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 FILM FORMING AGENT IN THE AQUEOUS PHASE FIELD OF 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 aqueous-phase film-forming agent, 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 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, in the keratin-based skincare and makeup market, many products claim to offer all-day wear and resistance to external factors such as water, sebum, mechanical friction, etc. (waterproof mascara, meal-resistant lipsticks, long-lasting foundations). Long-lasting products for lips, eyelashes, eyebrows, or face, which can be used at home, are primarily based on synthetic coating polymers in the presence of organic solvents.For lip makeup and face makeup compositions, some formulas contain an unmodified silicone resin as a film-forming agent, such as the compound with the INCI name: Trimethylsiloxysilicate or a compound with the INCI name: Polypropylsilsesquioxane, or alternatively, a silicone acrylate copolymer such as the product with the INCI name: Acrylates / polytrimethylsiloxymethacrylate copolymer. Long-lasting makeup products for eyelashes and / or eyebrows (mascaras, eyeliners) typically use waxes or film-forming polymer particles in aqueous suspension, such as latex (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, traditional makeup products have found themselves competing 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.), eyebrow makeup (semi-pigmentation, also known as micropigmentation), and complexion makeup (freckles, beauty marks or the entire face, a healthy glow or radiant complexion) or lips (semi-permanent tattoo). This new trend is driving consumers to seek increasingly longer-lasting results for greater convenience (avoiding daily makeup application and removal, a healthy glow from the moment they wake up, etc.).

[0004] The object of the present invention is to propose 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 keratinous materials, as well as to improve the hold of the cosmetic composition on keratinous materials and its resistance to external forces such as one or more of the following: mechanical friction, water, sweat and perspiration, sebum, oil, etc.

[0005] Furthermore, the aim of the present invention is to offer compositions which allow persistence of the expected cosmetic effects, in particular of the colour 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] Any 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 nonionic 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 which has an inadequate thickening effect; • CN 111801092 discloses compositions for the impregnation of a material, where the compositions contain PEG- or polyether-modified silicones and dendrimer-type siloxanes; • FR 3 104 958 discloses compositions containing polyurethane dispersions among other ingredients; and • FR 3 110 849 discloses compositions containing polyurethane and / or acrylic dispersions among other ingredients, with little or no fat.

[0007] There remains a need for improved compositions such as emulsion compositions having enhanced properties with regard to the ease and / or comfort of application of the composition, and / or in particular with regard to enhanced properties related to better adhesion of the cosmetic composition to 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 aqueous-phase film-forming agent. Preferably, the composition is 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 applying makeup to keratinous material such as skin by applying compositions of the present invention to the keratinous material in a sufficient quantity to treat, care for, and / or apply makeup to 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 for producing a water-in-oil (w / o) emulsion composition comprising the combination of at least one hydrophobically modified pullulan compound and at least one film-forming agent 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 annexed thereto, it shall be understood that the terms used have their ordinary and usual meanings in the art, unless otherwise specified.

[0012] “Approximately” as used here means to within 10% of the number indicated (for example, “ "Approximately 10%" means from 9% to 11% and "approximately 2%" means from 1.8% to 2.2%.

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

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

[0015] As used here, all the proposed ranges are intended to include each specific range within the given ranges, and all combinations of intermediate sub-ranges. Thus, a range from 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-forming”, “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-forming agent has evaporated, been absorbed into the substrate and / or dissipated on it.

[0017] “Wax” as used here is a lipophilic fatty compound that is solid at temperature ambient (25 °C) and changes from solid to liquid reversibly, having a melting point 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 report.

[0019] “Substitute” as used herein means comprising at least one substitute. Non-limiting examples of substituents include atoms, such as oxygen 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 also be substituted.

