COMPOSITIONS INCLUDING AN ORGANOSILICONE POLYMER AND A FILM-FORMING AGENT IN THE AQUEOUS PHASE

Abstract

COMPOSITIONS INCLUDING AN ORGANOSILICONE POLYMER AND AN AQUEOUS-PHASE FILM-FORMING AGENT. The invention relates to compositions including (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and (d) at least one aqueous-phase film-forming agent, such as a copolymer including a vinyl pyrrolidone monomer. Skin-makeup processes are also proposed. Figure for abstract: none

Description

Title of the invention: COMPOSITIONS INCLUDING AN ORGANOSILICONE POLYMER AND A FILM FORMER IN AQUEOUS PHASE FIELD OF THE INVENTION

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

[0002] Currently, on the market for the care and makeup of keratinous materials, many products claim persistence throughout the day, resistance to external factors such as water, sebum, mechanical friction, etc. (water-resistant mascara, meal-resistant lipsticks, long-lasting foundations). Long-lasting products for lips, eyelashes, eyebrows or the face, which can be used at home, are mainly based on synthetic coating polymers in the presence of solvent.

[0003] One particular application, the "setting" of makeup, is traditionally accomplished by spraying a composition including a water-soluble polymer over makeup that has been previously applied, for example, to the face. However, traditional makeup setting agents often do not significantly improve the wear of the underlying makeup and its resistance to external forces such as mechanical friction, water, sweat and perspiration, sebum and / or oil. The present inventors recognized the need for improved materials and compositions in this regard. Summary of the invention

[0004] The present invention relates to oil-in-water emulsion compositions including (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerolated silicone resin, and combinations thereof; and (d) at least one aqueous-phase film former, such as a copolymer including a vinyl pyrrolidone monomer.

[0005] In some embodiments, the compositions include a copolymer of N-vinyl pyrrolidone, methacrylamide, and N-vinylimidazole. In some other embodiments, the compositions are in the form of a gel. In some other embodiments, the compositions further include (e) at least one compound selected from the group consisting of at least one gelling agent, at least one colorant, at least one active agent, and mixtures thereof. In some other embodiments, at least two of gelling agent, colorant, and active agent are present in the composition. In some other embodiments, the at least one organosilicone polymer is or includes a silicone acrylate copolymer. In some other embodiments, the at least one organosilicone polymer is or includes a glycerolated silicone resin.In certain other embodiments, the (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and the (d) at least one copolymer comprising a vinyl pyrrolidone monomer are present in a weight ratio, (c):(d) which is from about 0.5:1 to about 3:1. In certain other embodiments, the composition is free of colorant. In certain other embodiments, the compositions include one, more than one, or even all of the limitations described in this paragraph.

[0006] According to another aspect of the invention, a method of making up the skin includes applying to the skin on which a make-up film is formed, a composition comprising (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and (d) at least one aqueous-phase film-former (such as any of the compositions described above). The present invention also relates to methods of fixing a color cosmetic composition (for example, a composition containing a colorant such as a foundation) by applying any of the compositions described above to a color cosmetic composition previously applied to a keratinous material in an amount sufficient to obtain fixing of the color cosmetic composition previously applied to a keratinous material.

[0007] It is to be understood that both the foregoing general description and the following detailed description are provided by way of example and explanation only, and do not limit the invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] Outside of the working examples, or unless otherwise indicated, all numbers expressing amounts (e.g., concentrations, ratios, etc.) of ingredients and / or reaction conditions should be understood to be modified in certain embodiments by the term "about," meaning to within 10% to 15% of the number indicated (e.g., "about 10%" means from 8.5% to 11.5%, especially from 9% to 11%, and about 2% means from 1.7% to 2.3%, especially from 1.8% to 2.2%).

[0010] Similarly, for ratios, the modifier "about" means to within 10% or 15% of the number. For example, about 4:1 means from 3.4:1 to 4.6:1, preferably from 3.6:1 to 4.4:1. As will be readily understood by those skilled in the art, when the first ingredient in a ratio is less than the second, then a ratio may be expressed "inversely." For example, if a second ingredient, B, is present in an amount or concentration 2.5 times greater than that of ingredient A, this may be identified as an A:B ratio of 1:2.5. "About 1:10" means from 1:8.5 to 1:11.5, preferably from 1:9 to 1:11. Unless otherwise indicated, all concentrations stated as percentages are concentrations by weight and also, unless otherwise indicated, relate to the entire cosmetic adhesive composition.

[0011] “A” or “an” as used herein means “at least one”.

[0012] “At least one” means one or more and thus includes components individuals as well as mixtures / combinations.

[0013] Numerical ranges include the bounds and are intended to include all combinations and subcombinations. For example, from about 5%, 10% or 15% to about 20%, 50% or 60% may refer to from about 5% to about 20%, from about 5% to about 50%, from about 5% to about 60%, from about 10% to about 20%, from about 10% to about 50%, from about 10% to about 60%, from about 15% to about 20%, from about 15% to about 50% or from about 15% to about 60%. As used herein, a ratio range is intended to include each specific ratio within the subranges and a combination of subranges between the given ranges.

[0014] “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.

[0015] “Wax” as used herein means a lipophilic fatty compound that is solid at 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.

[0016] “Surfactant” and “emulsifier” are used interchangeably throughout throughout this patent specification.

[0017] “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.

[0018] “Volatile,” as used herein, means having a flash point less than about 115° C.

[0019] “Non-volatile,” as used herein, means having a flash point greater than about 115°C.

[0020] “Polymer” as used herein means a compound that is made up of at least two monomers.

[0021] “Mat” in compositions as used herein refers to compositions having little or no light reflection. For example, matte compositions may have average gloss properties, measured at 60°, of less than or equal to 10, e.g., 9, preferably less than or equal to 8, 6, 5, 4, or 1, including all intermediate ranges and subranges such as 1 to 10, 1 to 5, 2 to 10, 3 to 8, less than 1, less than 3, less than 5, etc. Such measurements may be made by depositing films to be tested onto a substrate (e.g., a P121-10N black abrasion board or a BYK No. 2810 opacity card) using a pinch bar (e.g., 1 mil, 3 mil, or 6 mil thick) and an automatic pinching machine. The films can then be dried at room temperature and analyzed using a glossometer (BYK: micro-TRI-gloss) at a 60° angle.

[0022] “Exempt” or “substantially free” or “devoid of” as used herein means that although it is preferred that no amount of the specific component be present in the composition, it is possible for there to be very small amounts thereof in the compositions of the invention provided that such amounts do not materially affect at least one, preferably most, of the beneficial properties of the conditioning compositions of the invention. Thus, for example, "colorant-free" means that an effective amount (i.e., greater than trace amounts) of colorant is omitted from the composition, "substantially colorant-free" means that a colorant is present in amounts not greater than 0.1% by weight, and "colorant-free" means that a colorant is present in amounts not greater than 0.25% by weight, based on the total weight of the composition. The same nomenclature applies to all other identified ingredients throughout the application and in this paragraph, such as, for example, silicone oils (compositions of the invention that are “free of silicone oils,” “substantially free of silicone oils,” and “free of silicone oil” have meanings consistent with the discussion within this paragraph), even if not specifically discussed for each identified ingredient.Thus, for example, "free of phenylated silicone oil" means that an effective amount (i.e., a dullness-inhibiting effective amount) of phenylated silicone oil is omitted from the composition (i.e., about 0% by weight), "substantially free of phenylated silicone oil" means that the phenylated silicone oil is present in amounts no greater than 0.25% by weight, and "free of phenylated silicone oil" means that the phenylated silicone oil is present in amounts no greater than 0.5% by weight, based on the total weight of the composition.The same nomenclature applies to all other ingredients identified throughout the application and in this paragraph, such as, for example, (1) matting fillers (compositions of the invention that are “free of matting fillers,” “substantially free of matting fillers,” and “lacking matting fillers”) and (2) additional film formers other than the hydrophobically modified polysaccharide compound and the aqueous-phase film former (compositions of the invention that are “free of additional film formers,” “substantially free of additional film formers,” and “lacking additional film formers”) have meanings consistent with the discussion in this paragraph, even if not specifically discussed for each identified ingredient. The discussed examples of the use of such language such as those in this paragraph are intended to be provided by way of example, not limitation.

[0023] “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 an extended period of time. The “makeup result” may be evaluated by evaluating long-lasting properties by any method known in the art for evaluating 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 evaluating the color of the composition after an extended period of time. For example, the color of a composition may be evaluated immediately after application to keratinous materials such as the lips and these characteristics may then be re-evaluated and compared after a period of time. In addition, these characteristics may be evaluated relative to other compositions, such as commercially available compositions.

