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.

[0012] “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%.

[0013] “A” or “an” as used herein means “at least one”

[0014] “At least one” means one or more and thus includes components in individual as well as mixtures / combinations.

[0015] As used herein, all proposed ranges are intended to include each specific range within the given ranges, and all combinations of sub-ranges therein. Thus, a range of 1 to 5 specifically includes 1, 2, 3, 4, and 5, as well as sub-ranges such as 2 to 5, 3 to 5, 2 to 3, 2 to 4, 1 to 4, etc.

[0016] “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.

[0017] “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.

[0018] “Surfactant” and “emulsifier” are used interchangeably throughout throughout this memorandum.

[0019] “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.

[0020] “Volatile,” as used herein, means having a flash point less than about 115°C.

[0021] “Non-volatile,” as used herein, means having a flash point greater than about 115°C.

[0022] “Polymer” as used herein means a compound that is made up of at least two monomers.

[0023] “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, for example 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., P121-10N Black Exfoliating Panel or 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-TRI-gloss) at a desired angle, such as 60° or 85°.

[0024] “Exempt” or “substantially free” or “devoid of” as used herein means that although it is preferable that no amount of the specific component is present in the composition, it is possible that there are very small amounts thereof in the compositions of the invention provided that these amounts do not materially affect at least one, preferably most, of the advantageous properties of the conditioning compositions of the invention.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 phenylated silicone oil is present in amounts no greater than 0.25% by weight, and "free of phenylated silicone oil" means that 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 pullulan 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 that in this paragraph are intended to be provided by way of example, not limitation.

[0025] “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 may be evaluated 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 can be evaluated immediately after application to keratinous materials such as the lips and these characteristics can then be re-evaluated and compared after a period of time. In addition, these characteristics can be evaluated relative to other compositions, such as commercially available compositions.

[0026] “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.

[0027] “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. Acceptable pH levels for the internal aqueous phase of the compositions of the present invention are preferably acidic, i.e., less than 7, preferably 6.5 or less, preferably 6.0 or less, preferably 5.5 or less, including all intermediate ranges and sub-ranges, such as, for example, 3 to 5, 4 to 6, 5.5 to 6.5, 3 to 4.5, etc. The compositions of the present invention may be in the form of a gel composition.

[0028] “Natural compound” means any compound derived directly from a natural substance such as a plant without having undergone any chemical modification.

[0029] “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.

[0030] “Synthetic compound” means any compound that is not a compound natural nor a naturally occurring compound.

[0031] “Room temperature” means 25°C.

[0032] “Atmospheric pressure” means 760 mmHg, i.e. 105 pascals.

[0033] 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 C2-C5 monohydric alcohol, and / or the film-forming system may consist essentially of the at least one pullulan compound and the at least one cyclic amide-containing polymer.

[0034] 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 “sebum resistance”.

[0035] 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.

[0036] 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 component or composition levels 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.

[0037] Film-forming agent in aqueous phase

[0038] 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.

[0039] 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.

[0040] Examples of aqueous-phase 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, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / acrylic acid copolymers, vinyl pyrrolidone / 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.; soluble polysaccharides in water such as pectin, unmodified pullulan or cellulose compounds; polyurethanes; latex; and mixtures thereof.

[0041] 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.

[0042] The cyclic amide and cyclic amine monomers useful in the first film-forming polymers include those having one or more aromatic or aliphatic ring structures. These rings may have sizes ranging from about 3 to 10, for example, 5 to 8 ring members.

[0043] 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 (γ-lactam), particularly vinylpyrrolidone.

[0044] 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.

[0045] In some embodiments, acrylamide monomers useful in these first film-forming polymers include those having -C3H5NO functional groups. Examples include (meth)acrylamides.

[0046] 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, polymer(s) containing cyclic amide residue(s) but no cyclic amine or acrylamide functionality include, but are not limited to, vinylpyrrolidone homopolymers (polyvinylpyrrolidone or PVP, such as those sold by BASF under the name Luviskol 30 or by Ashland under the name PVP K30L) and vinylpyrrolidone copolymers containing at least one non-vinylpyrrolidone monomer such as, for example, substituted or unsubstituted C2 (acrylic acid) or C3 (allyl) groups, optionally in the form of esters (e.g., acrylates or methacrylates) or ethers, such as vinylpyrrolidone / vinyl acetate (VP / VA) such as that sold as PVP / VA S 630 L by Ashland.