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

[0021] “Non-volatile”, as used here, means having a flash point greater than approximately 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°, 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 These tests are performed by depositing test films onto a substrate (e.g., a black exfoliating P121-10N panel or a BYK No. 2810 opacity card) using a necking bar (e.g., 1 mil, 3 mil, or 6 mil thick) and an automatic necking 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 exempt” or “devoid of” as used herein means that although it is preferable that no quantity of the specific component be present in the composition, it is possible that there may be very small quantities of it in the compositions of the invention provided that these quantities do not materially affect at least one, preferably most, of the advantageous properties of the revitalizing compositions of the invention.Thus, for example, "free from phenylated silicone oil" means that an effective amount (i.e., an effective amount of dullness inhibition) of phenylated silicone oil is omitted from the composition (i.e., about 0% by weight), "substantially free from phenylated silicone oil" means that phenylated silicone oil is present in amounts not exceeding 0.25% by weight, and "free from phenylated silicone oil" means that phenylated silicone oil is present in amounts not exceeding 0.5% by weight, relative to 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) mattifying fillers (compositions of the invention that are "free of mattifying fillers," "substantially free of mattifying fillers," and "devoid of mattifying fillers") and (2) additional film-forming agents other than the hydrophobically modified pullulan compound and the aqueous-phase film-forming agent (compositions of the invention that are "free of additional film-forming agents," "substantially free of additional film-forming agents," and "devoid of additional film-forming agents"). These terms have meanings consistent with the discussion in this paragraph, even if they are not specifically invoked for each identified ingredient. The examples given of the use of such language as that in this paragraph are intended to be provided by way of illustration, and not as a limitation.

[0025] The "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 with the naked eye, after a prolonged period of time. The "makeup result" can be evaluated by assessing the long-lasting properties using any method known in the art for evaluating such properties. For example, long-lasting performance can be assessed by a test involving the application of a composition to keratinous materials such as the lips and evaluating the color of the composition. after a prolonged 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 certain time. Furthermore, these characteristics can be evaluated in relation to other compositions, such as commercially available ones.

[0026] “Keratinous material” or “keratin material” means natural nails, the lips, skin such as that of the face, body, hands and the area around the eyes, and keratin fibers such as hair, eyelashes, eyebrows, human 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 pulling) likely to 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] “Compound of natural origin” means any compound derived from a 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 compound of natural origin.

[0031] “Ambient 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 essentially consist of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredient, component, or limitation described herein or otherwise useful. For example, the aqueous solvent system may "essentially consist of" water and the C2-C5 monoalcohol, and / or the film-forming system may essentially consist of at least one pullulan compound and at least one cyclic amide-containing polymer.

[0034] For the purposes of the present invention, the "fundamental and innovative property" associated with compositions, components and processes 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 limit themselves to the materials described and referenced by a particular trade name. Equivalent materials (for example, those obtained from a different source under a different name or catalogue (reference) number) to those referenced by a trade name may be substituted and used in the processes described and claimed herein.

[0036] All percentages and ratios are calculated by weight unless otherwise stated. All percentages are calculated on the basis of the total weight of a composition unless otherwise stated. All component or composition levels refer to the active level of that component or composition and are understood to be exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources.

[0037] Film-forming in aqueous phase

[0038] According to the present invention, compositions comprising one or more aqueous film-forming polymers (“first film-forming polymers” or “first film-formers”) that are water-soluble or water-dispersible nonionic polymers are proposed. For clarity, “water-soluble or water-dispersible nonionic” means that the polymer is nonionic. The polymer is also water-soluble or water-dispersible, in particular insofar as it can be readily stabilized in a vehicle (e.g., water) present in the composition.

[0039] 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-forming agent.

[0040] Examples of aqueous-phase film-forming polymers include, but are not limited to, homopolymers and copolymers containing at least one (meth)acrylic acid monomer and / or at least one vinylpyrrolidone monomer, such as polyvinylpyrrolidone copolymers, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / acrylic acid copolymers, vinyl pyrrolidone / acrylate copolymers, alkyl (e.g., butyl) 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 their mixtures.

[0041] According to preferred embodiments, the at least one aqueous-phase film-forming polymer is at least one polymer containing a cyclic amide. 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 that the at least one polymer may contain neither a cyclic amine nor an acrylamide functionality.

[0042] Useful cyclic amide and cyclic amine monomers in early film-forming polymers include those having one or more aromatic or aliphatic ring structures. These rings can have sizes ranging from approximately 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. Therefore, 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, γ-lactam, γ-lactam, β-lactam, and ε-lactam. In a preferred embodiment, the cyclic amide is a pyrrolidone (a γ-lactam), in particular vinylpyrrolidone.

[0044] The 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, the 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 polymer containing cyclic amide preferably has at least one cyclic amine functionality and also acrylamide, preferably both, although it is possible that the polymer may not contain any functionality. For example, 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 or PVP, such as those sold by BASF as Luviskol 30 or by Ashland as PVP K30L) 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, possibly in the form of esters (e.g., acrylates or methacrylates) or ethers, such as the vinylpyrrolidone / vinyl acetate (VP / VA) such as that sold under the name PVP / VA S 630 L by Ashland.