[0024] “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.

[0025] “Physiologically acceptable” means compatible with keratinous material and having a pleasant color, odor, and feel, and which does not cause unacceptable discomfort (tingling or tightness) that would discourage a consumer from using the composition. The compositions of the present invention may be in the form of a gel composition.

[0026] “Gel composition” means a composition that does not flow like a liquid when applied to a substrate, a composition that has a three-dimensional network that prevents the composition from spreading on, or flowing from, a substrate after application due to gravity over a short period of time (e.g., in less than 10 seconds). G' (storage modulus) is greater than G” (loss modulus) in all strain ranges up to 300% strain. Preferably, G' (storage modulus) is greater than G” (loss modulus) at low strain, but with G' decreasing and G” increasing, and the gel has the crossover point at >0.1% strain, preferably >1% strain, and preferably less than 200% strain, preferably less than 150% strain.

[0027] The term "gel crossover point" (Sol / Gel point) means the point at which G" (loss modulus) intersects G' (storage modulus), reported as % strain. This is the point at which a composition changes from a fairly solid state to a fairly liquid state. An example of a method for determining gel crossover point is as follows: G” (loss modulus) and G' (storage modulus) using a TA Instruments Discovery HR-3 rheometer, having a 40 mm parallel plate geometry on a flat stainless steel peltier plate. The test may be conducted at 25°C with a test parameter of angular frequency of 1.0 rad / s and a logarithmic sweep: % strain from 0.01 to 1000.0%. 5 points per decade. Results reported as % strain.

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

[0029] “Naturally occurring compound” refers to 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” refers to any compound that is not a natural compound 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 a C2-C5 monohydric alcohol, and / or the film-forming system of the composition may consist essentially of the hydrophobically modified polysaccharide compound and the aqueous phase film-forming agent; likewise, the oil-phase film-forming system may consist essentially of the hydrophobically modified polysaccharide compound.

[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 transfer resistance.

[0035] Reference is made herein to trade names of materials including, but not limited to, polymers and optional components. The inventors do not intend herein 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, unless otherwise indicated, calculated by weight. All percentages are, unless otherwise indicated, calculated based on the total weight of a composition. All levels of component or composition refer to the active level of that component or composition, and are exclusive of impurities, e.g., residual solvents or by-products, which may be present in commercially available sources.

[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 "non-ionic water-soluble or water-dispersible" 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-forming agent.

[0040] Examples of aqueous film-forming polymer include, but are not limited to, homopolymers and copolymers containing at least one (meth)acrylic acid (meth)acrylate monomer and / or at least one vinyl monomer (e.g., vinylpyrrolidone) such as polyvinylpyrrolidone, polyvinyl alcohol, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / acrylic acid copolymers, vinylpyrrolidone / acrylate copolymers, alkyl (e.g., butyl) acrylate / hydroxyalkyl (e.g., propyl) dimethicone copolymers, hydroxyalkyl (e.g., propyl) dimethicone acrylate copolymers, styrene / acrylates / ammonium methacrylate copolymers, acrylamide / acryloyldimethyltaurate copolymers, and the like. sodium, etc.; water-soluble polysaccharides such as pectin, unmodified pullulan or cellulose compounds; polyurethanes; latex; and mixtures thereof.In some embodiments, the waterborne film-forming polymer is selected from a group consisting of polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / acrylic acid copolymer, polyvinyl alcohol, N-vinylpyrrolidone copolymer, methacrylamide, and N-vinylimidazole. In some other embodiments, the waterborne film-forming polymer is a copolymer comprising a vinyl pyrrolidone monomer (and one or more second monomers). The one or more second monomers may include, for example, cyclic amides, cyclic amines, (meth)acrylate, (meth)acrylamide, or other monomers other than vinylpyrrolidone.

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

[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 (a γ-lactam), in particular 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) and vinylpyrrolidone copolymers containing at least one monomer other than vinylpyrrolidone such as, for example, substituted or unsubstituted C2 (acrylic acid) or C3 (allyl) groups, optionally in the form of esters (acrylates or methacrylates) or ethers.

[0047] In some embodiments, the at least one aqueous-phase film-forming polymer has a weight average molecular weight in a range of about 10,000 daltons to about 1,000,000 daltons, including all intermediate ranges and sub-ranges such as, for example, 50,000 daltons to 500,000 daltons, 75,000 daltons to 300,000 daltons, and 100,000 daltons to 250,000 daltons.

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

[0052] According to the present invention, compositions including at least one silicone acrylate copolymer are provided. Silicone acrylate copolymers are polymers containing siloxane group(s) and hydrocarbon group(s). For example, suitable polymers include polymers comprising a hydrocarbon backbone such as, for example, a backbone selected from vinyl polymers, methacrylic polymers and / or acrylic polymers and at least one chain selected from pendant siloxane groups, and polymers comprising a backbone of siloxane groups and at least one pendant hydrocarbon chain such as, for example, pendant vinyl, methacrylic and / or acrylic group(s).Suitable silicone acrylate copolymers may comprise at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% silicone (siloxane groups) by weight, and may comprise at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% acrylate (hydrocarbon groups) by weight.

[0053] The at least one silicone acrylate copolymer may be chosen from silicone / (meth)acrylate copolymers, such as those described in US patents 5,061,481, 5,219,560 and 5,262,087, and patent application US 2012 / 0301415.

[0054] The at least one silicone acrylate copolymer may be chosen from polymers derived from non-polar silicone copolymers comprising repeating units of at least one polar (meth)acrylate unit and vinyl copolymers grafted with at least one non-polar silicone chain.Non-limiting examples of non-dendrimer copolymers are acrylates / dimethicone copolymers such as those commercially available from Shin-Etsu, e.g., products sold under the trade names KP-545 (cyclopentasiloxane (and) acrylates / dimethicone copolymer), KP-543 (butyl acetate (and) acrylates / dimethicone copolymer), KP-549 (methyl trimethicone (and) acrylates / dimethicone copolymer), KP-550 (isododecane (and) acrylate / dimethicone copolymer, INCI name: isododecane (and) acrylate / dimethicone copolymer), KP-561 (acrylates / stearyl acrylate / dimethicone copolymer), KP-562 (acrylates / acrylate behenyl / dimethicone acrylates), and mixtures thereof. Additional examples include acrylate / dimethicone dendrimer copolymers sold by Dow Corning under the trade names FA 4001 CM SILICONE ACRYLATE (cyclopentasiloxane (and) acrylates / trimethyl polysiloxymethacrylate copolymer). and FA 4002 ID SILICONE ACRYLATE (isodecane (and) acrylates / trimethyl polysiloxymethacrylate copolymer), and mixtures thereof.

[0055] Other non-limiting examples of these polymers and their synthesis are disclosed, for example, in U.S. Patents 4,972,037, 5,061,481, 5,209,924, 5,849,275 and 6,033,650, and PCT applications WO 93 / 23446, WO 95 / 06078 and WO 01 / 32737. These polymers may be sourced from various companies. One such company is Minnesota Mining and Manufacturing Company which offers these types of polymers under the trade names "Silicone Plus" polymers (e.g., poly(isobutyl methacrylate-co-methyl FOSEA)-g-poly(dimethylsiloxane), sold under the trade name SA 70-5 IBMMF).

[0056] Other non-limiting examples of useful silicone acrylate copolymers include silicone / acrylate graft terpolymers, e.g., the copolymers described in PCT application WO 01 / 32727.

[0057] Other useful polymers may include those described in U.S. Patent No. 5,468,477. A non-limiting example of such polymers is poly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which is commercially available from 3M under the trade name VS 70 IBM.

[0058] The silicone acrylate copolymer, if included, is preferably present in the compositions of the present invention in an active amount ranging from about 1% to about 25% such as 1%, 1.2%, 1.4% or 1.5%, 1.6%, 1.8% or 2% to about 2%, 4%, 5%, 10%, 15%, 20% or 25%, all weights being based on the weight of the composition as a whole. GLYCEROLATED SILICONE RESIN

[0059] In accordance with the present invention, compositions comprising at least one glycerolated silicone resin are provided.

[0060] Preferably, the compositions of the present invention comprise a film-forming component comprising at least one glycerolated silicone resin, at least two glycerolated silicone resins, at least three glycerolated silicone resins, at least four glycerolated silicone resins, etc. Accordingly, the film-forming components of the present invention may contain, for example, any number of glycerolated silicone resins such as from 1 to 10 of these resins, 1 to 5 of these resins, 1 to 3 of these resins, etc.

[0061] The expression "glycerolated silicone resin" means a resin which comprises, in its chemical structure, one or more monoglycerol or polyglycerol groups.

