W / O emulsion composition containing hydrophobic modified pullulan compound and aqueous phase-forming agent

Abstract

The present invention relates to a water-in-oil (W / O) emulsion composition, preferably for makeup application on skin, comprising at least one hydrophobic-modified pullulan compound and at least one aqueous phase film-forming agent, and to a method for applying such an emulsion composition.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the priority of U.S. Patent Application No. 18 / 345,499, filed on June 30, 2023. This application also claims the priority of French Patent Application No. 2311122, filed on October 16, 2023.

[0002] The present invention relates to a water - in - oil (w / o) emulsion (composition) comprising at least one hydrophobically modified pullulan compound and at least one aqueous - phase film - forming agent, and to methods and kits containing such an emulsion composition in a container or during application. The composition has beneficial cosmetic properties, including good or improved durability, water and / or sebum resistance, and / or transfer - resistance properties, particularly sebum resistance.

Background Art

[0003] Currently, in the market for keratin care and makeup products, many products claim to withstand external factors such as water, sebum, mechanical friction, etc. and have long - lasting power throughout the day (water - proof mascara, hood - proof lipstick, long - lasting foundation). Long - lasting products for lips, eyelashes, eyebrows or face that can be used at home are mainly based on synthetic coating polymers in the presence of organic solvents. For compositions for lip makeup and face makeup, compositions containing unmodified silicone resins as film - forming agents, such as compounds with INCI name: trimethylsiloxysilicate or compounds with INCI name: polypropylsilsesquioxane, or silicone acrylate copolymers such as products with INCI name: acrylate / methacrylic acid polytrimethylsiloxyl copolymer are known. On the other hand, long - lasting makeup products (mascara, eyeliner) for eyelashes and / or eyebrows typically use waxes or film - forming polymer particles (i.e., styrene / acrylate copolymers) in a latex - type aqueous suspension as film - forming agents.

[0004] Beyond these long-lasting products, the current trend is towards semi-permanent makeup. Specifically, in recent years, traditional makeup products have faced competition from the market for semi-permanent makeup offered in professional salons. This is encountered in the areas of eye makeup (semi-permanent mascara, permanent eyelash makeup, eyelash extensions, etc.), eyebrow makeup (semi-pigmentation, also known as microblading), complexion makeup (freckles, beauty spots, or full face makeup, or effects for a radiant or healthy complexion), or lip makeup (semi-permanent tattoos). This new trend has led consumers to increasingly demand longer-lasting effects for greater practicality (avoiding the need to apply and remove makeup daily, achieving a healthy complexion immediately upon waking, etc.).

[0005] The object of the present invention is to propose a composition that can extend the duration of cosmetic compositions on keratinous materials and improve the durability of cosmetic compositions on keratinous materials as well as their resistance to one or more external forces such as mechanical friction, water, sweat and perspiration, sebum, oil, etc., thereby providing the expected cosmetic effect, particularly excellent color retention of makeup on keratinous materials (skin, lips, nails, hair, eyelashes, eyebrows).

[0006] In addition, an object of the present invention is to propose a composition that provides the expected cosmetic effect, particularly the color retention of makeup on keratinous materials, in combination with a better comfort level compared to conventional systems, especially one based on unmodified silicone resin.

[0007] Potentially relevant patent references include the following:

[0008] US 11,253,462 discloses a low-wax composition containing a silicone polymer among many other components.

[0009] US 2020 / 0022898 discloses a film-forming composition comprising a first anionic or nonionic non-crosslinked polyacrylate random copolymer and a second cationic non-crosslinked polyamide random copolymer.

[0010] US 11,033,478 discloses a self-curling mascara composition containing at least about 7 mass percent of a nonionic, water-soluble or water-dispersible copolymer comprising a cyclic amide monomer, a cyclic amine monomer, and an acrylamide monomer.

[0011] US 11,253,462 discloses a composition containing polymethyl methacrylate polymer among many other components.

[0012] US 2003 / 0082221 discloses compositions containing pullulan.

[0013] US 2016 / 0113860 discloses compositions containing silicone-modified pullulan and a silicone oil that thickens it.

[0014] JP-A H08-208989 is characterized by disclosing a silicone-modified pullulan that, as described in a previous application, thickens a silicone oil component but has an insufficient thickening effect.

[0015] CN 111801092 discloses a composition for impregnating a substance, comprising PEG or polyether-modified silicone and a dendrimer-type siloxane.

[0016] FR 3,104,958 discloses a composition containing a polyurethane dispersion among many other components.

[0017] FR 3,110,849 discloses a composition containing, among many other components, a polyurethane and / or acrylic dispersion, and containing little to no fatty substances. [Prior art documents] [Chartered documents]

[0018]

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Non-licensed literature

[0019] [Non-licensed document 1] "Mineralogie des argiles" ["Clay Mineralogy"], S. Caillere, S. Henin, M. Rautureau, 2nd edition, 1982, Masson [Non-licensed document 2] International Cosmetic Ingredient Dictionary and Handbook (9th edition, 2002) [Overview of the Initiative] [Problems that the invention aims to solve]

[0020] There is still a need for improved compositions, such as emulsion compositions, that have improved properties with respect to ease of application and / or comfort of the composition, and / or in particular to improved durability of cosmetic compositions on keratinous materials and improved properties related to their resistance to external forces such as mechanical friction, water, sweat and perspiration, sebum and / or oil. [Means for solving the problem]

[0021] The present invention relates to a water-in-oil (w / o) emulsion composition comprising at least one hydrophobic-modified pullulan compound and at least one aqueous phase film-forming agent. Preferably, the composition is a composition for application to the skin. Most preferably, the composition is a foundation. Also preferably, the composition further comprises at least one thickener, at least one colorant, and / or at least one surfactant.

[0022] The present invention also relates to a method for treating, caring for, and / or makeuping a keratinous substance such as skin, the method comprising applying a composition of the present invention to a keratinous substance in an amount sufficient to treat, care for, and / or makeup the keratinous substance. Preferably, the composition is a composition for application to skin. Most preferably, the composition is a foundation.

[0023] The present invention also relates to a method for preparing a water-in-oil (w / o) emulsion composition, comprising the step of combining at least one hydrophobic-modified pullulan compound and at least one aqueous phase-forming agent during the formation of the emulsion composition. Preferably, the composition is a composition for application to the skin. Most preferably, the composition is a foundation. Also preferably, the composition further comprises at least one thickener, at least one colorant, and / or at least one surfactant. [Modes for carrying out the invention]

[0024] In the following description of the invention and the claims appended herein, terms used should be understood to have their common and conventional meanings in the art unless otherwise specified.