[0047] In some embodiments, at least one cyclic amide-containing 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.

[0048] In some embodiments, the at least one cyclic amide-containing polymer is a copolymer of N-vinyl pyrrolidone, methacrylamide, and N-vinylimidazole.

[0049] 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.

[0050] According to preferred embodiments, the compositions of the present invention are free, free of, or substantially free of polyurethanes.

[0051] Preferably, the at least one aqueous phase film former 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 1% to about 20% by weight, preferably from more than 2% to about 20%, and preferably from about 2.5% to about 15% by weight relative to the weight of the composition, including all intermediate ranges and sub-ranges such as, for example, from 4% to 15%, from 2.5% to 15%, from 3% to 25%, etc. Preferably, the at least one aqueous phase film former 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.

[0052] Hydrophobically modified pullulan compound

[0053] According to the present invention, compositions including one or more hydrophobically modified pullulan 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 film-forming system along with the at least one cyclic amide-containing polymer. Optionally, other film-forming agents may be in the film-forming system in the composition, if desired.

[0054] Pullulan is a natural polysaccharide produced from starch by the fungus Aureobasidium pullulans. Pullulan is an alpha-glucan consisting primarily of maltotriose repeating units linked linearly by alpha 1,6 glycosidic bonds. Natural pullulan is readily soluble in cold or hot water, forming clear, viscous solutions.

[0055] Pullulan can be produced, for example, from the fermentation of starch by partially hydrolyzed or using sucrose, sugarcane, milk, potato and other sources for carbohydrate raw materials.

[0056] Preferably, the hydrophobically modified pullulan compounds of the present invention are oil soluble. For example, the preferred pullulan compounds of the present invention have been modified with a hydrophobic group such as a siloxane group or a hydrocarbon group which 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 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).

[0057] A preferred siloxane-modified pullulan compound has a structure corresponding to:

[0058] a pullulan-linker-siloxane group;

[0059] wherein the siloxane 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, wherein the C1-C6 alkyl group is straight, cyclic or branched, substituted or unsubstituted; and

[0060] when the linker does not adversely affect either the film-forming properties or the 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.

[0061] Preferably, the hydrophobically modified pullulan compound is a trialkylsiloxysilylcarbamoyl pullulan, a particularly preferred compound being trimethylsiloxysilylcarbamoyl pullulan.

[0062] Preferably, the hydrophobically modified 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.

[0063] Preferably, the at least one hydrophobically modified pullulan 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 1% to about 20% by weight, preferably from about 2.5% to about 17.5%, and preferably from about 5% to about 15% 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 15%, 5% to 25%, etc.

[0064] According to preferred embodiments, the at least one aqueous-phase film former and the at least one hydrophobically modified pullulan compound are present in the compositions of the present invention in a weight ratio of about 3:1 to about 1:3, preferably about 2:1 to about 1:2, and most preferably about 1:1.

[0065] Aqueous phase

[0066] 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 5% 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 oil, preferably a water-in-oil (w / o) emulsion.

[0067] 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% by weight, preferably greater than 25% by weight, and preferably greater than 30% 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%.

[0068] Suitable C2-C5 monohydric alcohols, where applicable, include ethanol, propanol, butanol, pentanol, isopropanol, isobutanol and isopentanol. Ethanol is particularly preferred.

[0069] 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 5% to about 30%, and preferably from about 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%.

[0070] 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.

[0071] Oily phase

[0072] According to the present invention, compositions comprising at least one oil are proposed. The compositions of the present invention preferably comprise sufficient oil to form a water-in-oil emulsion, preferably from about 5% to about 80% oil, more preferably from about 10% to about 60% oil, and most preferably from about 15% to about 40% oil by weight based on the total weight of the composition, including all intermediate ranges and sub-ranges.

[0073] 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.

[0074] 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.

[0075] Non-limiting examples of volatile silicone oils are listed in Table 1 below.

[0076] [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

[0077] 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 that is more volatile than the decamethyltetrasiloxane.