[0047] In some embodiments, at least one polymer containing the cyclic amide 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, at least one cyclic amide-containing polymer is a copolymer of N-vinyl pyrrolidone, methacrylamide and N-vinylimidazole.

[0049] In some embodiments, 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 devoid of, free from or substantially free from polyurethanes.

[0051] Preferably, the at least one aqueous-phase film-forming agent 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-forming agent 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 comprising one or more hydrophobically modified pullulan compounds (“second film-forming polymers” or “second film-forming agents”) are proposed. One or more of these second film-forming polymers form part of a film-forming system, as does at least one polymer containing cyclic amide. Optionally, other film-forming agents may be included in the film-forming system within the composition, if desired.

[0054] Pullulan is a natural polysaccharide produced from starch by the fungus Aureobasidium pullulans. Pullulan is an alpha-glucan primarily composed of repeated maltotriose units linearly linked 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 fully hydrolyzed or using sucrose, sugar cane, 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 that confers 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 hydrocarbon groups of C8 or higher (for example, 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-binder-siloxane group;

[0059] where 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, where the C1-C6 alkyl group is linear, cyclic, or branched, substituted or unsubstituted; and

[0060] when the linker does not negatively affect either the film-forming properties or the oil solubility properties of the compound. Preferably, the linker is an alkyl (-C-), an ester or an ether (-O-), an amide or an 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 trialkylsi-loxysilylcarbamoyl pullulan, a particularly preferred compound being trimethylsi-loxysilylcarbamoyl 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, 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 relative to the weight of the composition, including all the intermediate ranges and sub-ranges such as, for example, 4% to 14%, 1% to 15%, 5% to 25%, etc.

[0064] According to preferred embodiments, at least one aqueous-phase film-forming agent and 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 preferably about 1:1.

[0065] Aqueous phase

[0066] According to preferred embodiments of the present invention, compositions comprising an aqueous solvent system including (i) water in an amount of at least about 5% by weight relative to the total weight of the composition; and (ii) optionally, at least one C2-C5 monoalcohol are proposed. Preferably, the composition is in the form of an emulsion with a continuous external phase that 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 more than 20% by weight, preferably more than 25% by weight, and preferably more than 30% by weight, preferably in amounts from about 10% to about 80%, preferably more than 20% to about 75%, preferably from about 25% to about 60%, and preferably from about 30% to about 50%, by weight, relative to the total weight of the composition, including all intermediate ranges and sub-ranges, such as, for example, from about 30% to about 60%.

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

[0069] Preferably, the C2-C5 monoalcohol(s), if any, 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 solvent system of the compositions of the present invention consists essentially of, or consists of, water and, optionally, C2-C5 monoalcohols. Preferably, the aqueous solvent system is "free of", "devoid of", or "substantially free of" solvents other than water and, optionally, C2-C5 monoalcohols.

[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 relative to 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] According to certain embodiments, the oil carrier comprises one or more volatile silicone oils. Examples of these volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6 cSt and having from 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that can be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that can 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 KF-96 A from Shin Etsu PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) from Dow Corning PDMS DC 200 (2 cSt) from Dow Corning 87 2

[0077] Furthermore, a volatile linear silicone oil may be used in the present invention. Suitable volatile linear silicone oils include those described in US patent no. 6,338,839 and WO03 / 042221. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

[0078] According to other embodiments, the oil vector 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 8 to 16 carbon atoms and mixtures thereof, and in particular, C8-Ci6 branched alkanes such as C8-Ci6 isoalkanes (also known as isoparaffins), isododecane, isodecane, and, for example, oils marketed under the Isopar or Permethyl brand names. 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 n-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 presented in US 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 may be used in the present invention include, but are not limited to, polar oils such as:

[0083] 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 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 oil, pumpkin oil, sesame seed oil, cucurbit oil, avocado oil, hazelnut oil, grapeseed oil, blackcurrant seed oil, evening primrose oil, millet oil, rye oil, quinoa oil, olive oil, barley oil, safflower oil, candlenut oil, passionflower 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, alkyl benzoate in Ci2 to Ci5, 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 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] In addition, examples of non-volatile oils that can 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, in particular Vaseline (petrolatum), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene and mixtures thereof.

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

[0090] According to preferred embodiments, the compositions of the present invention are devoid of, free from, or substantially free from waxes.