[0025] As used herein, "about" means within 10% of the indicated number (for example, "about 10%" means 9% to 11%, and "about 2%" means 1.8% to 2.2%).

[0026] As used herein, “a” or “an” means “at least one.”

[0027] "At least one" means one or more, and therefore includes individual components and mixtures / combinations.

[0028] When used herein, all provided ranges are intended to include any specific range within a given range, and combinations of subranges between given ranges. Thus, the ranges 1-5 specifically include 1, 2, 3, 4, and 5, as well as subranges such as 2-5, 3-5, 2-3, 2-4, 1-4, etc.

[0029] As used herein, “film-forming agent,” “film-forming polymer,” or “film-forming agent” means, for example, a polymer or resin that leaves a film on a substrate after the solvent accompanying the film-forming agent has evaporated, been absorbed, and / or disappeared on the substrate to which it is applied.

[0030] As used herein, "wax" is a lipophilic aliphatic compound that is solid at ambient temperature (25°C), reversibly changes from a solid to a liquid state, has a melting point above 30°C, for example above 45°C, and a hardness above 0.5 MPa at ambient temperature.

[0031] "Surfactants" and "emulsifiers" are used interchangeably throughout this specification.

[0032] As used herein, “substituted” means including at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen and nitrogen atoms, and 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. Substituents may be further substituted.

[0033] As used herein, "volatile" means having a flash point of less than approximately 115°C.

[0034] As used herein, "non-volatile" means having a flash point above approximately 115°C.

[0035] As used herein, "polymer" means a compound composed of at least two monomers.

[0036] In this specification, “matte” refers to a composition with little or no light reflection. For example, a matte composition may have an average gloss characteristic of 10 or less, e.g., 9, preferably 8, 6, 5, 4, or 1 or less, measured at 60°, and includes all and partial ranges in between, such as 1-10, 1-5, 2-10, 3-8, less than 1, less than 3, less than 5, etc. Such measurements can be performed by depositing the film to be tested onto a substrate (e.g., black scrub panel P121-10N or opaque card BYK No. 2810) using a drawdown bar (e.g., 1 mil, 3 mil, or 6 mil thickness) and an automatic drawdown machine. The film can then be dried at room temperature and analyzed at a desired angle, e.g., 60° or 85°, using a gloss meter (BYK: micro-TRI-gloss).

[0037] As used herein, “free of,” “substantially free of,” or “lacking of” means that it is preferable that a particular component is not present in any amount in the composition, but it is possible that it may be present in very small amounts in the composition of the present invention, provided that these amounts do not significantly affect at least one, preferably most, of the advantageous properties of the conditioning composition of the present invention. Therefore, for example, “free of phenylated silicone oil” means that an effective amount (i.e., an effective amount to suppress mattiness) of phenylated silicone oil is omitted from the composition (i.e., about 0% by mass), “substantially free of phenylated silicone oil” means that phenylated silicone oil is present in an amount of 0.25% by mass or less, and “lacking of phenylated silicone oil” means that phenylated silicone oil is present in an amount of 0.5% by mass or less relative to the total mass of the composition. The same nomenclature applies throughout this application and to all other components identified in this paragraph, even if not specifically stated for each identified component, for example, (1) matte-finishing fillers (compositions of the present invention that "do not contain matte-finishing fillers," "substantially do not contain matte-finishing fillers," and "lack matte-finishing fillers") and (2) additional film-forming agents other than hydrophobic-modified pullulan compounds and aqueous phase film-forming agents (compositions of the present invention that "do not contain additional film-forming agents," "substantially do not contain additional film-forming agents," and "lack additional film-forming agents") having the same meaning as described in this paragraph. The descriptions of examples of the use of such language, as in this paragraph, are intended to be illustrative and not limiting.

[0038] As used herein, “makeup result” refers to a composition whose color, after a long period of time, remains the same or substantially the same as when applied, as observed with the naked eye. “Makeup result” can be evaluated by assessing long-term durability by any method known in the art to evaluate such properties. For example, long-term durability can be evaluated by a test involving applying the composition to a keratinous substance such as lips and evaluating the color of the composition after a long period of time. For example, the color of the composition can be evaluated immediately after application to a keratinous substance such as lips, and then these characteristics can be re-evaluated and compared after a certain length of time. Furthermore, these characteristics can be evaluated in relation to other compositions, e.g., commercially available compositions.

[0039] "Keratinous material" or "keratinous material" means skin such as natural nails, lips, face, body, hands, and the area around the eyes, as well as keratin fibers such as human hair, eyelashes, eyebrows, and body hair, and synthetic adducts such as false eyelashes, false eyebrows, and false nails.

[0040] "Physiologically acceptable" means that it is compatible with keratinous substances, has a pleasant color, scent and feel, and does not produce any unacceptable discomfort (such as stinging pain or tightness) that would cause consumers to avoid using the composition. The acceptable pH level of the internal aqueous phase of the composition of the present invention is preferably acidic, i.e., less than 7, preferably 6.5 or less, preferably 6.0 or less, and preferably 5.5 or less, and includes all and partial ranges in between, such as 3 to 5, 4 to 6, 5.5 to 6.5, 3 to 4.5, etc. The composition of the present invention may also be in the form of a gel composition.

[0041] "Natural compounds" refer to any compounds that originate directly from natural substances, such as plants, without undergoing any chemical modification.

[0042] "Naturally occurring compounds" refer to any compound derived from a naturally occurring compound that has undergone one or more chemical modifications, for example, through an organic synthesis reaction, without altering the properties of the natural compound.

[0043] A "synthetic compound" refers to any compound that is neither a natural compound nor a compound of natural origin.

[0044] "Room temperature" means 25℃.

[0045] Atmospheric pressure is 760 mmHg, that is, 10 5 It means Pascal.

[0046] The compositions and methods of the present invention may consist of, or be essentially composed of, any essential elements and limitations of the present invention as described herein, as well as any additional or optional components, components, or limitations described herein or otherwise useful. For example, the aqueous phase solvent system may essentially consist of water and C2-C5 monoalcohols, and / or the film-forming system may essentially consist of at least one pullulan compound and at least one cyclic amide-containing polymer.

[0047] For the purposes of the present invention, a "basic and novel property" relating to compositions, components and methods "essentially derived from" a specified component or action is "sebum resistance".

[0048] Trademark names of substances, including but not limited to polymers and optional components, are referred to herein. The inventors herein are not intended to be limited to any substance described and referred to by a particular trade name. Substances equivalent to those referred to by a trade name (e.g., obtained from a different source under a different name or catalog (reference) number) may be substituted and used in the manner described herein and claimed.