[0078] According to other 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 marketed under the trademarks Isopar or Permethyl. Preferably, the non-silicone volatile oils have a flash point of at least 40°C.

[0079] Non-limiting examples of non-silicone volatile oils are given in Table 2 below.

[0080] [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

[0081] The volatility of solvents / oils can be determined using the evaporation rate as shown in U.S. Patent No. 6,338,839.

[0082] 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, but are not limited to, polar oils such as:

[0083] Hydrocarbon-based vegetable oils 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 optionally 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, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil, rye oil, quinoa oil, olive oil, barley 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;

[0084] 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, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate and octanoates, decanoates or ricinoleates of alcohols or po- lyalcohols; hydroxylated esters, for example isostearyl lactate or dii-sostearyl malate; and pentaerythritol esters;

[0085] synthetic ethers containing from 10 to 40 carbon atoms;

[0086] C8 to C26 fatty alcohols, for example oleyl alcohol, cetyl alcohol, stearyl alcohol and cetearyl alcohol; and

[0087] 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 Vaseline (petrolatum), 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 waxes.

[0091] Low HLB surfactants

[0092] According to preferred embodiments of the present invention, compositions comprising at least one low HLB surfactant are provided. "HLB" refers to the "hydrophilic-lipophilic balance" associated with 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 typically more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (W / O) emulsifiers. Emulsifiers with higher HLB are typically 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 "low HLB surfactant" means a surfactant having an HLB value of less than or equal to 6, preferably less than 5, and preferably less than 4.Preferably, the HLB value is 3 or higher.

[0093] The low HLB surfactant is present as all or part of a "surfactant component" in the compositions of the present invention. According to preferred embodiments of the present invention, the surfactant component has an HLB value of less than or equal to 6, preferably less than 5, and most preferably less than 4. Preferably, the HLB value is 3 or greater.

[0094] According to preferred embodiments, the low HLB surfactant is non-ionic.

[0095] According to preferred embodiments, the low HLB surfactant comprises a backbone and one or more pendant groups, wherein (1) the backbone is hydrophobic and one or more pendant groups are hydrophilic, or (2) the backbone is hydrophilic and one or more pendant groups are hydrophobic. The backbone may be silicone-based or hydrocarbon-based. By "backbone" is meant that the surfactant comprises a backbone chain. By "pendant" group(s) is meant that one or more groups are attached to the backbone or backbone chain of the surfactant. The pendant group(s) may be silicone-based or hydrocarbon-based, and may be attached at any location along the backbone or backbone chain, e.g., at one or both ends of the chain, at one or more locations that are not at a terminal end of the chain, or both. In preferred embodiments, the pendant group(s) include one or more ester groups attached to the backbone or backbone chain.

[0096] A preferred backbone is a hydrophobic compound such as, for example, C8-C24 fatty compound(s), preferably C12-C20 fatty compound(s), and most preferably C16-C18 fatty compound(s) such as, for example, stearate, isostearate, laurate, etc., and a preferred pendant group for such a backbone is a hydrophilic group such as a polyethylene glycol (PEG) polymer or a polyglyceryl polymer.

[0097] Another preferred backbone is a hydrophilic hydrocarbon-based backbone such as a polyethylene glycol (PEG) polymer or a polyglyceryl polymer, and a preferred pendant group for such a backbone is a hydrophobic group such as, for example, C8-C24 fatty compound(s), preferably C12-C20 fatty compound(s), and preferably C16-C18 fatty compound(s) such as, for example, stearate, isostearate, laurate, etc.

[0098] The low HLB surfactant of the present invention may be a silicone surfactant, preferably comprising dimethicone (e.g., PEG-10 dimethicone or PEG-9 lauryl polydimethylsiloxyethyl dimethicone), or a non-silicone surfactant, free of dimethicone (e.g., PEG-30 dihydroxystearate). The low HLB surfactant of the present invention may have alkoxylation (e.g., ethoxylation or propoxylation) through groups such as, for example, (C2H4O)— / polyethylene glycol (PEG), (C3H6O)— / polypropylene glycol (PPG) groups, etc. Suitable emulsifiers include alkoxylated compounds, partial glycerides of alkoxylated compounds, polyglycerolated compounds, and mixtures thereof, etc. Polyglycerolated compounds are preferred.