[0062] According to preferred embodiments of the invention, the glycerolated silicone resin(s) is (are) preferably present in a content as active material ranging from 0.1% to 40% by weight, relative to the total weight of the composition, preferably ranging from 1% to 30% by weight and more preferably from 5% to 15%. by weight, relative to the total weight of the composition, including all intermediate ranges and sub-ranges such as 1% to 5%, 5% to 25%, 12.5% ​​to 30%, 2% to 12.5%, etc.

[0063] The glycerolated silicone resin(s) according to the invention is (are) preferably chosen from those of formula (1) below: (R^SiOv2)a(R2(CH3)2SiOv2MH3sSÎO^)£(R'2SiO2 / 2^ (1)

[0064] in which

[0065] - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof;

[0066] - each R2 is a mono- or polyglycerol group of the following general formula (2): HCHz)2“ CsHsî—O—(CH2CH(OH)CH2O)iR~ (2)

[0067] in which

[0068] - R4 is a substituted or unsubstituted monovalent hydrocarbon group or an atom of hydrogen, and

[0069] - the indices 1 and i are numbers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5,

[0070] - each R3 is an identical or different group of general formula (3), of formula general (4), general formula (5) or general formula (6) below [Chem 3] -4CHz>-CmH2n^^ (3) [Chem 4] —(CHî);;—CmHgm—SiRki—(4) [Chem 5] —(CHsl^mHsnr-SiR-kîHOSi^^ (5) [Chem 6] —(CH-2)2—CmHan—StR'kl (OSlR !«(OSiR',k3(OSiR'!3)3-k3b-*2)3-kl (6)

[0071] Where

[0072] - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof;

[0073] - the indices m, j and ki to k3 are numbers which satisfy the conditions m < 5, 0 sj < 500, 0s kl s 2, 0 s ks s 2and0 s k3 s 2;

[0074] - the indices a, b, c, d, e and f are numbers which satisfy the conditions 0 < a < 400.0 < b < 200.0 <c < 400, 0 < d < 320, 0 <e < 320, 0 < f < 1000 et 0,5 < (a + b + c) / f < 1,5.

[0075] The glycerolated silicone resins according to the invention are described in patent application US20200332065A1 from SHIN-ETSU.

[0076] According to a specific embodiment, the glycerolated silicone resin(s) of formula (1) as defined above is (are) chosen from those for which

[0077] - the indices b and c satisfy the conditions 0 < b < 30 and 0 < c < 30;

[0078] - the index i of the general formula (2) of the monoglycerol or polyglycerol group R2 is a number that satisfies the condition 0 < i < 3.

[0079] According to a specific embodiment, the glycerolated silicone resin(s) of formula (1) is (are) in solid form at 25°C when the index c satisfies the condition 0 < c < 400 and R3 is a group of general formula (3) where the index j satisfies the condition 0 < j < 10.

[0080] According to a specific embodiment, the glycerolated silicone resin(s) has(have) a weight average molecular weight ranging from 1000 to 100,000.

[0081] The glycerolated silicone resin(s) according to the invention is / are amphiphilic, that is to say that it / they have two parts of different polarities. In general, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (hydrophilic-lipophilic balance), the HLB being the ratio between the hydrophilic part and the lipophilic part of the molecule. This term HLB is well known to those skilled in the art and is described, for example, in "The HLB System. A Time-Saving Guide to Emulsifier Selection" published by ICI Americas Inc., 1984). The HLB value of the glycerolated silicone resins according to the invention preferably varies from 0.1 to 15 according to the Griffin method.

[0082] The glycerolated silicone resin(s) according to the invention may be obtained by a preparation process comprising the hydrosilylation step

[0083] A) of a silicone resin containing a hydrosilyl group of formula (7) below (RSSIO«)aHnRS.nSiO^)b*c(R^SiO^W^^ (7)

[0084] in which:

[0085] - each R1, identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof;

[0086] - the indices a, b, c, d, e and f are numbers which satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0 < d < 320, 0 < e < 320, 0 < f < 1000 and 0.5 < (a + b + c) / f < 1.5;

[0087] - n is a number that satisfies the condition 1 < n < 3, with

[0088] B) of one or more compounds chosen from the compounds terminated by an alkenyl group of general formulas (8), (9), (10), (11) and (12) below CHs^H-QHa-O-CCHsCHp^ (8) [Chem S] CH^HC^HsnASiORL^ (9) [Chem 10] CHs^sCH—CmHa-n—Si R '50—(OSiR '3)w (10) [Chem 11] CH^CH—CmHam—SîR\i—(OSIR^OSiR'SJa-ksX^d (11) [Chem 12] CH^H'-CrsH^SiRVMOSi^MOSiRM^ (12)

[0089] Where

[0090] - R4 is a substituted or unsubstituted monovalent hydrocarbon group or an atom of hydrogen,

[0091] - the indices 1 and i are numbers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5 ;

[0092] - the indices m, j and ki to k3 are numbers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 <ki<2, 0<k2<2et0<k3<2; ladite résine de silicone contenant un groupe hydrosilyle de formule (7) qui réagit avec au moins un composé dans la formule (8).

[0093] The hydrosilylation reaction is carried out in the presence of, for example, a platinum or rhodium catalyst. The preferred ranges for b, c, d, e, f, R4,1, m, i, j and ki to k3 are as defined above.

[0094] Process for preparing glycerol silicone resin

[0095] A specific example of a process for preparing the glycerol silicone resin according to the invention is described below.

[0096] As mentioned above, the glycerolated silicone resin according to the invention can be obtained by the hydrosilylation step

[0097] (A) of a silicone resin containing a hydrosilyl group of average formula (7) below :

[0098] in which

[0099] - each R1 is an alkyl, aryl or aralkyl group identical or different from 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof;

[0100] - the indices a, b, c, d, e and f are numbers that satisfy the conditions 0 < a < 400, 0 < b < 200, 0 < c < 400, 0< d< 320, 0 # e < 320, 0 < f < 1000 and 0.5 < (a + b + c) / f < 1.5;

[0101] - n is a number that satisfies the condition 1 < n < 3, with

[0102] (B) of one or more compounds chosen from compounds terminated by a alkenyl group of general formulas (8), (9), (10), (11) and (12) below CH—CH-C.Hz-O-(CHïCH(OH}CHzO):R4 (8) CHz—CH-CmHsrnHSsOR^LSiRH (9) CH2=CH—CmH2n>—SiR^i—COSiR^Jwo (10) CH2^H^mH2m^iR\iHOSiRMOSiRSM (11) CH^HC^Hznr-SiR^—COSiRMOSiRMOSiRS)^^^ ​​(12)

[0103] Where

[0104] - R4 is a substituted or unsubstituted monovalent hydrocarbon group or an atom of hydrogen,

[0105] - the indices 1 and i are numbers that satisfy the conditions 0 < 1 < 15 and 0 < i < 5 ;

[0106] - the indices m, j and ki to k3 are numbers which satisfy the conditions 0 < m < 5, 0 < j < 500, 0 <ki<2, 0<k2<2et0<k3<2; lesdits comprennent un composé de formule générale (8).

[0107] The organosilicon resin containing hydrosilyl groups of average composition formula (7) and the compound having terminal alkenyl groups of general formula (8), (9), (10), (11) or (12) are mixed in a molar ratio, expressed as hydrosilyl groups / terminal unsaturated groups, which is preferably from 0.5 to 2.0 and more preferably from 0.8 to 1.2.

[0108] The addition reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid / vinylsiloxane complexes. When an excessive amount of catalyst is included, discoloration of the sample occurs, and thus the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0109] In addition, if necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of organic solvents include cyclic organopolysiloxanes, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons, such as toluene and xylene; ketone solvents, such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbons, such as hexane, heptane, octane, and cyclohexane; and alcohols. aliphatics, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the point of view of reactivity, ethanol, 1-propanol and 2-propanol are preferred.

[0110] The amount of solvent used is preferably 1% to 80% and more preferably 5% to 50% of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0111] The conditions of the addition reaction are not particularly limited, although it is preferable to heat under reflux at a temperature between 50 and 150°C, particularly between 80 and 120°C, for approximately 1 to 10 hours.

[0112] After the addition reaction, the step of removing the rhodium or platinum catalyst used with the activated carbon can be included. The amount of activated carbon used is preferably 0.001% to 5.0% and particularly 0.01% to 1.0% of the overall system. The discoloration of the sample can be better suppressed by setting the amount of activated carbon within this range.