[0049] All percentages and ratios are calculated by mass unless otherwise specified. All percentages are calculated based on the total mass of the composition unless otherwise specified. All component or composition levels relate to the activity level of that component or composition, excluding impurities that may be present in commercially available sources, such as residual solvents or by-products.

[0050] All U.S. patents or patent applications disclosed herein are expressly incorporated in their entirety by reference.

[0051] Aqueous phase-forming agent The present invention provides a composition comprising one or more aqueous film-forming polymers ("first film-forming polymer" or "first film-forming agent") which are nonionic, water-soluble or water-dispersible polymers. For clarity, "nonionic, water-soluble or water-dispersible" means that the polymer is nonionic. The polymer is also water-soluble or water-dispersible to such an extent that it can be easily stabilized throughout the vehicle (e.g., water) present in the composition.

[0052] One or more of these first film-forming polymers are part of an aqueous phase film-forming system. The aqueous phase film-forming system comprises, and may consist of, an aqueous phase film-forming agent.

[0053] Examples of aqueous film-forming polymers include, but are not limited to, homopolymers and copolymers containing at least one (meth)acrylic acid ((meth)acrylate) monomer and / or at least one vinylpyrrolidone monomer, such as polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / acrylic acid copolymer, vinylpyrrolidone / acrylate copolymer, alkyl acrylate (e.g., butyl) / hydroxyalkyl acrylate (e.g., propyl) dimethicone copolymer, styrene / acrylate / ammonium methacrylate copolymer, acrylamide / sodium acryloyldimethyltaurate copolymer, etc.; water-soluble polysaccharides such as pectin, unmodified pullulan, or cellulose compounds; polyurethanes; latex; and mixtures thereof.

[0054] According to a preferred embodiment, at least one aqueous phase-forming polymer is at least one cyclic amide-containing polymer. Preferably, the at least one cyclic amide-containing polymer also has at least one, preferably both, of a cyclic amine and / or acrylamide functional group, but the at least one polymer may not contain either a cyclic amine or acrylamide functional group.

[0055] The cyclic amides and cyclic amine monomers useful in the first film-forming polymer include those having one or more aromatic or aliphatic ring structures. These rings may have a size ranging from about 3 to 10 ring members, for example, from 5 to 8.

[0056] In certain embodiments, monomers useful in forming these first film-forming polymers are polymerizable ethylenically unsaturated monomers having a cyclic amine residue or a cyclic amide residue. Therefore, the cyclic amide monomers of these first film-forming polymers may include cyclic amide residues that are heterocyclic ring structures or contain heterocyclic ring structures such as lactams. These may include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. In one preferred embodiment, the cyclic amide is pyrrolidone (γ-lactam), particularly vinylpyrrolidone.

[0057] Useful cyclic amine residues may include any of the various heterocyclic amines such as azoles, pyrroles, pyrrolidines, and carbamates. In one preferred embodiment, the cyclic amine residue is an imidazole.

[0058] In certain embodiments, useful acrylamide monomers in these first film-forming polymers include those having a -C3H5NO functional group. Examples include (meth)acrylamide.

[0059] As described above, the polymer containing at least one cyclic amide preferably also contains at least one, preferably both, of a cyclic amine and an acrylamide functional group, but the polymer may not contain either functional group. For example, polymers containing a cyclic amide residue but not containing a cyclic amine or acrylamide functional group include, but are not limited to, vinylpyrrolidone homopolymers (polyvinylpyrrolidone or PVP, for example, sold by BASF as Luviskol 30 or by Ashland as PVP K30L) and vinylpyrrolidone copolymers containing at least one monomer other than vinylpyrrolidone, such as a substituted or unsubstituted C2 (acrylic acid) or C3 (allyl) group, for example, vinylpyrrolidone / vinyl acetate (VP / VA) copolymers, for example, sold by Ashland as PVP / VA S 630 L.

[0060] In a particular embodiment, at least one cyclic amide-containing polymer has a mass-average molecular weight in the range of about 10,000 daltons to about 1,000,000 daltons, including all and partial ranges in between, such as 50,000 daltons to 500,000 daltons, 75,000 daltons to 300,000 daltons, and 100,000 daltons to 250,000 daltons.

[0061] In a particular embodiment, the polymer containing at least one cyclic amide is a copolymer of N-vinylpyrrolidone, methacrylamide, and N-vinylimidazole.

[0062] In certain embodiments, the cyclic amide-containing polymer may be a commercially available variety, such as Ludwigshafen or LUVISET CLEAR AT3, which is commercially available from BASF in Germany.

[0063] According to a preferred embodiment, the composition of the present invention lacks, does not contain, or substantially does not contain polyurethane.

[0064] Preferably, at least one aqueous phase-forming agent is present in the composition of the present invention in an amount ranging from about 0.5% to about 25% by mass, preferably about 1% to about 20% by mass, preferably more than 2% to about 20% by mass, and preferably about 2.5% to about 15% by mass, based on the mass of the composition, and includes all and partial ranges in between, such as 4% to 15%, 2.5% to 15%, 3% to 25%, etc. Preferably, at least one aqueous phase-forming agent is present in the composition of the present invention in an amount exceeding 1.5% by mass of the total mass of the composition.

[0065] Hydrophobic modified pullulan compounds The present invention provides a composition comprising one or more hydrophobic-modified pullulan compounds ("second film-forming polymer" or "second film-forming agent"). One or more of these second film-forming polymers, together with at least one cyclic amide-containing polymer, constitute part of a film-forming system. Optionally, other film-forming agents may be present in the film-forming system of the composition if desired.

[0066] Pullulan is a naturally occurring polysaccharide produced from starch by the fungus Aureobasidium pullulans. Pullulan is an alpha-glucan primarily composed of linearly linked maltotriose repeating units connected via alpha-1,6-glycosidic bonds. Natural pullulan is readily soluble in cold or warm water, forming a clear, viscous solution.

[0067] Pullulan can be produced, for example, from the fermentation of partially hydrolyzed starch or by using sucrose, sugarcane, milk, potatoes, and other sources of carbohydrate starting materials.

[0068] Preferably, the hydrophobic modified pullulan compounds of the present invention are oil-soluble. For example, preferred pullulan compounds of the present invention are modified with a hydrophobic group such as a siloxane group or a hydrocarbon group that confers oil solubility to the compound. Such modifications may include, for example, a silicone group such as a siloxysilyl group (-[-SiRR'-SiOR''R'''-]-) (wherein R, R', R'' and R''' are alkyl groups preferably containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms), or a hydrocarbon group of C8 or more (for example, a hydrocarbon group containing 8 to 24 carbon atoms, including intermediate and partial ranges such as 12 to 22 carbon atoms and 12 to 18 carbon atoms).