[0091] Low HLB surfactants

[0092] According to preferred embodiments of the present invention, compositions comprising at least one surfactant with a low HLB are proposed. "HLB" refers to the "hydrophilic-lipophilic balance" associated with emulsifiers / surfactants. In particular, the "HLB" value relates to the ratio between hydrophilic and lipophilic groups in the emulsifiers, and also relates to the solubility of the emulsifiers. Emulsifiers with a lower HLB are typically more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (W / O) emulsions. Emulsifiers with a 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 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 less than or equal to 6, preferably less than 5, and 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. "Backbone" means that the surfactant comprises a main chain. "Pendant group(s)" means that one or more groups are attached to the backbone or main 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 main chain, for example, 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 main chain.

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

[0097] Another preferred skeleton is a hydrocarbon-based hydrophilic skeleton such as a polyethylene glycol (PEG) polymer or a polyglyceryl polymer, and a preferred pendant group for such a skeleton is a hydrophobic group such as, for example, one or more C8-C24 fatty compounds, preferably one or more C12-C20 fatty compounds, and preferably one or more C16-C18 fatty compounds 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 (for example, PEG-10 dimethicone or PEG-9 lauryl polydimethylsiloxyethyl dimethicone), or a non-silicone surfactant, free of dimethicone (for example, PEG-30 dihydroxystearate). The low HLB surfactant of the present invention may have alkoxylation (for example, ethoxylation or propoxylation) through groups such as, for example, the (C2H4O)- / polyethylene glycol (PEG) groups, (C3H6O)- / polypropylene glycol (PPG) groups, etc. Suitable emulsifiers include alkoxylated compounds, partial glycerides of alkoxylated compounds, polyglycerol compounds, and mixtures thereof, etc. Polyglycerol compounds are preferred.

[0099] Suitable polyglycerol compounds include, but are not limited to, compounds preferably containing 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] The following are particularly preferred low HLB surfactants:

[0101] [Tables3] HLB Surfactants: Polyglyceryl-4-5-Isostearate, Polyglyceryl-4-5-Isostearate, Polyglyceryl-2-5-Isostearate, Glycol 5-6-Isostearate, Glyceryl 5.8-Isostearate, PEG-30 5.5-Isostearate, PEG-10 4.5-Isostearate, Lauryl Polydimethylsiloxyethyl DL-Methicone, PEG-9 3-Isostearate, PEG-9 Polydimethylsiloxyethyl DL-Methicone 4-Isostearate, PEG-6 5-Isostearate

[0102] 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 / Colorant / Active agent

[0104] Thickening agent

[0105] According to preferred embodiments of the present invention, compositions further comprising at least one thickening agent are proposed. Suitable thickening agents include agents for thickening an oily 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 "carbomers" as well as amphiphilic polymers. Preferably, the gelling agent is an am- polymer Philophile or a clay, or one of their combinations.

[0107] According to preferred embodiments, the gelling agent(s) may be at least one clay. Among the clays, examples may include clays of the smectite family, such as laponite, of the kaolinite family, such as kaolinite, dickite or nacrite, optionally modified clays of the halloysite, dombassite, antigorite, berthierine, pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, saponite, chlorite, sepiolite and illite families.

[0108] Clays are products already well known in themselves, which are described, for example, in the publication "Mineralogy of clays", S. Caillère, S. Hénin, M. Rautureau, 2nd edition 1982, Masson, the teaching of which is included here as a 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 that are cosmetically compatible and acceptable with keratinous materials are used. Clays that may be mentioned include kaolinite, montmorillonite, saponite, laponite, hectorite, and illite. Mixtures of clays and natural clays may also be used.

[0113] Natural clays that may be cited include green clays, particularly those rich in illite; clays rich in montmorillonite, known as Fuller's earth; or clays such as bentonite; or white clays rich in kaolinite. Bentonites, or modified bentonites, include in particular 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 an example of a clay rich in montmorillonite, one can cite the aluminium silicate hydrate sold under the name Gel White H® by the Rockwood company.

[0115] As an example of saponite, which belongs to the montmorillonite family, synthetic saponite can be cited, in particular the product sold by the Kunimine company under the name Sumecton®.

[0116] As examples of talc, one 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® of US Corporation and Micro ACE-P-3® sold by the company Nippon Talc.