[0099] Suitable polyglycerolated compounds include, but are not limited to, compounds containing preferably 2 to 20 glyceryl groups, preferably 3 to 15 glyceryl groups, and preferably 4 to 10 glyceryl groups. Polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate, sold under the trade name Isolan GPS by Evonik, is particularly preferred.

[0100] Particularly preferred low HLB surfactants are:

[0101] [Tables 3] Surfactants HLB POLYGLYCERYL-4 DIISOSTEARATE / POLYHYDROXYSTEARATE / SEBAC ATE 5 POLYGLYCERYL-4 ISOSTEARATE 5 POLYGLYCERYL-2 DIISOSTEARATE 5,5 GLYCOL DISTEARATE 5-6 GLYCERYL STEARATE 5,8 PEG-30 DIPOLYHYDROXYSTEARATE 5,5 PEG-10 DIMETHICONE 4,5 LAURYL POLYDIMETHYLSILOXYETHYL DL METHICONE PEG-9 3 PEG-9 POLYDIMETHYLSILOXYETHYL DL METHICONE 4 PEG-6 DIISOSTEARATE 5

[0102] The at least one low HLB surfactant is preferably present in the compositions of the present invention in an amount of about 1% to about 15%, preferably about 1.5% to about 10%, and preferably about 2% to about 8%, by weight relative to the total weight of the composition, including all intermediate ranges and sub-ranges.

[0103] Thickening agent / Coloring agent / Active agent

[0104] Thickening agent

[0105] According to preferred embodiments of the present invention, compositions further comprising at least one thickening agent are provided. Suitable thickening agents include agents for thickening an oil phase of a composition, agents for thickening an aqueous phase of a composition, and mixtures thereof.

[0106] According to preferred embodiments, the thickening agent is a gelling agent for gelling the water (aqueous phase) in the composition. Suitable gelling agents include any gelling agent, such as, for example, clay 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 an amphiphilic polymer. phiphile or a clay, or a combination thereof.

[0107] 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, optionally modified clays from the halloysite, dombassite, antigorite, berthierine, pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, saponite, chlorite, sepiolite and illite family.

[0108] 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.

[0109] Natural clay is a sedimentary rock composed largely of specific minerals, generally aluminum silicates. Kaolin is therefore a natural clay.

[0110] Clays can also be synthetic. Thus, Sumecton mentioned below is a synthetic saponite.

[0111] Clays can also be chemically modified with various compounds, such as acrylic acids, polysaccharides (e.g. carboxymethyl cellulose) or organic cations.

[0112] Preferably, in the context of the present invention, clays are used which are cosmetically compatible and acceptable with keratinous materials. Clays which may be cited in particular include kaolinite, montmorillonites, saponites, laponites, hectorites and illites. Mixtures of clays and natural clays may also be used.

[0113] Natural clays that may be cited include green clays, in particular rich in illite; clays rich in montmorillonite, known as Fuller's earth, or such as bentonite or white clays rich in kaolinite. As bentonites, or modified bentonites, mention may be made in particular of those sold under the names Bentone 38 VCG®, Bentone Gel CAO V®, Bentone 27 V®, Bentone Gel ISD V and Bentone Gel MIO V® by the company Elementis.

[0114] As a montmorillonite-rich clay, mention may be made of aluminum silicate hydrate sold under the name Gel White H® by the Rockwood company.

[0115] 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®.

[0116] 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.

[0117] Preferably, where applicable, the thickening 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.

[0118] Active agent

[0119] 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).

[0120] 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 hydroxyalkyl urea, in particular hydroxyalkylurea, and mixtures thereof; • a desquamating agent, which may be a compound capable of acting either 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 comeodesmosomes, glycosidases, the chymotryptic enzyme of the stratum corneum (SCCE), or even other proteases (trypsin, chymotrypsin type). Examples of mineral salt chelating agents include: EDTA; N-acyl-N.N' acid.N'-Ethylenediaminetriacetic 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 methylglycine diacetate 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 components that improve skin texture, 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 copemicia 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 their 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 root extract of Paeonia suffructicosa, 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 phenyl alanine of a decylenoyl, such as Sepiwhite MSH® from Seppic; . an amino acid such as arginine, histidine, methionine, lysine, proline, leucine, lycine, sarcosine, etc.; 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, in in particular niacinamide, 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.