[0069] Preferred siloxane-modified pullulan compounds are as follows: pullulan-linker-siloxane group The structure corresponds to the following, where the siloxane group is preferably a C1-C6 alkyl-substituted siloxysilyl group such as a monoalkyl-substituted siloxysilyl group, a dialkyl-substituted siloxysilyl group, or a trialkyl-substituted siloxysilyl group, where the C1-C6 alkyl group is linear, cyclic, or branched, substituted, or unsubstituted. Here, the linker does not adversely affect either the film-forming properties or the oil-solubility properties of the compound. Preferably, the linker is an alkyl (-C-), ester or ether (-O-), amide or amine (-N-), or a combination thereof such as a carbamoyl group. Preferably, the linker is a carbamoyl group.

[0070] Preferably, the hydrophobic modified pullulan compound is trialkylsiloxysilylcarbamoyl pullulan, and a particularly preferred compound is trimethylsiloxysilylcarbamoyl pullulan.

[0071] Preferably, the hydrophobic modified pullulan compound in the composition of the present invention has a molecular weight of 50,000 to 10,000,000 daltons, preferably 100,000 to 5,000,000 daltons, preferably 250,000 to 1,000,000 daltons, and includes all and partial ranges in between, for example, 200,000 to 7,600,000 daltons, 350,000 to 8,750,000 daltons, 225,000 to 700,000 daltons, etc.

[0072] Preferably, at least one hydrophobic modified pullulan compound is present in the composition of the present invention in an amount ranging from about 0.5% to about 25% by mass, preferably about 1% to about 20% by mass, preferably about 2.5% to about 17.5% by mass, and preferably about 5% to about 15% by mass, based on the mass of the composition, and includes all and partial ranges in between, such as 4% to 14%, 1% to 15%, 5% to 25%, etc.

[0073] According to a preferred embodiment, at least one aqueous phase-forming agent and at least one hydrophobic-modified pullulan compound are present in the composition of the present invention in a mass ratio of about 3:1 to about 1:3, preferably about 2:1 to about 1:2, and preferably about 1:1.

[0074] aqueous phase A preferred embodiment of the present invention provides a composition comprising an aqueous phase solvent system containing (i) water in an amount of at least about 5% by mass relative to the total mass of the composition, and (ii) optionally at least one C2-C5 monoalcohol. Preferably, the composition is in the form of an emulsion having a continuous outer phase which is oil, preferably a water-in-oil (w / o) emulsion.

[0075] According to a preferred embodiment, the composition of the present invention contains water. Preferably, the composition contains at least about 10% by mass of water, preferably more than 20% by mass, preferably more than about 25% by mass, preferably more than about 30% by mass, preferably from about 10% to about 80% by mass, preferably more than 20% to about 75% by mass, preferably from about 25% to about 60% by mass, preferably from about 30% to about 50% by mass, and includes all and partial ranges in between, for example, from about 30% to about 60%.

[0076] If present, suitable C2-C5 monoalcohols include ethanol, propanol, butanol, pentanol, isopropanol, isobutanol, and isopentanol. Ethanol is particularly preferred.

[0077] Preferably, if present, C2-C5 monoalcohols are present in the composition of the present invention in an amount ranging from about 1% to about 50% by mass, preferably about 2.5% to about 40% by mass, preferably about 5% to about 30% by mass, and preferably about 5% to about 25% by mass, based on the total mass of the composition, including all and partial ranges in between, for example, about 1% to about 25%.

[0078] Preferably, the aqueous phase solvent system of the composition of the present invention essentially consists of water and optionally C2-C5 monoalcohols, or comprises them. Preferably, the aqueous phase solvent system "does not contain," "lacks," or "substantially does not contain" any solvent other than water and optionally C2-C5 monoalcohols.

[0079] Oil phase The present invention provides a composition comprising at least one oil. The composition of the present invention preferably comprises enough oil to form a water-in-oil emulsion, preferably about 5% to about 80% by mass of oil, more preferably about 10% to about 60% by mass of oil, and more preferably about 15% to about 40% by mass of oil, based on the total mass of the composition, and includes all and partial ranges therein.

[0080] Suitable oils include volatile and / or non-volatile oils. Such oils may be any acceptable oil, including, but are not limited to, silicone oils and / or hydrocarbon oils.

[0081] According to certain embodiments, the oil carrier comprises one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having a viscosity of 6 cSt or less at room temperature and containing 2 to 7 silicon atoms, wherein these silicones are optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that can be used in the present invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that can be used include KF 96A, a commercially available product from Shin Etsu with a viscosity of 6 cSt and a flash point of 94°C. Preferably, the volatile silicone oil has a flash point of at least 40°C.

[0082] A non-limiting list of volatile silicone oils is provided in Table 1 below.

[0083] [Table 1]

[0084] Furthermore, volatile linear silicone oils can be used in the present invention. Suitable volatile linear silicone oils include those described in U.S. Patent No. 6,338,839 and WO03 / 042221, the contents of which are incorporated herein by reference. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

[0085] According to other embodiments, the oil carrier comprises one or more non-silicone volatile oils, which can be selected from volatile hydrocarbon oils, volatile esters, and volatile ethers. Examples of such volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, particularly branched C8 to C6. 16 Alkanes, for example, from C8 to C 16 This includes isoalkanes (also known as isoparaffins), isododecanes, and oils sold under trade names such as Isopar or Permethyl. Preferably, the volatile non-silicone oil has a flash point of at least 40°C.

[0086] A non-limiting list of volatile non-silicone volatile oils is shown in Table 2 below.

[0087] [Table 2]

[0088] The volatility of the solvent / oil can be determined using the evaporation rates described in U.S. Patent No. 6,338,839, the contents of which are incorporated herein by reference.

[0089] 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: A hydrocarbon vegetable oil having a high triglyceride content, consisting of glycerol fatty acid esters, wherein the fatty acids may have various chain lengths, and these chains may be linear or branched, and saturated or unsaturated; these oils include, in particular, wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, mallow 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, kukui nut oil, passionflower oil or rosehip oil; or caprylic / capric acid triglyceride, for example, as sold by Stearineries Dubois or Dynamit These are sold by Nobel under the names Miglyol 810, 812, and 818; Synthetic oils or esters of the formula R5COOR6 (wherein R5 represents a linear or branched higher fatty acid residue containing 1 to 40 carbon atoms, for example, 7 to 19 carbon atoms, and R6 represents a branched hydrocarbon chain containing 1 to 40 carbon atoms, for example, 3 to 20 carbon atoms), such as Purcellin oil (cetostearyl octanoate), isononyl isononanoate, and C benzoate. 12 From C 15 Alkyl compounds, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates, or ricinoleates of alcohols or polyalcohols; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; Synthetic ethers containing 10 to 40 carbon atoms; C8 to C26 aliphatic alcohols, such as oleyl alcohol, cetyl alcohol, stearyl alcohol, and cetearyl alcohol; and A mixture of those.