[0117] Preferably, where appropriate, the thickening agent or agents 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 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 proposed. 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, particularly 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 include mineral salt chelating agents: EDTA; N-acyl-N.N' acid.N'-Ethyloxyl-Diamin-Triacetic Acid; amino-sulfonic 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 mattifying agent, which may include, but is not limited to, mattifying 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, including but not limited to 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, clotrimazole, butoconazole, oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox, ciclopirox olamine, undecylenic acid and its salts, benzoyl peroxide, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, N-acetyl-L-cysteine, acid 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 patent 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 for decreasing tyrosinase expression.Other examples include ceramides, vitamin C and its derivatives, particularly vitamins CG, CP, and 3-ethyl vitamin C, alpha- and beta-arbutin, ferulic acid, kojic acid, resorcinol and their derivatives, calcium sulfonate, D-pantheine, lipoic acid, ellagic acid, vitamin B3, phenylethyl resorcinol (e.g., Symwhite 377® from Symrise), kiwi juice (Actinidia chinensis) sold by Gattefosse, Paeonia suffructicosa root extract (e.g., Botanpi Liquid B® sold by Ichimaru Pharcos), brown sugar extract (Saccharum officinarum) (e.g., Molasses Liquid sold by Taiyo Kagaku), and a mixture of undecylenic acid and decylenoyl phenylalanine (e.g., Sepiwhite). Seppic's MSH®; . an amino acid such as arginine, histidine, methionine, lysine, proline, leucine, lycine, sarcosine, etc.; a vitamin such as a vitamin A compound like 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] diphenyl acrylate 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 concerned. 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, perfumes, fillers, antioxidants, neutralizing agents, silicone elastomers, and mixtures thereof may be added. A non-exhaustive list of these ingredients can be found in US Patent Application Publication No. 2004 / 0170586. Further examples of these additional ingredients can be found in the International Cosmetic Ingredient Dictionary and Handbook (9th ed. 2002).However, it must be understood that embodiments of the present invention include compositions that are "free", "substantially free" or "devoid" of the ingredients mentioned in this paragraph such as additional film-forming agents and waxes as previously mentioned, as well as fillers, in particular mattifying fillers (the compositions are "free of mattifying fillers", "substantially free of mattifying fillers", or "devoid of mattifying fillers").

[0123] A person skilled in the art shall ensure that the optional additional additives and / or their quantity are selected so that the advantageous properties of the composition according to the invention are not, or substantially not, compromised by the envisaged addition.

[0124] These substances can be selected in various ways by a person skilled in the art 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, it must contain a physiological support practically acceptable, non-toxic and must be able to be applied to human skin.

[0126] According to other preferred embodiments, methods for treating, caring for, and / or enhancing the appearance of the skin by applying compositions of the present invention to the skin in a sufficient quantity to treat, care for, and / or enhance the appearance of the skin are proposed. In accordance with these preceding preferred embodiments, the compositions of the present invention are applied topically to the desired area of ​​the skin in a sufficient quantity to treat, care for, and / or enhance the appearance of the skin. The compositions can be applied to the desired area as needed, preferably once or twice a day, more preferably once a day, and then preferably allowed to dry before being subjected to contact such as with clothing or other objects (for example, a top coat).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 on 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 preparing a water-in-oil (w / o) emulsion composition comprising combining (adding) at least one hydrophobically modified pullulan compound and at least one aqueous-phase film-forming agent during the preparation of the emulsion composition are proposed. Preferably, the composition is a skin composition. Preferably, the at least one hydrophobically modified pullulan compound and at least one aqueous-phase film-forming agent are combined or added in the quantities and / or ratios mentioned 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 mentioned above, in particular a foundation, comprising at least one hydrophobically modified pullulan compound and at least one aqueous-phase film-forming agent and (B) at least one other composition such as a primer composition, a base coat composition, or a top coat composition is offered. 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 contained in different containers within the kit.

[0130] Unless otherwise stated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the description and claims shall be understood as modified in all cases by the term "approximately". Consequently, unless otherwise stated, the numerical parameters presented in the following descriptive document and the attached claims are approximations that may vary depending on the desired properties that one seeks to obtain by the present invention.

[0131] Although the numerical ranges and parameters illustrating the broad scope of the invention are approximations, the numerical values ​​presented in the specific examples are reported as accurately as possible. However, every numerical value inherently contains certain errors necessarily resulting from the standard deviation found in its 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 W / O emulsion foundation formulation Total % 100.00 - General Total 100% - Preferred Chemical Name / Function % by Weight % by Weight Surfactants 1 to 10% 1 to 5% Aqueous Film Forming Agent 0.5 to 10% 1 to 5% Hydrophobically Modified Pullulan 0.5 to 10% 1 to 5% Oils 5 to 50% 20 to 40% Colorants 1 to 30% 5 to 20% Water QS QS Monoalcohol 1 to 20% 3 to 10% Polyol 1 to 10% 2 to 8% Active Agent (Vitamin) 1 to 20% 5 to 20% Clays 0.1 to 10% 0.1 to 5% Fillers 0.5 to 10% 1 to 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 degrees of shine at 60° for film-forming foundations in oil phase and in oil phase + combined aqueous phase.