[0113] After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups can be included. Particularly in cases where use in applications such as cosmetic preparations is intended, there is a possibility that these hydrosilyl groups may become deactivated over time due to dehydrogenation reactions, which presents a problem from a safety point of view. It is therefore preferable to include a step of maintaining the hydrosilyl groups.

[0114] An example of a hydrosilyl group removal step is the process of hydrolyzing unreacted hydrosilyl groups by the addition of a basic catalyst, such as an alkali metal carbonate, an alkali metal bicarbonate, or an alkali metal hydroxide, and then neutralizing by the addition of an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include strong basic catalysts, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide; and weak basic catalysts, such as sodium carbonate, calcium carbonate, and sodium bicarbonate. From the point of view of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being particularly preferred. Acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. In general, instead of using the acid alone or the base alone, it is better to use them with water and heat them to a temperature no higher than the boiling point of water.

[0115] After the addition reaction, if necessary, the deodorization step to reduce the odor can be included. When use in applications such as cosmetic preparations in particular is considered, since the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of ordinary polyether-modified silicones can be explained as follows. When an addition reaction between an allyl-etherified polyether and a hydropolyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally in the form of side reactions, forming a propenyl-etherified polyether. This propenyl-etherified polyether has no reactivity with the polyorganosiloxane hydrogen and therefore remains in the system as an impurity.It is believed that when water acts on this propenyl etherified polyether, the propenyl ether hydrolyzes, giving rise to propionaldehyde, which has an unpleasant odor. It is known that the above hydrolysis reaction is also promoted in the presence of an acid catalyst. Therefore, when the polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the hydrolysis reaction described above and resulting in the appearance of an unpleasant odor.

[0116] Typical examples of the deodorization step include two approaches. The first is that, by adding an acid catalyst to the solution after the addition reaction, any propenyl ether remaining in the system is hydrolyzed and the propionaldehyde that forms is removed by strip purification (JP No. 2137062).

[0117] Specific examples of the acid catalyst used in the first approach include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. These acids are used in combination with water. In the case where it is necessary to remove the acid that has been used, it is preferable to use an acid having a low boiling point, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Likewise, from the point of view of treatment efficiency, it is preferable to use a strong acid, such as hydrochloric acid or trifluoroacetic acid.

[0118] The treatment temperature is preferably set at 80°C or lower in order to prevent oxidation of hydrophilic groups. The amount of acidic aqueous solution added is preferably set at 0.1% to 100%, relative to the organosilicon resin modified with organic groups. The use of 5% to 30% is more preferred.

[0119] From the productivity point of view, the process of adding an aqueous solution to the post-reaction solution so as to regulate the pH to 7 or less and performing strip purification after stirring under heating is preferred. Strip purification can be performed at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to effectively purify the strip under these temperature conditions, it is preferable to perform this operation under reduced pressure; when performed at normal pressure, the operation is preferably performed under a flow of inert gas, such as nitrogen or argon.

[0120] The second approach is that in which, by adding hydrogen to the solution after the addition reaction, the unsaturated double bonds are alkylated (subjected to a hydrogenation reaction) and the formation of propionaldehyde over time is stably controlled (US Patent No. 5,225,509; JP-A H07-330907).

[0121] Hydrogenation reactions include processes involving the use of hydrogen and processes involving the use of metal hydrides, and there are also homogeneous reactions and heterogeneous reactions. These processes can be used alone, but it is also possible to use them in combination. However, given the advantage of having no trace of catalyst used in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is preferable.

[0122] The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron and others, in uncombined form or in compound form. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support may, for example, be activated carbon, silica, silica / aluminum, aluminum or zeolite. These catalysts can be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. In addition, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

[0123] It is preferable to carry out the hydrogenation reaction at a pressure generally between 1 and 100 MPa and between 50 and 200 °C. The hydrogenation reaction can be carried out batchwise or continuously. When it is a non-continuous process, the reaction time depends, for example, on the amount of catalyst and the temperature, but is generally between 3 and 12 hours. The hydrogen pressure can be set at a suitable fixed pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing and can therefore be determined by carefully monitoring a pressure gauge.

[0124] The amount of aldehyde included in the glycerol silicone resin which has been purified by this acid treatment and this hydrogenation treatment can be set at 70 ppm or less, preferably at 20 ppm or less and more preferably at 10 ppm or less.

[0125] It is also possible to combine the two types of deodorization steps mentioned above. In the approach involving acid treatment, decomposition and removal of the aldehyde compound is possible, but, since there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehydes cannot be completely suppressed. In the approach involving a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound that is formed thereby. However, the aldehyde condensate formed with the condensation of a portion of the aldehyde remains in the system even after such treatment is carried out and removal by strip purification is also difficult.Therefore, by alkylation of the unsaturated double bonds remaining when the solution, following the addition reaction, is subjected to hydrogenation, and by subsequent decomposition of the aldehyde condensate in the system by addition of an acid catalyst, complete deodorization is possible (WO2002 / 05588).

[0126] The weight average molecular weight of the glycerol silicone resin of average formula (1) preferably ranges from 1000 to 100,000; from the viewpoint of performance qualities and ease of operations, such as filtration, the weight average molecular weight preferably ranges from 3000 to 50,000. Here and hereinafter, the weight average molecular weight can be determined as the weight average molecular weight of polystyrene equivalent in gel permeation chromatography (GPC).

[0127] The glycerol silicone resin according to the invention is in a form at 25°C which can be solid or liquid; from the point of view of film formability, it is preferably solid.

[0128] In particular, the glycerolated silicone resin according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 <b<30et0<c< 30, l’indice i dans la formule générale (2) est un nombre qui satisfait à condition 0 < i < 3 et j (3) < j < 10 sous forme solid at 25°C and preferably has a weight average molecular weight which preferably varies from 1000 to 100,000 and more preferably from 3000 to 50,000.

[0129] The glycerolated silicone resins according to the invention have a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, preferably from 0.1 to 15 and more preferably from 1.0 to 8.0.

[0130] According to a preferred form, the composition of the invention comprises at least one glycerolated silicone resin in formula (1) of the (3-glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type corresponding to the following formula (21): [(CHsJsSÎCMa [R(CH3)2SiOi / 2]b(SiO4 / 2)f (21)

[0131] Where

[0132] - R denotes the 3-glyceroxypropyl group of structure

[0133] - C3H6OCH2-CH(OH)CH2OH;

[0134] - the indices a, b and f are numbers which satisfy the conditions 0 < a < 400, 0 < b < 30, 0 < f < 1000 and 0.5 < (a + b) / f < 1.5.

[0135] According to a particularly preferred form, the glycerolated silicone resin of the (3-glyceroxypropyl) Dimethylsiloxyl Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

[0136] The term "volatile oil" is understood, within the meaning of the invention, to mean any oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, in particular having a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa and more particularly ranging from 2.66 Pa to 1300 Pa.

[0137] The volatile oil in accordance with the invention may be chosen from the group consisting of hydrocarbon oils, silicone oils, and mixtures thereof.

[0138] The expression “hydrocarbon oil” means an oil containing mainly carbon and hydrogen atoms and optionally one or more functions chosen from hydroxyl, ester, ether and carboxyl functions.

[0139] For the purposes of the present invention, the expression “silicone oil” designates an oil comprising at least one Si-O group and more particularly an organopolysiloxane.

[0140] The volatile hydrocarbon oils which can be used in the compositions according to the invention can be chosen from branched C8-C16 alkanes.

[0141] Mention may be made in particular of C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane or “IDD”), isodecane, isohexadecane and, by example, oils sold under the trade names Isopar® or Permethyl®. More preferably, isododecane will be used.

[0142] Mention may be made, as an example of a volatile silicone oil which can be used in the invention, of volatile silicone oils, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 centistokes (2.106 to 8.106 m2 / s) and containing in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. In particular, volatile silicone oils that can be used in the invention include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane; and mixtures thereof. More preferably, decamethylcyclopentasiloxane (D5) will be used.

[0143] According to a particularly preferred form, the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution comprising 49.5% by weight of active material in isododecane, such as the product manufactured under the trade name X-25-9138A® by SHIN ETSU with a weight average molecular weight of 11,000.

[0144] The glycerolated silicone resin, if included, is preferably present in the compositions of the present invention in an active amount ranging from about 1% to about 25% such as 1%, 1.2%, 1.4% or 1.5%, 1.6%, 1.8% or 2% to about 2%, 4%, 5%, 10%, 15%, 20% or 25%, all weights being on an active basis and being based on the weight of the composition as a whole.