[0090] Furthermore, examples of non-volatile oils that can be used in the present invention include, but are not limited to, branched and unbranched hydrocarbons and non-polar oils such as hydrocarbon waxes containing polyolefins, particularly petrolatum, paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

[0091] According to a preferred embodiment, the composition of the present invention lacks, does not contain, or substantially does not contain silicone oil.

[0092] According to a preferred embodiment, the composition of the present invention is wax-free, wax-free, or substantially wax-free.

[0093] Low HLB surfactants A preferred embodiment of the present invention provides a composition comprising at least one low-HLB surfactant. "HLB" refers to the "hydrophilic-lipophilic balance" related to emulsifiers / surfactants. In particular, the "HLB" value relates to the ratio of hydrophilic groups to lipophilic groups in the emulsifier and also relates to the solubility of the emulsifier. Emulsifiers with lower HLB typically have higher solubility in oil (lipophilic substances) and are more suitable for use in water-in-oil (W / O) emulsions. Emulsifiers with higher HLB typically have higher solubility in water (hydrophilic substances) and are more suitable for oil-in-water (O / W) emulsions. In relation to the present invention, "low-HLB surfactant" means a surfactant having an HLB value of 6 or less, preferably less than 5, and preferably less than 4. Preferably, the HLB value is 3 or more.

[0094] A low-HLB surfactant is present as all or part of the "surfactant component" in the composition of the present invention. According to a preferred embodiment of the present invention, the surfactant component has an HLB value of 6 or less, preferably less than 5, and preferably less than 4. Preferably, the HLB value is 3 or more.

[0095] According to a preferred embodiment, the low-HLB surfactant is nonionic.

[0096] According to a preferred embodiment, the low-HLB surfactant comprises a skeleton and pendant groups, wherein (1) the skeleton is hydrophobic and one or more pendant groups are hydrophilic, or (2) the skeleton is hydrophilic and one or more pendant groups are hydrophobic. The skeleton may be silicone-based or hydrocarbon-based. "Skeleton" means that the surfactant includes a main chain. "Pendant" group means that one or more groups are attached to the skeleton or main chain of the surfactant. The pendant groups may be silicone-based or hydrocarbon-based and may be attached to any position along the skeleton or main chain, for example, at one or both ends of the chain, at a position other than the ends of the chain, or to both. According to a preferred embodiment, the pendant groups include one or more ester groups attached to the skeleton or main chain.

[0097] A preferred skeleton is a hydrophobic skeleton such as one or more C8-C24 aliphatic compounds, preferably C12-C20 aliphatic compounds, preferably C16-C18 aliphatic compounds, such as stearate, isostearate, or laurate, and a preferred pendant group for such a skeleton is a hydrophilic group such as polyethylene glycol (PEG) polymer or polyglyceryl polymer.

[0098] Another preferred skeleton is a hydrophilic hydrocarbon skeleton such as polyethylene glycol (PEG) polymer or polyglyceryl polymer, and preferred pendant groups for such a skeleton are hydrophobic groups such as C8-C24 aliphatic compounds, preferably C12-C20 aliphatic compounds, and preferably C16-C18 aliphatic compounds, such as stearate, isostearate, laurate, etc.

[0099] The low-HLB surfactant of the present invention may preferably be a silicone surfactant containing dimethicone (e.g., PEG-10 dimethicone or lauryl PEG-9 polydimethylsiloxyethyl dimethicone), or a non-silicone surfactant that does not contain dimethicone (e.g., PEG-30 dihydroxystearate). The low-HLB surfactant of the present invention may have alkoxylation (e.g., ethoxylation or propoxylation) via a group such as (C2H4O)- / polyethylene glycol group (PEG), (C3H6O)- / polypropylene glycol group (PPG), etc. Suitable emulsifiers include alkoxylated compounds, partial glycerides of alkoxylated compounds, polyglycerolated compounds, and mixtures thereof. Polyglycerolated compounds are preferred.

[0100] Suitable polyglycerol compounds include, but are not limited to, compounds that preferably contain 2 to 20 glyceryl groups, preferably 3 to 15 glyceryl groups, and preferably 4 to 10 glyceryl groups. Diisostearate / polyhydroxystearate / sebacate polyglyceryl-4, sold by Evonik under the trade name Isolan GPS, is particularly preferred.

[0101] Particularly preferred low-HLB surfactants are as follows:

[0102] [Table 3]

[0103] At least one low-HLB surfactant is preferably present in the composition of the present invention in an amount of about 1% to about 15% by mass, preferably about 1.5% to about 10% by mass, and preferably about 2% to about 8% by mass, based on the total mass of the composition, and this range includes all and partial ranges therein.

[0104] Thickeners / Colorants / Activators Thickening agent A preferred embodiment of the present invention provides a composition further comprising at least one thickening agent. Suitable thickening agents include substances that thicken the oil phase of the composition, substances that thicken the aqueous phase of the composition, and mixtures thereof.

[0105] According to a preferred embodiment, the thickener is a gelling agent for gelling the water (aqueous phase) in the composition. Suitable gelling agents include, for example, clay and acrylic acid (co)polymers, high molecular weight homo- or copolymers (including several polymers specified as "carbomers") containing acrylic acid crosslinked with an optional polyalkenyl polyether, and any other gelling agent such as amphiphilic polymers. Preferably, the gelling agent is an amphiphilic polymer or clay, or a combination thereof.

[0106] In a preferred embodiment, the gelling agent may be at least one type of clay. Examples of clays include smectite clays such as laponite, kaolinite clays such as kaolinite, dickite, and nacrite, and optionally modified clays from the halloysite, dombassite, antigorite, bertierine, pyrophyllite, montmorillonite, beiderite, vermiculite, talc, stebbensite, hectorite, saponite, chlorite, sepiolite, and illite groups.

[0107] Clay is a product that is already well known, for example, in the publication "Mineralogie des argiles" ["Clay Mineralogy"], S. Caillere, S. Henin, M. Rautureau, 2nd edition, 1982, Masson, the teachings of which are included herein by reference.

[0108] Natural clay is a sedimentary rock composed mostly of certain minerals, generally aluminum silicates. Therefore, kaolin is a type of natural clay.