[0121] Additional additives

[0122] The composition of the invention may also include any additive commonly used in the field. For example, additional film-forming agents (in addition to the carbosiloxane dendrimer compound and the cyclic amide-containing polymer), 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. 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 embodiments of the present invention include compositions that are "free", "substantially free" or "lacking" the ingredients discussed in this paragraph such as additional film-forming agents and waxes as discussed above as well as fillers, particularly matting fillers (the compositions are "free of matting fillers", "substantially free of matting fillers", or "lacking matting fillers".

[0123] 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.

[0124] These substances can be selected in various ways by the person skilled in the art in order to prepare a composition which has the desired properties, for example, consistency or texture.

[0125] 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 physiological support logically acceptable non-toxic and must be suitable for application to human skin.

[0126] According to other preferred embodiments, methods of treating, caring for and / or enhancing the appearance of skin by applying compositions of the present invention to the skin in an amount sufficient to treat, care for and / or enhance the appearance of the skin are provided. In accordance with these foregoing preferred embodiments, the compositions of the present invention are applied topically to the desired area of ​​skin in an amount sufficient to treat, care for and / or enhance the appearance of the skin. The compositions may be applied to the desired area as needed, preferably once or twice daily, more preferably once daily and then preferably allowed to dry before subjecting them to contact such as with clothing or other objects (e.g., a topcoat).Preferably, the composition is allowed to dry for about 1 minute or less, more preferably for about 45 seconds or less. The composition is preferably applied to the desired area which is dry or has been dried prior to application, or to which a base coat has been previously applied.

[0127] 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. Most preferably, the composition is a foundation further comprising at least one colorant, preferably a surface-treated pigment.

[0128] According to a preferred embodiment of the present invention, methods for making a water-in-oil (w / o) emulsion composition comprising combining (adding) at least one hydrophobically modified pullulan compound and at least one aqueous film former during the preparation of the emulsion composition are provided. Preferably, the composition is a skin composition. Preferably, the at least one hydrophobically modified pullulan compound and at least one aqueous film former are combined or added in the amounts and / or ratios discussed above. Most preferably, the composition is a foundation further comprising at least one colorant, preferably a surface-treated pigment.

[0129] 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 as discussed above, in particular a foundation, comprising at least one hydrophobically modified pullulan compound and at least one film former in aqueous phase and (B) at least one other composition such as a primer composition, a basecoat composition, or a topcoat composition are provided. 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.

[0130] 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 cases 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.

[0131] 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. Percentages are given on a weight basis. EXAMPLES

[0132] Example 1 - Sample of E / O emulsion foundation formulation Total % 100.00 - General Total 100% - Preferred Chemical Name / Function % by Weight % by Weight Surfactants 1-10% 1-5% Water-Based Film Former 0.5-10% 1-5% Hydrophobically Modified Pullulan 0.5-10% 1-5% Oils 5-50% 20-40% Colorants 1-30% 5-20% Water QS QS Monoalcohol 1-20% 3-10% Polyol 1-10% 2-8% Active Agent (Vitamin) 1-20% 5-20% Clays 0.1-10% 0.1-5% Fillers 0.5-10% 1-5% Example 2 - Example of E / O emulsion foundations