[0145] For embodiments wherein both a silicone acrylate copolymer and a glycerolated silicone resin are included, the total amount of these materials, on an active basis, may also range from about 1% to about 25% such as 1%, 1.2%, 1.4% or 1.5%, 1.6%, 1.8% or 2% to about 2%, 4%, 5%, 10%, 15%, 20% or 25%, all weights being based on the weight of the composition as a whole.

[0146] Preferably, the weight ratio of the active ingredient (1) of the sum of the silicone acrylate copolymer and the glycerol silicone resin to (2) of the aqueous phase film former (e.g., copolymer of N-vinyl pyrrolidone, methacrylamide and N-vinylimidazole) is from about 0.5:1, 1:1 or 15:1 to about 1.75:1, 2:1, 3:1 or 5:1. Aqueous phase

[0147] According to preferred embodiments of the present invention, compositions comprising an aqueous phase solvent system comprising (i) water in an amount of at least about 10% by weight relative to the total weight of the composition; and (ii) optionally, at least one C2-C5 monohydric alcohol are provided. Preferably, the composition is in the form of an emulsion with a continuous external phase which is aqueous, preferably an oil-in-water (o / w) emulsion.

[0148] 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% water by weight, preferably more than about 25% water by weight, and preferably more than 30% water by weight, preferably in amounts ranging from about 30%, 40%, or 50% to about 50%, 60%, 70%, 80%, or 90%, all weights being based on the weight of the composition as a whole.

[0149] Suitable C2-C5 monohydric alcohols, where applicable, include ethanol, propanol, butanol, pentanol, isopropanol, isobutanol and isopentanol. Ethanol is particularly preferred.

[0150] Preferably, the C2-C5 monoalcohol(s), if any, is / are present in the compositions of the present invention in an amount ranging from about 1% to about 50%, preferably in amounts ranging from about 1%, 5%, or 10% or 15% to about 15%, 20%, 25%, 30%, or 50%, all weights being based on the weight of the composition as a whole.

[0151] 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. Oily phase

[0152] According to the present invention, compositions comprising at least one oil are provided. The compositions of the present invention preferably comprise an oil sufficient to form an oil-in-water emulsion, and preferably having one or more oils in an amount ranging from about 1%, 5%, or 10% or 5% to about 5%, 10%, 15%, 20%, 25%, 30% or 50%, all weights being based on the weight of the composition as a whole.

[0153] 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.

[0154] According to some 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 temperature ambient temperature of 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 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, the volatile silicone oils have a flash point of at least 40°C.

[0155] Non-limiting examples of volatile silicone oils are listed in Table 1 below.

[0156] [Tables 1] Compound Flash point (°C) Viscosity (cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5) - - Octamethylcyclotetrasiloxane 55 2.5 (cyclotetramethylsiloxane or D4) - - Dodecamethylcyclohexasiloxane (D6) 93 7 Decamethyltetrasiloxane (L4) 63 1.7 Shin Etsu KF-96 A 94 6 Dow Corning PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) 56 1.5

[0157] Furthermore, a volatile linear silicone oil may be employed in the present invention. Suitable volatile linear silicone oils include those described in U.S. Patent No. 6,338,839 and WO03 / 042221. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, the decamethyltetrasiloxane is further combined with another solvent more volatile than the decamethyltetrasiloxane.

[0158] According to certain 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 from 8 to 16 carbon atoms and mixtures thereof and in particular, alkanes branched C8-C16 such as C8-C16 isoalkanes (also known as isoparaffins), isododecane, isodecane, and for example, oils sold under the trade names Isopar or Permethyl. Preferably, the volatile non-silicone oils have a flash point of at least 40 °C.

[0159] Non-limiting examples of non-silicone volatile oils are given in Table 2 below.

[0160] [Tables2] Compound Flash point (°C) Isododecane 43 Propylene glycol N-butyl ether 60 Ethyl 3-ethoxypropionate 58 Propylene glycol methyl ether acetate 46 Isopar L (Cn-Cu isoparaffin) 62 Isopar H (Cn-Ci2 isoparaffin) 56 Undecane 62 Tridecane 94 Isohexadecane 96

[0161] The volatility of oils / solvents can be determined using the evaporation rate presented in U.S. Patent No. 6,338,839.

[0162] 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:

[0163] - 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, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil or rosehip oil;or caprylic / capric acid triglycerides, for example those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

[0164] - 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 polyalcohols; hydroxylated esters, for example, isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

[0165] - synthetic ethers containing from 10 to 40 carbon atoms;

[0166] - C8 to C26 fatty alcohols, for example oleyl alcohol, cetyl alcohol, stearyl alcohol and cetearyl alcohol; and

[0167] - their mixtures.

[0168] Further, examples of non-volatile oils that may be used in the present invention include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons and hydrocarbon waxes including polyolefins, particularly petrolatum (vaseline), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

[0169] According to preferred embodiments, the compositions of the present invention are free, free of, or substantially free of silicone oils.

[0170] According to preferred embodiments, the compositions of the present invention are free, free of, or substantially free of non-volatile oils.

[0171] According to preferred embodiments, the compositions of the present invention are free, free or substantially free of waxes. High HLB surfactant

[0172] According to certain embodiments of the present invention, the compositions may include at least one high HLB surfactant. "HLB" refers to the "hydrophilic-lipophilic balance" associated with the emulsifiers / surfactants. In particular, the "HLB" value relates to the ratio of hydrophilic groups to lipophilic groups in the emulsifiers, and also relates to the solubility of the emulsifiers. Emulsifiers with lower HLB are more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (W / O) emulsifiers. Emulsifiers with higher HLB are more soluble in water (hydrophilic material) and are more suitable for oil-in-water (O / W) emulsions. In the context of the present invention, a "high HLB surfactant" means a surfactant having an HLB value greater than 8. Also, in the context of the present invention, a " “high HLB value” means a surfactant having an HLB value greater than or equal to 8, preferably greater than or equal to 9, preferably greater than or equal to 10, preferably greater than or equal to 12, and preferably greater than or equal to 13.

[0173] Examples of surfactants include, but are not limited to, the following:

[0174] - polyethylene glycol (PEG) and / or glycerolated esters or ethers, such as branched or linear C8-C24 polyethylene glycol and / or glycerolated compounds, for example, Oleth-50, Oleth-20, Oleth-10, Ceteth-10, Steareth-20, Laureth-23, PEG-8 stearate, PEG-8 isostearate, PEG-20 stearate, PEG-40 stearate, etc.;

[0175] - sorbitan esters or ethers, such as mono- or polyalkyl esters or ethers of oxyethylenated or non-oxyethylenated sorbitan, such as polysorbate 21, polysorbate 40, polysorbate 80, polysorbate 60, polysorbate 61, sorbitan isostearate, glyceryl sorbitan isostearate, sorbitan sesquioleate, sorbitan laurate, sorbitan monopalmitate, sorbitan oleate, sorbitan trioleate, sorbitan monostearate and sorbitan tristearate, etc.;

[0176] - mono- or polyalkyl esters or sugar ethers, such as mono- or polyalkyl sugar esters or ethers as described in US patent 6,689,371. Examples include methyl glucose isostearate, sucrose distearate, sucrose stearate, etc.;

[0177] - alkoxylated alkenyl succinates; and

[0178] - silicone derivatives, such as dimethicone copolyols, for example the mixture of cyclomethicone and dimethicone copolyol sold under the name "DC 5225 C" by Dow Corning, and alkyl dimethicone copolyols, such as lauryl methicone copolyol, sold under the name "Dow Corning 5200 Formulation Aid" by Dow Corning, and cetyl dimethicone copolyol, sold under the name "Abil EM 90" by Goldschmidt, or the mixture of polyglyceryl-4 isostearate / cetyl dimethicone copolyol / hexyl laurate sold under the name "Abil WE 90" by Goldschmidt.

[0179] The at least one high HLB surfactant is preferably present in the compositions of the present invention in an amount of about 0.1% to about 5%, preferably about 0.1% to about 4%, and preferably about 0.1% to about 3% by weight based on the total weight of the composition, including all intermediate ranges and sub-ranges. Gelling agent / Coloring agent / Active agent

[0180] Gelling agent

[0181] According to preferred embodiments of the present invention, compositions further comprising at least one gelling agent are provided. Suitable gelling agents include any gelling agent, such as, for example, gums, clays and acrylic acid (co)polymers, such as high molecular weight homo- or copolymers comprising acrylic acid, optionally crosslinked with a polyalkenyl polyether, including certain polymers identified as "carbomers" as well as amphiphilic polymers. Preferably, the gelling agent is a gum, an amphiphilic polymer or a clay, or a combination of any of these.

[0182] According to preferred embodiments, the at least one gelling agent is preferably at least one gum. Suitable examples of thickening gums include, but are not limited to, xanthan, sclerotium, pectin, karaya, arabic, gelatin, agar, guar, carrageenan, alginate, and combinations thereof.