[0109] Clay can also be synthetic. Therefore, Sumecton, listed below, is a synthetic saponite.

[0110] The clay may also be chemically modified with various compounds, such as acrylic acid, polysaccharides (e.g., carboxymethylcellulose), or organic cations.

[0111] Preferably, in relation to the present invention, a keratinous substance and a cosmetically compatible and acceptable clay are used. Clays that can be mentioned in particular include kaolinite, montmorillonite, saponite, laponite, hectorite, and illite. Mixtures of clay and natural clays can also be used.

[0112] Examples of natural clays include green clay, which is particularly rich in illite; montmorillonite-rich clay, such as bentonite, also known as Fuller's clay; or kaolinite-rich white clay. Bentonite, or modified bentonite, is particularly known as Bentonite 38 VCG®, Bentonite Gel CAO V®, Bentonite 27 V®, Bentonite Gel ISD V, and Bentonite Gel MIO V®, which are sold by Elementis.

[0113] One example of a clay rich in montmorillonite is aluminum silicate hydrate, sold by Rockwood under the name Gel White H (registered trademark).

[0114] Examples of saponites belonging to the montmorillonite group include synthetic saponites, particularly the product sold by Kunimine under the name Sumecton®.

[0115] Examples of talc include Rose Talc® and Talc SG-2000® sold by Nippon Talc, Luzenac Pharma M® sold by Luzenac, J-68BC® from US Corporation, and Micro ACE-P-3® sold by Nippon Talc.

[0116] Preferably, if present, the thickener is present in the composition of the present invention in an amount ranging from about 0.1 to about 30% by mass, preferably 0.5 to 25% by mass, preferably 1 to 20% by mass, and preferably 2.5 to 15% by mass, where all masses are relative to the mass of the composition as a whole, and include all and partial ranges in between, for example, 0.1 to 1.5%, 2 to 20%, 10 to 20%, etc.

[0117] Activating agent According to a preferred embodiment of the present invention, a composition is provided which further comprises at least one activator. Preferably, the activator is present in the aqueous phase (hydrophilic activator), but the activator may be present in the oil phase (hydrophobic activator).

[0118] In some embodiments, the activator may be: Humectants, such as polyols, such as glycerin and sugars, urea and its derivatives, such as hydroxyalkylurea in particular, especially hydroxyalkylurea, and mixtures thereof; Desquamating agents are compounds that can directly act on desquamation by promoting exfoliation, such as β-hydroxy acids, especially 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; oligofucose; cinnamic acid; extracts of Sophora japonica; resveratrol and certain jasmonic acid derivatives; or compounds that can act on enzymes involved in the desquamation or degradation of corneodesmosomes, such as glycosidases, stratum corneum chymotrypsinase (SCCE), or other proteases (trypsin, chymotrypsin-like). Substances that chelate inorganic salts include: EDTA; N-acyl-N,N',N'-ethylenediaminetriacetic acid; aminosulfonic acid compounds, especially (N-2-hydroxyethylpiperazine-N-2-ethane)sulfonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) derivatives; α-amino acid derivatives of the glycine type (as described in EP-0 852 949 and sodium methylglycine diacetate sold by BASF under the trade name Trilon M); honey; and sugar derivatives such as O-octanoyl-6-D-maltose and N-acetylglucosamine. humectant; Anti-aging agents, which may include, for example, C-beta-D-xylopyranoside-2-hydroxypropane (Pro-Xylane), retinol, peptides, caffeine, and other ingredients that improve skin texture, any other suitable soluble / dispersible targeted active ingredients, and one or more combinations thereof.

[0119] Matte finish imparters, which may include, but are not limited to, matte finish imparters such as talc, silica, silicone elastomers, and polyamides, as well as waxes such as beeswax and carnauba palm (Copernicia cerifera) (carnauba) wax.

[0120] Antimicrobial agents, including non-exclusive examples, are 2,4,4'-trichloro-2'-hydroxydiphenyl ether (or triclosan), 3,4,4'-trichlorovanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, hexamidine isethionate, metronidazole and its salts, miconazole and its salts, itraconazole, terconazole, econazole, ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole, oxiconazole, sulfaconazole, and sulfo This includes nazole, terbinafine, cyclopirox, cyclopiroxolamine, undecylenic acid and its salts, benzoyl peroxide, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid, N-acetyl-L-cysteic acid, lipoic acid, azelaic acid and its salts, arachidonic acid, resorcinol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanilide, octopirox, octoxyglycerin, octanoylglycine, caprylyl glycol, 10-hydroxy-2-decanoic acid, dichlorophenylimidazole dioxolane and its derivatives (as described in patent WO 93 / 18743), farnesol and phytosphingosine, and mixtures thereof; Pigment modifiers and / or skin brightening agents, such as double-stranded RNA oligonucleotides, are useful for reducing tyrosinase expression. Ceramides, vitamin C and its derivatives, especially 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 (registered trademark) from Symrise, kiwi fruit (Actinidia chinensis) juice sold by Gattefosse, peony (Paeonia suffructicosa) root extract, for example the product sold by Ichimaru Pharcos under the name Botanpi Liquid B (registered trademark), brown sugar (succharum officinarum) extract, for example the honey extract sold by Taiyo Kagaku under the name Molasses Liquid, mixtures of undecylenic acid and undecylenoyl phenylalanine, for example Sepiwhite from Seppic MSH (registered trademark) can also be mentioned; Amino acids, such as arginine, histidine, methionine, lysine, proline, leucine, lysine, sarcosine, etc. Vitamins, such as vitamin A compounds like retinol or retinoic acid, vitamin B compounds like vitamin B1, B3, or B6, especially niacinamide, vitamin C compounds like ascorbyl phosphate (e.g., magnesium or sodium), and / or derivatives thereof; Ultraviolet (UV) shielding agents, such as aminobenzoic acid derivatives, dibenzoylmethane derivatives, salicylic acid derivatives, cinnamic acid derivatives, β,β-diphenyl acrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, and mixtures thereof. In particular, ethylhexyl methoxycinnamate sold by BASF under the trade name UVINUL MC 80 (registered trademark), ethylhexyl salicylate sold by SYMRISE under the trade name NEO HELIOPAN OS (registered trademark), and octocrylene sold by SYMRISE under the trade name NEO HELIOPAN 303 (registered trademark); and / or A combination of those.