[0137] 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 aqueous-phase active film-forming agent (Luviset, VP / VA, PVP). A 6 mil necking bar was used to create a film of each composition A, B, D, E, F, G, and H on an opacity card. The films were then oven-dried at 32°C and measured using a BYK Trigloss glossmeter on the black side of the card. It was observed that formulations containing both oil-phase (TSPL) and aqueous-phase film-forming agents exhibited lower degrees of gloss compared to the oil-phase film-forming agent alone (composition A) when measured at 60°C, 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 degrees of shine at elK 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 necking 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 glossmeter on the black side of the card. It was observed that formulations containing both oil-phase (TSPL) and aqueous-phase film formers exhibited lower degrees of gloss 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 - Degree of shine 60° of foundations with increasing concentration of film-forming agent in aqueous phase.

[0143] The Simplex A, B, C, and D foundation formulations were created with a constant concentration of pullulan compound (TSPL) in isododecane in combination with 0%, 0.87%, 1.74%, or 2.61% of the active polymer content of the film-forming agent Luviset AT Clear 3. A 6 mil necking 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 glossmeter on the black side of the card. It has been observed that formulations containing both oil-based (TSPL) and aqueous-based (Luviset) film formers exhibit reduced degrees of gloss compared to the oil-based film former alone (when measured at 60°).Furthermore, it has been observed that increasing the concentration of the film-forming agent 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 gloss at 85° of foundations with increasing concentration of aqueous phase film-forming agent.

[0146] Example 5 was repeated, with a measurement at 85°. It was observed that formulations containing both oil-based (TSPL) and aqueous (Luviset) film-forming agents exhibited reduced degrees of gloss compared to the oil-based film-forming agent alone. Furthermore, it was observed that increasing the concentration of the aqueous film-forming agent decreased the degree of gloss 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 pL of foundation compositions A and J were applied to a square of A 2.5 cm x 2.5 cm patch was applied to a bare forearm and dried for 45 minutes. The foundations were then wiped five times in alternating directions with a Crock ISO 105 F09 pad, each time with consistent pressure. The foundation containing both TSPL and Luviset (composition J) proved 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 pL of Compositions K and L were applied to a imitation leather substrate Protein white was applied to a 3.2 cm x 3.2 cm square using a nitrile-gloved finger. The 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 the substrate + foundation. A Crock ISO 105 F09 square was soaked in artificial sebum, and any excess sebum was blotted with a lint-free paper towel. The samples were then rubbed twice in alternating directions with constant force. The samples were then allowed to dry for at

[0155]

[0156]

[0157]

[0158] minus 6 hours, the readings were taken 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: AL normalized = x 10 0 Or : • ABS = absolute value • Lfinal = final L value in the LAB color space of the repository • Initial value L = 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 the aqueous phase... exhibited a significantly smaller change in L value compared to the foundation containing only TSPL, indicating resistance to rubbing in the presence of sebum, as reflected in Table II below: [Tables II] NOTE Composition AL standardized average Standard deviation AL standardized TSPL only Composition J 12.91 1.51 TSPL + Luviset Composition K 0.80 0.69

Claims

Demands

1. 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-forming agent.

2. Composition according to 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. 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. Composition according to any one of the preceding claims, wherein at least one hydrophobically modified pullulan compound is a siloxane-modified pullulan compound, preferably trimethylsiloxysilylcarbamoyl pullulan.

5. Composition according to any one of the preceding claims, wherein at least one aqueous-phase film-forming agent is at least one cyclic amide-containing polymer, preferably a copolymer of N-vinylpyrrolidone, methacrylamide and N-vinylimidazole, a copolymer of polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate, or a mixture thereof.

6. Composition according to any one of the preceding claims, wherein the weight ratio between the aqueous phase film-forming compound and the hydrophobically modified pullulan compound is from about 3:1 to about 1:3, preferably about 1:

1.

7. Composition according to any one of the preceding claims, wherein 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 skin makeup method comprising applying the composition of any of the preceding claims to the skin in sufficient quantity to make up the skin.

9. Composition according to claim 1, comprising (a) water, (b) in less a 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.