[0183] According to preferred embodiments, the at least one gelling agent is preferably at least one amphiphilic polymer, comprising at least one ethylenically unsaturated monomer, preferably containing a sulfonic group, in free or partially or totally neutralized form.

[0184] The amphiphilic polymers may comprise at least one hydrophobic portion. The hydrophobic portion present in these polymers preferably contains from 6 to 50 carbon atoms, preferably from 6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms and preferably from 12 to 18 carbon atoms, including all intermediate ranges and sub-ranges.

[0185] The amphiphilic polymers may have a molar mass ranging from 50,000 g / mol to 10,000,000 g / mol, preferably from 80,000 g / mol to 8,000,000 g / mol, and preferably from 100,000 g / mol to 7,000,000 g / mol.

[0186] The amphiphilic polymers may be based on at least one ethylenically unsaturated hydrophilic monomer A and at least one hydrophobic monomer B. Preferably, the monomer A comprises a strong acid function, in particular a sulfonic acid or phosphonic acid function. The hydrophobic monomer B comprises at least one hydrophobic radical, chosen from: saturated or unsaturated C6-C18 linear alkyl radicals (for example, n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl or oleyl); branched alkyl radicals (for example, isostearic) or cyclic alkyl radicals (for example, cyclododecane or adamantane); C6-C18 fluoro or alkylfluoro radicals (for example, the group of formula —(CH2)2—(CF2)q—CF3); a cholesteryl radical or radicals derived from cholesterol (e.g., cholesteryl hexanoate); aromatic polycyclic groups, e.g., naphthalene or pyrene; and silicone or alkylsilicone or alkylfluorosilicone radicals.Among these radicals, linear and branched alkyl radicals are preferred.

[0187] Amphiphilic polymers may be water-soluble or water-dispersible in neutralized form.

[0188] The amphiphilic polymers can be crosslinked. The crosslinking agents can be chosen, for example, from polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by polymerization by free radicals. According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA). The degree of crosslinking preferably ranges from 0.01 mol% to 10 mol%, and preferably from 0.2 mol% to 2 mol%, relative to the polymer, including all intermediate ranges and sub-ranges.

[0189] The amphiphilic polymers can be homopolymers or copolymers.

[0190] Amphiphilic polymers can be partially or completely neutralized with an inorganic base (e.g., sodium hydroxide, potassium hydroxide, or liquid ammonia) or an organic base such as monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, N-methylglucamine, or basic amino acids, e.g., arginine and lysine, and mixtures thereof.

[0191] The amphiphilic polymers may be water-soluble or water-dispersible homopolymers such as, for example, optionally crosslinked polymers of sodium 2-acrylamido-2-methylpropane sulfonate acid such as that used in the commercial product SIMULGEL 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of ammonium 2-acrylamido-2-methyl propane sulfonate acid (INCI name: AMMONIUM POLYACRYLDIMEHYLTAURAMIDE) such as the product sold under the trade name HOSTACERIN AMPS@ by Clariant.

[0192] The amphiphilic polymers may be chosen from crosslinked or non-crosslinked amphiphilic polymers of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and at least one ethylenically unsaturated monomer comprising at least one hydrophobic portion containing from 6 to 30 carbon atoms, preferably from 6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms and preferably from 12 to 18 carbon atoms, including all intermediate ranges and sub-ranges.

[0193] Suitable examples of amphiphilic polymers include, but are not limited to, hydrophobically modified sulfonic acid copolymers such as ammonium acryloyldimethyltaurate / VP copolymer (Clariant's Aristoflex AVC), ammonium acryloyldimethyltaurate / beheneth-25 methacrylate crosslinked polymer (Clariant's Aristoflex HMB) (crosslinked and ethoxylated AMPS / behenyl methacrylate), ammonium acryloyldimethyltaurate / steareth-25 methacrylate crosslinked polymer (Aristoflex HMS) (ethoxylated AMPS / stearyl methacrylate copolymer crosslinked with trimethylol triacrylate), Aristoflex SNC (crosslinked and ethoxylated AMPS / C16-C18), Aristoflex LNC (AMPS / C12-C14 uncrosslinked), acrylamide / sodium acryloyldimethyl taurate / isohexadecane / polysorbate 80 copolymer) (Simulgel 600), and mixtures thereof.

[0194] 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 family of smectites, such as laponite, of the kaolinite family, such as kaolinite, dickite or nacrite, facultatively modified clays of the halloysite, dombassite, antigorite, berthierine, pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, saponite, chlorite, sepiolite and illite family.

[0195] 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.

[0196] Natural clay is a sedimentary rock composed largely of specific minerals, generally aluminum silicates. Kaolin is therefore a natural clay.

[0197] Clays can also be synthetic. Thus, Sumecton mentioned below is a synthetic saponite.

[0198] 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.

[0199] 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, mention may be made in particular of those sold under the names Bentone 38 VCG®, Bentone Gel CAO V®, Bentone 27 V® and Bentone Gel MIO V® by the company Elementis.

[0200] As a montmorillonite-rich clay, we can cite the hydrated aluminum silicate sold under the name Gel White H® by the Rockwood company.

[0201] 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®.

[0202] 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.

[0203] Preferably, where appropriate, the gelling agent(s) is(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.

[0204] Dye (Coloring agent)

[0205] According to embodiments of the present invention, compositions optionally further comprising at least one coloring agent are provided. According to preferred embodiments, the at least one coloring agent, if any, is at least one surface-treated pigment. "Surface-treated pigment" means pigments which have undergone, totally or partially, a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with a surface treatment agent. Preferably, the pigments are selected from inorganic pigments or mixed inorganic / organic pigments.

[0206] The surface treatment agents may be selected from the group consisting of alkyl silanes, organotitanates, halogenated phosphonates and halogenated organosilanes. According to preferred embodiments, the pigments have been surface-treated with a surface-treating agent selected from the group consisting of alkoxylated alkyl silanes such as, for example, ethoxylated and / or propoxylated C2-C8 alkyl silanes, and salts thereof, organotitanates such as, for example, titanium salts of fatty acids such as, for example, C2-C8 alkylated titanium salts of C9-C24 fatty acids such as stearic acid, isostearic acid, oleic acid, cetearic acid, cetyl acid, etc., halogenated organophosphonates such as, for example, perfluoroalkyl phosphonates, and salts thereof, and halogenated organosilanes such as, for example, C2-C8 perfluoro alkyl silanes (optionally ethoxylated and / or propoxylated), and their salts.Specific examples of suitable surface treatment agents include (1) triethoxy caprylylsilane, (2) perfluorooctyltriethoxysilane, (3) sodium perfluorohexylethylphosphonate, and (4) isopropyl titanium triisosteate.

[0207] Preferred surface treatment agents are selected from the group consisting of alkyl silanes and halogenated organosilanes. In preferred embodiments, the pigments have been surface treated with a surface treatment agent selected from the group consisting of alkoxylated alkyl silanes such as, for example, ethoxylated and / or propoxylated C2-C8 alkyl silanes, and salts thereof, and halogenated organosilanes such as, for example, perfluoro (optionally ethoxylated and / or propoxylated) C2-C8 alkyl silanes, and salts thereof. Specific examples of suitable surface treatment agents include (1) triethoxy caprylylsilane and (2) perfluorooctyltriethoxysilane.

[0208] The surface-treated pigments of the present invention may be prepared according to surface treatment techniques well known to one of ordinary skill in the art or may be commercially available.

[0209] For example, the surface treatment agent with which the pigments are treated may be deposited on the pigments by solvent evaporation, chemical reaction between molecules of the surface treatment agent, or creation of a covalent bond. between the surface treatment agent and the pigments. The surface treatment can thus be achieved, for example, by chemically reacting a surface treatment agent with the surface of the pigments and creating a covalent bond between the surface treatment agent and the pigments. An exemplary method is described, for example, in US Patent No. 4,578,266.

[0210] The at least one surface-treated pigment, if any, is preferably present in the compositions of the present invention at an active solids content of from about 1% to about 30%, preferably from about 3% to about 25%, and preferably from about 5% to about 20%, by weight relative to the total weight of the composition, including all intermediate ranges and sub-ranges.

[0211] According to preferred embodiments of the present invention, compositions further comprising at least one non-surface-treated coloring agent are provided. Such coloring agents, if desired, may be in addition to or replace the surface-treated pigment discussed above.

[0212] According to this embodiment, the coloring agent is preferably chosen from pigments which have not been surface treated, dyes, such as fat-soluble dyes, pearlescent pigments and pearlescent agents.