[0121] Additional additives The compositions of the present invention may also contain any additives commonly used in the field under consideration. For example, additional film-forming agents (in addition to carbosiloxane dendrimer compounds and cyclic amide-containing polymers), waxes, dispersants such as poly(12-hydroxystearic acid), preservatives, fragrances, fillers, antioxidants, neutralizing agents, silicone elastomers, and mixtures thereof may be added. A non-exclusive enumeration of such components can be found in U.S. Patent Application Publication 2004 / 0170586, the full contents of which are incorporated herein by reference. Further examples of suitable additional components can be found in other references incorporated herein by reference. Further examples of such additional components can be found in the International Cosmetic Ingredient Dictionary and Handbook (9th edition, 2002). However, preferred embodiments of the present invention should be understood to include compositions that “do not contain,” “substantially do not contain,” or “lack” the components described in this paragraph, such as the additional film-forming agents and waxes and fillers previously mentioned, particularly matte-finishing fillers (compositions that “do not contain matte-finishing fillers,” “substantially do not contain matte-finishing fillers,” or “lack matte-finishing fillers”).

[0122] Those skilled in the art will carefully select optional additional additives and / or their amounts so that the advantageous properties of the compositions according to the present invention are not adversely affected or substantially affected by the intended additions.

[0123] These substances can be selected in various ways by those skilled in the art to prepare compositions having desired properties, such as consistency or texture.

[0124] Needless to say, the compositions of the present invention should be cosmetically or dermatologically acceptable, that is, they should contain non-toxic, physiologically acceptable media and be applicable to human skin.

[0125] Other preferred embodiments provide a method for treating, caring for, and / or improving the appearance of skin, comprising applying a composition of the present invention to the skin in an amount sufficient to treat, care for, and / or improve the appearance of the skin. According to these prior preferred embodiments, the composition of the present invention is applied topically to a desired area of ​​skin in an amount sufficient to treat, care for, and / or improve the appearance of the skin. The composition is applied to the desired area, preferably once or twice daily, more preferably once daily, and then preferably allowed to dry before being exposed to, for example, clothing or other items (e.g., a topcoat). Preferably, the composition is allowed to dry for about 1 minute or less, more preferably about 45 seconds or less. The composition is preferably applied to a desired area that is dry or dried before application, or to which a base coat has been previously applied.

[0126] According to one preferred embodiment of the present invention, a composition having improved cosmetic properties such as enhanced water resistance, sebum resistance, and / or migration resistance is provided. Preferably, the composition is a skin composition. Most preferably, the composition is a foundation further comprising at least one colorant, preferably a surface-treated pigment.

[0127] According to one preferred embodiment of the present invention, a method is provided for preparing a water-in-oil (w / o) emulsion composition, comprising the step of combining (adding) at least one hydrophobic-modified pullulan compound and at least one aqueous phase-forming agent during the preparation of the emulsion composition. Preferably, the composition is a skin composition. Preferably, at least one hydrophobic-modified pullulan compound and at least one aqueous phase-forming agent are combined or added in the amounts and / or ratios described above. Most preferably, the composition is a foundation further comprising at least one colorant, preferably a surface-treated pigment.

[0128] A preferred embodiment of the present invention provides a kit comprising, as separate compositions in one or more containers within the kit, (A) at least one composition of the present invention described above, particularly a foundation, comprising at least one hydrophobic-modified pullulan compound and at least one aqueous phase-forming agent, and (B) at least one other composition, such as a primer coat composition, a base coat composition, or a top coat composition. Compositions (A) and (B) may be contained in different parts or compartments of the same container within the kit. However, compositions (A) and (B) may also be present in different containers within the kit.

[0129] Particularly preferred embodiments include the following:

[0130] A water-in-oil emulsion composition comprising (a) water, (b) at least one oil, (c) at least one hydrophobic modified pullulan compound, and (d) at least one aqueous phase film-forming agent.

[0131] (e) The composition according to the preceding embodiment, further comprising at least one compound selected from the group consisting of at least one thickener, at least one colorant, and at least one activator, preferably at least two of the thickener, colorant, and activator are present in the composition, and preferably all three of the thickener, colorant, and activator are present in the composition.

[0132] The composition according to any of the preceding embodiments, wherein at least one thickening agent is present in the composition, and at least one thickening agent is clay, preferably hectorite.

[0133] The composition according to any of the preceding embodiments, wherein at least one coloring agent is present in the composition, and at least one coloring agent is a surface-treated pigment.

[0134] The composition according to any of the preceding embodiments, wherein at least one activator is present in the composition, and at least one activator is a vitamin, preferably a vitamin B compound.

[0135] The composition according to any of the preceding embodiments, wherein at least one hydrophobic modified pullulan compound is a siloxane-modified pullulan compound, preferably trimethylsiloxysilylcarbamoyl pullulan.

[0136] The composition according to any of the preceding embodiments, wherein at least one aqueous phase-forming agent is at least one cyclic amide-containing polymer, preferably a copolymer of N-vinylpyrrolidone, methacrylamide, and N-vinylimidazole, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, or a mixture thereof.

[0137] The composition according to any of the preceding embodiments, wherein the mass ratio of the aqueous phase film-forming agent to the hydrophobic modified pullulan compound is about 3:1 to about 1:3, preferably about 1:1.

[0138] The composition according to any of the preceding embodiments, wherein water is present in an amount exceeding 20% ​​by mass of the total mass of the composition, preferably between about 25% by mass and 60% by mass of the total mass of the composition.

[0139] A water-in-oil emulsion composition comprising (a) water, (b) at least one volatile hydrocarbon oil, (c) at least one siloxane-modified pullulan compound, (d) at least one cyclic amide-containing polymer, (e) at least one thickener which is clay, (f) at least one surface-treated pigment, and (g) at least one vitamin compound.

[0140] A method for applying makeup to skin, comprising the step of applying a composition described in any of the preceding embodiments to the skin in an amount sufficient to apply makeup to the skin.

[0141] Unless otherwise indicated, all numbers used in this specification and in the claims to represent quantities of components, reaction conditions, etc., should be understood in all cases to be modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described in the following specification and in the appended claims are approximate values ​​that may vary depending on the desired properties to be obtained by the present invention.

[0142] The numerical ranges and parameters describing the broad scope of this invention are approximations, but the numerical values ​​described in the specific examples are reported as accurately as possible. However, each numerical value inherently contains a certain degree of error that inevitably arises from the standard deviation observed in each measurement. The following examples are intended to illustrate the invention and, as a result, do not limit its scope. Percentages are given on a mass basis. [Examples]

[0143] (Example 1) Sample of W / O emulsion foundation formulation

[0144] [Table 4]

[0145] (Example 2) Example of a W / O emulsion foundation

[0146] [Table 5]

[0147] (Example 3) Comparison of 60° gloss values ​​for oil-phase and oil-phase + aqueous-phase combined film-forming foundations. Simple foundation formulations were prepared containing a constant concentration of pullulan compound (TSPL) in isododecane combined with an activated aqueous film-forming agent (Luviset, VP / VA, PVP) at a concentration of 0.87% or 2.61%. Films of each composition A, B, D, E, F, G, and H were created on opaque cards using a 6 mil drawdown bar. The films were then dried in an oven at 32°C, and the gloss on the black side of the card was measured with a BYK trigloss meter. As reflected in the table below, formulations containing both the oil phase (TSPL) and the aqueous film-forming agent were observed to exhibit reduced gloss values ​​compared to the oil phase film-forming agent alone (composition A) when measured at 60°C.