[0134] INCI US Com positi on A Com positi on B Com positi on C Com positi on D Com positi on E Com positi on F Com positi on G Com positi on H WATER 36,30 31,95 27,60 23,25 35,43 33,69 35,43 33,69 MAGNESIUM SULFATE 0,87 0,87 0,87 0,87 0,87 0,87 0,87 0,87 BUTYLENE GLYCOL 2,61 2,61 2,61 2,61 2,61 2,61 2,61 2,61 PHENOXYETHANOL 0,17 0,17 0,17 0,17 0,17 0,17 0,17 0,17 VP / METHACRYLAMI DE / VINYL IMIDAZOLE COPOLYMER (LUVISET CLEAR AT3) 4,35 8,70 13,05 VP / VA COPOLYMER (PVP / VA 630L) — — — — 0,87 2,61 — — PVP (LUVISKOL K30) — — — — — — 0,87 2,61 ALCOHOL DENAT.4.35 4.35 4.35 4.35 4.35 4.35 4.35 4.35 POLYGLYCERYL-4 ISOSTEARATE 0.87 0.87 0.87 0.87 0.87 0.87 0.87 0.87 DIISOSTEARATE / POLYHYDROXYSTEARATE / SEBACATE OF POLY-GLYCERYL-4 2.61 2.61 2.61 2.61 2.61 2.61 2.61 2.61 ACETYL TRIBUTYL CITRATE 0.29 0.29 0.29 0.29 0.29 0.29 0.29 0.29 DIMETHICONE 1.52 1.52 1.52 1.52 1.52 1.52 1.52 1.52 ISODODECANE 10.73 10.73 10.73 10.73 10.73 10.73 10.73 10.73 DISTEARDIMONIUM HECTORITE (and) 11.31 11.31 11.31 11.31 11.31 11.31 11.31 11.31 . PROPYLENE CARBONATE ISOPROPYL LAUROYL SARCOSINATE 0.87 0.87 0.87 0.87 0.87 0.87 0.87 0.87 ISOHEXADECANE 5.80 5.80 5.80 5.80 5.80 5.80 5.80 5.80 TRIMETHYLSILOXYS ILYL-CARBAMOYL PULLULAN (TSPL-ID-30) 8.70 8.70 8.70 8.70 8.70 8.70 8.70 8.70 HYDROPHOBICALLY MODIFIED PIGMENTS 13.00 13.00 13.00 13.00 13.00 13.00 13.00 13.00

[0136] Example 3 - Comparison of gloss levels at 60° for film-forming foundations in oil phase and in combined oil phase + aqueous phase.

[0137] The simplex foundation formulations were created with a constant concentration of pullulan compound (TSPL) in isododecane in combination with concentrations of 0.87% or 2.61% of waterborne active film former (Luviset, VP / VA, PVP). A 6 mil pinch bar was used to create one film of each composition A, B, D, E, F, G, and H on an opacity card. The films were then dried at 32°C in an oven and measured using a BYK Trigloss gloss meter on the black side of the card. It was observed that formulations containing both oilborne (TSPL) and waterborne film formers exhibited reduced gloss levels compared to the oilborne film former alone (composition A) when measured at 60° as reflected in the Table below. Summary description Composition Degree of gloss 60° TSPL only Composition A 55.1 TSPL + Luviset (0.87%) Composition B 26.4 TSPL + Luviset (2.61%) Composition D 1 TSPL + VP / VA (0.87%) Composition E 28.5 TSPL + VP / VA (2.61%) Composition F 36.3 TSPL + PVP (0.87%) Composition G 14.7 TSPL + PVP (2.61%) Composition H 13.1

[0139] Example 4 - Comparison of the degrees of shine at élK for foundations with artificial sebum.

[0140] The same simplex foundation formulations tested in Example 3 were mixed at 95% of the formulation + 5% artificial sebum in a high-speed mixer, and then a 6 mil pinch bar was used to create a film of each on an opacity card. The films were then dried at 32°C in an oven and measured using a BYK Trigloss gloss meter on the black side of the card. It was observed that the formulations containing both oil-phase (TSPL) and water-phase film formers exhibited reduced gloss levels compared to the formulation containing oil-phase film formers alone when measured at 60°, as reflected in the Table below.

[0141] [Tables?] Summary description Composition Shine level 60° + 5% sebum TSPL only Composition A 69.8 TSPL + Luviset (0.87%) Composition B 27.8 TSPL + Luviset (2.61%) Composition D 0.6 TSPL + VP / VA (0.87%) Composition E 25.9 TSPL + VP / VA (2.61%) Composition F 31.3 TSPL + PVP (0.87%) Composition G 31.9 TSPL + PVP (2.61%) Composition H 26

[0142] Example 5 - Shine level 60° of foundations with increasing concentration of film-forming agent in aqueous phase.