[0213] Representative fat-soluble dyes that may be used in accordance with the present invention include Sudan Red, DC Red 17, DC Green 6, [3-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, annatto, and quinoline yellow. Fat-soluble dyes, if any, generally have a concentration of up to 40% by weight of the total weight of the composition, such as from 0.0001% to 30%, including all intermediate ranges and sub-ranges.

[0214] The pearlescent pigments that can be used according to the present invention can be chosen from colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and pearlescent pigments based on bismuth oxychloride. The pearlescent pigments, if any, are present in the composition at a concentration of up to 50% by weight of the total weight of the composition, such as from 0.0001% to 40%, preferably from 0.001% to 30%, including all intermediate ranges and sub-ranges.

[0215] The non-surface-treated pigments, which may be used according to the present invention, may be selected from white, colored, inorganic, organic, polymeric and non-polymeric pigments. Representative examples of inorganic pigments include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Representative examples of organic pigments include carbon black, pigments of type D & C, and lakes based on cochineal carmine, barium, strontium, calcium and aluminum.

[0216] Optionally, the coloring agents may be present in the composition at a concentration of up to 50% by weight of the total weight of the composition, such as from 0.0001% to 40%, and further such as from 0.001% to 30%, including all intermediate ranges and sub-ranges.

[0217] According to preferred embodiments, the compositions of the present invention are free, free or substantially free of coloring agents.

[0218] Active agent

[0219] 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).

[0220] In some embodiments, the active agent may be:

[0221] - a moisturizing agent, such as a polyol such as, for example, glycerin and sugars, urea and its derivatives, such as in particular a hydroxyalkyl urea, in particular a hydroxyalkylurea, and mixtures thereof;

[0222] - a desquamating agent, which may be a compound capable of either acting directly on desquamation by promoting exfoliation, such as [3-hydroxy acids, in particular salicylic acid and its derivatives (including 5-n-octanoylsalicylic acid); α-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; an extract of Saphora japonica; resveratrol and certain jasmonic acid derivatives; or to act on the enzymes involved in desquamation or the degradation of comeodesmosomes, glycosidases, the stratum corneum chymotryptic enzyme (SCCE), or even other proteases (trypsin, chymotrypsin type). Examples include mineral salt chelating agents: EDTA; N-acyl-N.N' acid.N'-Ethylenediaminctriacetic acid; aminosulfonic compounds and in particular (N-2-hydroxyethylpiperazine-N-2-ethane)sulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid derivatives (procysteine); α-amino acid derivatives of the glycine type (as described in EP-0 852 949 and sodium methylglycinediacetate sold by BASF under the trade name Trilon M); honey; sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine; .

[0223] - a humectant;

[0224] - 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.

[0225] - a matting agent, which may include, but is not limited to, fillers mattifying agents such as, for example, talc, silica, silicone elastomers and polyamides, and waxes such as, for example, beeswax and copernicia cerifera (carnauba) wax.

[0226] - an antimicrobial agent, non-limiting examples of which include ether of 2,4,4'-trichloro-2'-hydroxydiphenyl (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, ciclopiroxolamine, 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, acid 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, farnesol and phytosphingosines, and mixtures thereof;

[0227] - a pigment modifying agent and / or skin lightening agents, such as than double-stranded RNA oligonucleotides, are useful in decreasing tyrosinase expression. Other examples include ceramides, vitamin C and its derivatives, in particular vitamin CG, CP and 3-O ethyl vitamin C, alpha- and beta-arbutin, ferulic acid, kojic acid, resorcinol and its derivatives, calcium D-pantetheine sulfonate, lipoic acid, ellagic acid, vitamin B3, phenylethyl resorcinol, for example Symwhite 377® from the company Symrise, a kiwi juice (Actinidia chinensis) sold by Gattefosse, a root extract of Paeonia suffructicosa, such as the product sold by the company Ichimaru Pharcos under the name Botanpi Liquid B®, a brown sugar extract (Saccharum officinarum), such as the molasses extract sold by the company Taiyo Kagaku under the name Molasses Liquid, a mixture of undecylenic acid and undecylenoyl phenyl alanine, such as Sepiwhite MSH® from Seppic;

[0228] - a vitamin such as a vitamin A compound such as retinol or acid retinoic acid, a vitamin B compound such as vitamin B1, B3 or B6, a vitamin C compound such as an ascorbyl phosphate salt (e.g., magnesium or sodium, and / or their derivatives;

[0229] - 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. In particular, 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 a combination thereof.

[0230] According to certain embodiments, the compositions of the present invention include at least two of the gelling agent, the colorant and the active agent.

[0231] Additional additives

[0232] The composition of the invention may also include any additive commonly used in the art. For example, additional film-forming agents (in addition to the hydrophobically modified polysaccharide compound and the aqueous-phase film-forming agent), waxes, dispersants such as poly(12-hydroxystearic acid), preservatives, fragrances, fillers, antioxidants, neutralizing agents, silicone elastomers, and mixtures thereof, may be added. A non-exhaustive list of such ingredients may be found in U.S. Patent Application Publication No. 2004 / 0170586. Other examples of suitable additional components may be found in other references. Still other examples of such additional ingredients may be found in the International Cosmetic Ingredient Dictionary and Handbook (9th ed. 2002).However, it should be understood that preferred embodiments of the present invention include compositions that are "free", "substantially free" or "devoid of" the ingredients discussed in this paragraph such as additional film-forming agents and waxes.

[0233] According to preferred embodiments, the compositions of the present invention contain a total solids content (excluding film formers) of 10% by weight or less, preferably 5% by weight or less, or preferably 3% by weight or less based on the weight of the composition. Preferably, the compositions of the present invention are free, free of, or substantially free of solids (excluding film formers).

[0234] 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.

[0235] 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.

[0236] It goes without saying that the composition of the invention must be cosmetically or dermatologically acceptable, that is to say that it must contain a physiologically acceptable non-toxic carrier and must be able to be applied to the keratinous material of human beings.

[0237] According to preferred embodiments of the present invention, methods of caring for, and / or making up, keratinous material by applying compositions of the present invention to the keratinous material in an amount sufficient to care for and / or make up the keratinous material are provided. Similarly, preferred embodiments of the present invention include methods of priming the keratinous material for a cosmetic composition and / or fixing a cosmetic composition that has been previously applied to the keratinous material by applying compositions of the present invention over the keratinous material before applying a cosmetic composition (priming) and / or by applying compositions of the present invention over a cosmetic composition previously applied to the keratinous material (fixing).Preferably, the cosmetic composition used in conjunction with the compositions of the present invention is a color cosmetic composition.

[0238] Preferably, "making up" the keratinous material includes applying at least one coloring agent to the keratinous material (either in the composition itself or in a color layer composition applied either over or under the composition as described above) in an amount sufficient to impart color to the keratinous material.

[0239] According to particularly preferred embodiments of the present invention, methods of making up keratinous material such as skin comprising (1) applying a color cosmetic composition such as a foundation to the keratinous material (e.g., skin), (2) allowing the color cosmetic composition to dry on the keratinous material (e.g., skin), preferably allowing it to dry for about 1 minute to about 15 minutes, preferably for about 5 minutes to 10 minutes, and (3) applying a composition of the present invention over the dried color cosmetic composition that has been applied to the keratinous material (e.g., skin) are provided.Preferably, compositions of the present invention are applied over the dried color cosmetic composition in an amount sufficient to improve the transfer resistance of the color cosmetic composition relative to the transfer resistance provided by the color cosmetic composition when applied alone to a keratinous material.

[0240] According to certain preferred embodiments, a method of making up the skin includes applying a composition of the present invention to skin having a makeup film formed thereon. The makeup film may result, for example, from the application of a foundation or other first makeup composition such as one including a coloring agent applied to the skin and optionally allowed to dry, for example by waiting a period of time described in the paragraph above. The composition of the present invention includes (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and (d) at least one aqueous-phase film former. In this embodiment, the composition of the present invention acts as a makeup fixative.

[0241] The compositions of the present invention may be applied by spraying or rubbing with a pad or applicator.

[0242] According to preferred embodiments of the present invention, kits comprising, as separate compositions in one or more containers within the kits, (A) at least one composition of the present invention, in particular a fixative or primer composition for cosmetics, comprising at least one hydrophobically modified polysaccharide compound and at least one aqueous-phase film former; and (B) at least one other composition such as a cosmetic composition comprising at least one colorant are provided.

[0243] 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.