[0148] [Table 6]

[0149] (Example 4) Comparison of 60° gloss values ​​for foundations containing artificial sebum. The same simple foundation formulations tested in Example 3 were mixed in a speed mixer with 95% formulation + 5% artificial sebum, and then each film was created on an opaque card using a 6 mil drawdown bar. The films were then dried in an oven at 32°C, and the gloss on the black side of the card was measured with a BYK trigloss meter. As reflected in the table below, formulations containing both the oil phase (TSPL) and the aqueous phase film-forming agent were observed to show reduced gloss values ​​when measured at 60°C compared to formulations containing the oil phase film-forming agent alone.

[0150] [Table 7]

[0151] (Example 5) The 60° gloss value of the foundation as the concentration of the aqueous film-forming agent increases. Simple foundation formulations A, B, C, and D were prepared, each containing a constant concentration of pullulan compound (TSPL) in isododecane combined with Luviset AT Clear 3 film-forming agent with active polymer content of 0%, 0.87%, 1.74%, or 2.61%. Each film was prepared on an opaque card using a 6-mil drawdown bar. Separate films were prepared from the base foundation to produce a 95% / 5% mixture of foundation and artificial sebum. The films were then dried in an oven at 32°C, and the gloss on the black side of the card was measured using a BYK trigloss meter. Formulations containing both oil-phase (TSPL) and aqueous-phase (Luviset) film-forming agents were observed to exhibit reduced gloss values ​​compared to the oil-phase film-forming agent alone (measured at 60°C). In addition, it was observed that increasing the concentration of the aqueous-phase film-forming agent resulted in a concentration-dependent decrease in gloss values.

[0152] [Table 8]

[0153] (Example 6) The 85° gloss value of the foundation increases with increasing concentration of the aqueous film-forming agent. Example 5 was repeated and measured at 85°. It was observed that formulations containing both oil-phase (TSPL) and aqueous-phase (Luviset) film-forming agents showed reduced gloss values ​​compared to the oil-phase film-forming agent alone. In addition, it was observed that increasing the concentration of the aqueous-phase film-forming agent resulted in a concentration-dependent decrease in gloss values.

[0154] [Table 9]

[0155] (Example 7) Dry migration test The following compositions were prepared.

[0156] [Table 10]

[0157] 20 μL of foundation compositions A and J were applied to the bare skin of the forearm in a 2.5 cm x 2.5 cm square area and allowed to dry for 45 minutes. The foundations were then wiped off five times in alternating directions with consistent pressure using an ISO 105 F09 clock square. Foundation containing both TSPL and Luviset (composition J) was found to have higher resistance to breakdown and migration under friction compared to foundation without Luviset (composition A).

[0158] (Example 8) Resistance to friction in the presence of sebum The following compositions were prepared.

[0159] [Table 11]

[0160] 20 μL of compositions K and L were applied to a white artificial protein leather substrate in a 3.2 cm × 3.2 cm square using a nitrile gloved finger. The sample was dried in an oven at 32°C. The sample was then read using a spectrophotometer to obtain the CIE LAB values ​​for the initial substrate and the substrate + foundation. An ISO 105 F09 clock square was immersed in artificial sebum, and excess sebum was absorbed with a lint-free paper wipe. The sample was then rubbed twice in alternating directions with consistent force. The sample was then dried for at least 6 hours and read again to obtain the LAB value of the foundation color after rubbing. Using the L value, the following formula was used:

[0161]

number

[0162] (In the formula, ABS = absolute value. L-Final = The final L value in the LAB color space of the sediment. Initial L = the initial L value of the sediment. L base material = L value of the base material (supplare, artificial protein leather), (Normalized ΔL = percentage change in the darkness of the makeup product) The normalized ΔL was calculated from this.

[0163] As reflected in the table below, foundations containing aqueous film-forming agents showed significantly less change in L value compared to foundations containing TSPL alone, demonstrating resistance to friction in the presence of sebum.

[0164] [Table 12]

Claims

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

2. (e) The composition according to claim 1, further comprising at least one compound selected from the group consisting of at least one thickener, at least one colorant, and at least one activator, preferably at least two of the thickener, colorant, and activator are present in the composition, and preferably all three of the thickener, colorant, and activator are present in the composition.

3. The composition according to claim 2, wherein at least one thickening agent is present in the composition, and at least one thickening agent is clay, preferably hectorite.

4. The composition according to claim 2, wherein at least one coloring agent is present in the composition, and at least one coloring agent is a surface-treated pigment.

5. The composition according to claim 2, wherein at least one activator is present in the composition, and at least one activator is a vitamin, preferably a vitamin B compound.

6. The composition according to any one of claims 1 to 5, wherein at least one hydrophobic modified pullulan compound is a siloxane-modified pullulan compound, preferably trimethylsiloxysilylcarbamoyl pullulan.

7. The composition according to any one of claims 1 to 6, wherein at least one aqueous phase-forming agent is at least one cyclic amide-containing polymer, preferably a copolymer of N-vinylpyrrolidone, methacrylamide, and N-vinylimidazole, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, or a mixture thereof.

8. The composition according to any one of claims 1 to 7, wherein the mass ratio of the aqueous phase film-forming agent to the hydrophobic modified pullulan compound is about 3:1 to about 1:3, preferably about 1:

1.

9. The composition according to any one of claims 1 to 8, wherein water is present in an amount exceeding 20% ​​by mass relative to the total mass of the composition, preferably between about 25% by mass and 60% by mass relative to the total mass of the composition.

10. A method for applying makeup to skin, comprising the step of applying a composition according to any one of claims 1 to 9 to the skin in an amount sufficient to apply makeup to the skin.

11. A water-in-oil emulsion composition comprising (a) water, (b) at least one volatile hydrocarbon oil, (c) at least one siloxane-modified pullulan compound, (d) at least one cyclic amide-containing polymer, (e) at least one thickener which is clay, (f) at least one surface-treated pigment, and (g) at least one vitamin compound.

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