[0143] Simplex Foundation Formulations A, B, C, and D were created with a constant concentration of pullulan compound (TSPL) in isododecane in combination with 0%, 0.87%, 1.74%, or 2.61% active polymer content of Luviset AT Clear 3 film former. A 6 mil pinch bar was used to create one film of each on an opacity card. Separate films were created from the base foundation, and a 95% / 5% mixture of foundation and artificial sebum was produced. The films were then dried at 32°C in an oven and measured using a BYK Trigloss gloss meter on the black side of the card. It has been observed that formulations containing both oil-phase (TSPL) and water-phase (Luviset) film formers exhibit reduced gloss levels compared to the oil-phase film former alone (when measured at 60°).Furthermore, it was observed that increasing the concentration of the film former in the aqueous phase decreases the degree of gloss in a concentration-dependent manner. Note Composition Shine level at 60° Shine level at 60° with 5% sebum TSPL only Composition A 55.1 69.8 TSPL + Luviset (0.87%) Composition B 26.4 27.8 TSPL + Luviset (1.74%) Composition C 2.9 1.2 TSPL + Luviset (2.61%) Composition D 1 0.6

[0145] Example 6 - Degrees of shine at 85° of foundations with an increasing concentration of film-forming agent in the aqueous phase.

[0146] Example 5 was repeated, with measurement at 85°. It was observed that formulations containing both oil-phase (TSPL) and aqueous-phase (Luviset) film formers exhibited reduced gloss levels compared to the oil-phase film former alone. In addition, it was observed that increasing the concentration of the aqueous-phase film former decreased the gloss level in a concentration-dependent manner.

[0147] [Tables9] Comment Composition Shine level 85° Shine level 85° + 5% sebum TSPL only Composition A 65.1 68 TSPL + Luviset (0.87%) Composition B 60.2 59.5 TSPL + Luviset (1.74%) Composition C 29 4 TSPL + Luviset (2.61%) Composition D 6.2 1 Example 7 - Dry transfer tests

[0148] The following compositions were prepared: INCI US Composition A Composition J WATER 36,29640000 21,79350000 MAGNESIUM SULFATE 0,87000000 0,87000000 BUTYLENE GLYCOL 2,61000000 2,61000000 PHENOXYETHANOL 0,17400000 0,17400000 SKINCARE INGREDIENTS — 5,61150000 VP / METHACRYLAMIDE / VINYL IMIDAZOLE COPOLYMER (en tant que Luviset Clear AT3, 20 % d'actif) — 8,70000000 ALCOHOL DENAT. 4,35000000 4,35000000 SODIUM HYDROXIDE — 0,19140000 POLYGLYCERYL-4 ISOSTEARATE 0,87000000 0,87000000 POLYGLYCERYL-4 DIL SOSTEARATE / POLYHYDROXYSTEARATE / SEBACATE 2,61000000 2,61000000 ACETYL TRIBUTYL CITRATE 0,28710000 0,28710000 DIMETHICONE 1,52250000 1,52250000 ISODODECANE 10,72710000 7,26450000 FRAGRANCE 0,08700000 DISTEARDIMONIUM HECTORITE (et) PROPYLENE CARBONATE 11,31000000 11,31000000 TRIHYDROXYSTEARIN — 0,26100000 ISOPROPYL LAUROYL SAR- COSINATE 0,87000000 0,87000000 ISOHEXADECANE 5,80290000 5,80290000 FILLER PARTICLES — 3,11460000 TRIMETHYLSILOXYSILYLCARB AMOYL PULLULAN 8,70000000 8,70000000 HYDROPHOBICALLY MODIFIED PIGMENTS 13 13

[0150] 20 μL of foundation compositions A and J were applied in a square of 2.5 cm x 2.5 cm on a bare forearm and dried for 45 minutes. The foundations were then wiped 5 times in alternating directions with a Crock ISO 105 F09 square, each with constant pressure. The foundation containing both TSPL and Luviset (composition J) was found to be more resistant to disturbance and transfer by rubbing than the foundation not containing Luviset (composition A).