[0244] According to preferred embodiments of the present invention, assemblies, as applied to a keratinous material, comprising (A) at least one first layer of at least one composition comprising at least one colorant; and (B) at least one second layer of at least one composition of the present invention, in particular a fixative or primer composition for cosmetics, comprising at least one hydrophobically modified polysaccharide compound and at least one aqueous film former are provided. Preferably, the at least one second layer is applied over the at least one first layer (in which case the second layer is a fixative layer formed by applying a fixative composition to the first layer).However, if the at least one first layer is applied over the at least one second layer, the at least one second layer is a primer layer formed by applying a primer composition over a keratinous material.

[0245] According to a preferred embodiment of the present invention, compositions having improved cosmetic properties such as, for example, increased water resistance, sebum resistance and / or transfer resistance are provided. Preferably, the composition is a skin composition. Preferably, the composition is a fixative or primer composition. Also preferably, the composition further comprises at least one gelling agent and / or at least one active agent.

[0246] According to a preferred embodiment of the present invention, methods for manufacturing oil-in-water (o / w) emulsions (compositions) of the present invention comprising the combination of at least one hydrophobically modified polysaccharide compound and at least one aqueous film former in the amounts and / or ratios discussed above during the formation of the emulsion composition are provided. Preferably, the composition is a composition for application to the skin. Most preferably, the composition is a fixative or primer composition, and / or is in the form of a gel. Also preferably, the composition further comprises at least one gelling agent and / or at least one active agent.

[0247] Unless otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, etc., used in the patent 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 patent specification and appended claims are approximations which may vary depending on the desired properties sought to be achieved by the present invention.

[0248] Although the numerical ranges and parameters defining the general scope of the invention are approximations, the numerical values ​​indicated in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without limiting its scope accordingly. Percentages are given on a weight basis. EXAMPLES

[0249] Example 1 - Samples of inventive compositions

[0250] Examples of inventive compositions are given in Table 3 below.

[0251] [Tables3] Total 100.00% - General Total 100% - Preferred Chemical Name / Function % wt / wt % wt / wt Surfactants 0-10% 0.1-3% Water-Based Film-Forming 0.5-20% 1-10% Silicon acrylate copolymer and / or glycerolated silicone resin 0.5 to 20% 1 to 10% Oils 1 to 30% 2 to 10% Colorant / fragrance / active Optional Substantially free Water QS QS Monoalcohol 0 to 30% 2.5 to 25% Gelling agent 0.1 to 10% 0.1 to 3%

[0252] Example 2 - Test Protocol - Transfer Resistance

[0253] The transfer resistance (dry) can be determined as follows.

[0254] A color cosmetic composition (e.g., a foundation such as L'Oréal Paris Makeup True Match Liquid Foundation) is applied to a keratinous material (e.g., skin) in a controlled amount (e.g., 0.020 grams) in a controlled area (e.g., 3 cm x 3 cm square). Wait 5 to 15 minutes until the solution has dried.

[0255] Apply a test composition (fixer) in a controlled amount (e.g., the same amount as the applied color cosmetic composition, such as 0.020 grams) over the applied color cosmetic composition, and allow it to dry.

[0256] A white cotton pad / ball is then used to rub over the area an identified number of times (e.g., 5 or more times) to assess the transfer resistance of the color cosmetic composition onto the pad / ball after such rubbing. Transfer resistance may be assessed by determining the difference in the amount of color cosmetic composition transferred onto the cotton pad / ball, with or without the fixing composition applied.Transfer resistance is rated on a scale of 1 to 5, with 1 = minimal improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball; 3 = moderate improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball; and 5 = significant improvement in transfer resistance of the color cosmetic composition to the cotton pad / ball, with little or no transfer of the color cosmetic composition to the cotton pad / ball.

[0257] Example 3 - Test protocol - Water resistance

[0258] Water resistance can be determined as follows. A color cosmetic composition (e.g., a foundation such as L'Oréal Paris Makeup True Match Liquid Foundation) is applied to a keratinous material (e.g., skin) in a controlled amount (e.g., 0.020 grams) in a controlled area (e.g., 3 cm x 3 cm square). Wait 5 to 15 minutes until the solution has dried.

[0259] Apply a test composition (fixer) in a controlled amount (e.g., the same amount as the applied color cosmetic composition, such as 0.020 grams) over the applied color cosmetic composition, and allow it to dry.

[0260] Place the keratinous material (e.g., skin) under water. Rub the area with the palm (e.g., 5 or more times). Dry the area before evaluating.

[0261] Water resistance can be evaluated by the color difference before and after the water rub test. Water resistance is evaluated on a scale of 1 to 5, with 1 = some color change after the water rub test; 3 = a slight color change after the water rub test; and 5 = no color change after the water rub test.

[0262] The following compositions: Inventive Examples Ex 1, Ex 2, as well as Comparative Examples C1 and C2 were prepared and tested as fixative compositions for L'Oréal Paris Makeup True Match Liquid Foundation according to the protocol of Examples 2 and 3.

[0263] Comparative Examples C1 and C2 did not include silicone acrylate copolymer and no glycerolated silicone resin.

[0264] Examples Ex 1 and Ex 2 were representative of the compositions of the invention containing silicone acrylate copolymer or glycerolated silicone resin.

[0265] The transfer resistance of the commercial foundation + prepared fixer compositions was determined according to the protocol of Example 2. The specific test compositions and test results are shown in Tables 4 and 5 below.

[0266] [Tables4] Exl Ex 2 Glycerin-modified MQ resin (50% in isododecane) 5 Acrylates / polytrimethylsiloxymethacrylate copolymer (40% in isododecane) 5 Isohexadecane 0.32 0.32 Sorbitan oleate 0.04 0.04 Polysorbate 80 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 Vinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer (20% in water) 6.25 6.25 Ethanol 25 25 water QS QS Oil-based film former 2.5 2 Water-based film former 1.25 1.25 Total film former 3.75 3.25 Transfer test - Water resistance 1 1 Transfer test - Dry transfer 2 3

[0267] [Tables5] Cl C2 Glycerin-modified MQ resin (50% in isododecane) 0 Acrylates / polytrimethylsiloxymethacrylate copolymer (40% in isododecane) 0 Isododecane 2.00 5.00 Isohexadecane 0.32 0.32 Sorbitan oleate 0.04 0.04 Polysorbate 80 0.10 0.10 Sodium acrylate / sodium acryloyldimethyl taurate copolymer 0.60 0.60 Vinyl pyrrolidone / methacrylamide / vinyl imidazole copolymer (20% in water) 6.25 12.5 Ethanol 25 25 Water QS QS Oil-phase film former 0 0 Water-based film-forming 1.25 2.5 Total film-forming 1.25 2.5 Transfer test - Water resistance No improvement No improvement Transfer test - Dry transfer 1 3

[0268] As can be seen, the fixative compositions corresponding to the present invention resulted in superior water resistance when used in conjunction with the commercial foundation product compared to comparative fixative compositions not containing silicone acrylate copolymer or glycerolated silicone resin.

Claims

Claims

1. An oil-in-water emulsion composition comprising (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and (d) at least one copolymer comprising a vinyl pyrrolidone monomer.

2. The composition of claim 1, wherein the at least one copolymer comprising a vinyl pyrrolidone monomer is a copolymer of N-vinyl pyrrolidone, methacrylamide and N-vinylimidazole.

3. A composition according to any preceding claim, wherein the composition further comprises (e) at least one compound selected from the group consisting of at least one gelling agent, at least one colorant, at least one active agent, and mixtures thereof.

4. A composition according to any preceding claim, wherein the at least one organosilicone polymer is a silicone acrylate copolymer.

5. A composition according to any preceding claim, wherein the at least one organosilicone polymer is a glycerolated silicone resin.

6. A composition according to any preceding claim, wherein the (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerol silicone resin, and combinations thereof; and the (d) at least one copolymer comprising a vinyl pyrrolidone monomer are present in a weight ratio, (c):(d) which is from about 0.5:1 to about 3:

1.

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

8. A method of making up the skin comprising applying a composition to skin having a make-up film formed thereon, wherein the composition comprises (a) water, (b) at least one oil, (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerolated silicone resin, and combinations thereof; and (d) at least one aqueous-phase film former.

9. The method of claim 8, wherein the at least one aqueous phase film former is selected from a group consisting of polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / acrylic acid copolymer, polyvinyl alcohol, N-vinylpyrrolidone copolymer, methacrylamide and N-vinylimidazole.

10. The method of claims 8 or 9, wherein the (c) at least one organosilicone polymer selected from a silicone acrylate copolymer, a glycerolated silicone resin, and combinations thereof; and the (d) at least one aqueous-phase film former are present in a weight ratio, (c):(d) which is from about 0.5:1 to about 3:1.