[0151] Example 8 - Resistance to friction in the presence of sebum

[0152] The following compositions were prepared:

[0153] [Tableauxll] INCI Name Composition K Composition L WATER 31.89 12.93 MAGNESIUM SULFATE 0.70 0.70 CAPRYLYL GLYCOL 0.18 0.09 PHENOXYETHANOL 0.09 0.09 SKINCARE INGREDIENTS 9.68 9.68 CELLULOSE GUM 0.26 0.26 VP / METHACRYLAMIDE / VINYL IMIDAZOLE COPOLYMER (Luviset Clear AT3) — 14.65 FRAGRANCE — 0.04 ALCOHOL DENAT. 4.40 4.36 DIISOSTEARATE / POLYHYDROXYSTEAR ATE / POLYGLYCERYL-4 SEBACATE 2.64 2.64 ACETYL TRIBUTYL CITRATE 0.29 0.29 ISODODECANE 4.40 5.72 DISTEARDIMONIUM HECTORITE (and) PROPYLENE CARBONATE 13.20 13.20 ISOHEXADECANE 6.16 9.24 FILLER PARTICLES 2.38 2.38 TRIMETHYLSILOXYSILYLCARBAMOYL PULLULAN (TSPL-ID-30) 11.73 11.73 HYDROPHOBICALLY MODIFIED PIGMENTS 12.00 12.00

[0154] 20 μL of Compositions K and L were applied to a leatherette substrate white protein in a 3.2 cm x 3.2 cm square with a nitrile gloved finger. Samples were dried at 32 °C in an oven. Samples were then read on a spectrophotometer to obtain CIE LAB values ​​for the initial substrate and substrate + foundation. A Crock ISO 105 F09 square was dipped in artificial sebum and any excess sebum was blotted with a lint-free paper towel. Samples were then rubbed twice in alternating directions with constant force. Samples were then allowed to dry for at least

[0155]

[0156]

[0157]

[0158] minus 6 hours and they were read again to obtain the LAB values ​​for the foundation color after rubbing. The L values ​​were used to calculate the normalized AL from the equation: Normalized AL = x 10 0 Or : • ABS = absolute value • Lfinal = final L value in the LAB color space of the deposit • Linitial = initial value L of the deposit • Lsubstrate = L value of the substrate (supplare, protein leatherette) • Normalized AL = % change in darkening of the makeup product It was observed that the foundation containing a film-forming agent in aqueous phase exhibited a significantly lower change in L value compared to the foundation containing only TSPL, indicating resistance to rubbing in the presence of sebum, as reflected in the Table below: [Tablell] NOTE Mean normalized AL composition Standard deviation Normalized AL TSPL only Composition J 12.91 1.51 TSPL + Luviset Composition K 0.80 0.69

Claims

Claims

1. A water-in-oil emulsion composition comprising (a) water, (b) at least one oil, (c) at least one hydrophobically modified pullulan compound; and (d) at least one aqueous-phase film former.

2. The composition of claim 1, further comprising (e) at least one compound selected from the group consisting of at least one thickening agent, at least one colorant and at least one active agent.

3. A composition according to claim 2, wherein at least one thickening agent is present in the composition, and the at least one thickening agent is a clay, preferably a hectorite; wherein at least one coloring agent is present in the composition, and the at least one coloring agent is a surface-treated pigment; and / or wherein at least one active agent is present in the composition, and the at least one active agent is a vitamin, preferably a vitamin B compound.

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

5. A composition according to any preceding claim, wherein the at least one aqueous film former is at least one cyclic amide-containing polymer, preferably a copolymer of N-vinyl pyrrolidone, methacrylamide and N-vinylimidazole, a copolymer of polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate, or a mixture thereof.

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

1.

7. A composition according to any preceding claim, wherein the water is present in an amount greater than 20% by weight relative to the total weight of the composition, preferably between about 25% and 60% by weight relative to the total weight of the composition.

8. A method of making up the skin comprising applying the composition of any one of the preceding claims to the skin in an amount sufficient to make up the skin.

9. A composition according to claim 1, comprising (a) water, (b) at at least one volatile hydrocarbon oil, (c) at least one siloxane-modified pullulan compound; (d) at least one cyclic amide-containing polymer; (e) at least one thickening agent that is a clay; (f) at least one surface-treated pigment; and (g) at least one vitamin compound.