Cosmetic composition in the form of a water-in-oil emulsion with a high non-volatile oil content and comprising a liposoluble polymer based on modified pullulan

Abstract

Cosmetic composition in the form of a water-in-oil emulsion with a high level of non-volatile oil and comprising a liposoluble polymer based on modified pullulan The invention relates to a cosmetic composition, and more particularly to a foundation composition, in the form of a water-in-oil emulsion comprising a liposoluble polymer based on modified pullulan and a mixture of volatile oil and non-volatile oil with a high level of non-volatile oil, which does not transfer and guarantees prolonged hold over time. The present invention also relates to a process for preparing a cosmetic composition according to the invention, as well as a makeup and / or skin care process comprising a step of applying a cosmetic composition according to the invention to the skin.

Description

Title of the invention: Cosmetic composition in the form of a water-in-oil emulsion with a high non-volatile oil content and comprising a liposoluble polymer based on modified pullulan Technical field

[0001] The present invention relates to a cosmetic composition, and more particularly a foundation composition, in the form of a water-in-oil emulsion comprising a liposoluble polymer based on modified pullulan and a mixture of volatile oil and non-volatile oil with a high level of non-volatile oil, which does not transfer and guarantees prolonged hold over time. The present invention also relates to a process for preparing a cosmetic composition according to the invention, as well as a makeup and / or skin care process comprising a step of applying a cosmetic composition according to the invention to the skin.

[0002] Foundation compositions are used to beautify and make irregularities and pores disappear in the skin. To maintain a beautiful finish throughout the day, these compositions must have a lasting effect over time.

[0003] Since the COVID 19 pandemic and with the wearing of masks, the absence of transfer of a foundation onto the mask, also referred to as a "non-transfer" property, has become an important property for consumers, in addition to the hold and durability characteristics mentioned above. These foundation compositions may include chemical sunscreens, which provide sun protection. It is known that chemical sunscreens in oily form degrade the non-transfer properties of foundation formulas, which are then less attractive to consumers.

[0004] Thus, the object of the present invention is to provide a cosmetic composition having not only a long-lasting effect, high covering power and a comfortable finish, but also an excellent non-transfer effect on a material (for example a mask) which would be in contact with the skin. The composition of the invention also makes it possible to achieve a high level of UV resistance (sun protection) when it incorporates a sun filter.

[0005] The inventors have succeeded in combining all these properties by using a liposoluble polymer based on pullulan modified by a hydrophobic group in combination with a high level of non-volatile oil mixed with a volatile oil, which leads to better homogeneity of the film obtained, which does not transfer and provides good hold throughout the day. The good compatibility of the liposoluble polymer mixture / non-volatile oil also ensures, when the composition also includes a sunscreen, a high SPF level. The good compatibility between the sunscreen and its dispersion medium makes it possible to obtain a more homogeneous film and to achieve a higher level of sun protection, which is not the case with cosmetic formulas containing a large quantity of volatile oils. In addition, limiting the level of volatile oils improves the tolerance of the cosmetic composition of the invention on the skin, comfort (more comfortable and less dry film), and the maintenance of hydration.

[0006] Pullulan derivatives modified by a hydrophobic group such as those of the invention have already been described in makeup compositions. For example, the Applicant has already described in application WO 2019 / 115949 the use of trialkylsiloxysilylcarbamoyl pullulan in combination with a silicone polymer, a mattifying filler and a volatile oil, in mascara compositions which are easy to apply and have improved flexibility and hold over time. Application KR2015100201 also describes very soft water-in-oil cosmetic compositions based on urethane polymer, of one or more species chosen from a silicone resin, trimethylsiloxysilylcarbamoyl pullulan and an acrylic silicone copolymer, and a silicone gum or a silicone polymer.

[0007] The use of pullulan modified by a hydrophobic group according to the invention in the presence of a mixture of volatile oil and non-volatile oil and with a high level of non-volatile oil, to improve the properties of non-transfer, durability and sun protection, has however never been described, nor suggested, in the state of the art. General description of the invention

[0008] The present invention has as its first subject a cosmetic composition comprising: - at least one liposoluble polymer selected from pullulans modified by at least one hydrophobic group, - at least one non-volatile oil, - at least one volatile oil, and the non-volatile oil representing at least 15% by weight relative to the total weight of the composition.

[0009] The cosmetic composition of the present invention is a water-in-oil type (W / O type) emulsion cosmetic composition.

[0010] In the following description, a liposoluble polymer, also called a liposoluble film-forming polymer, is a polymer soluble in a fatty phase comprising solid, liquid or pasty fatty substances, and which is capable of forming a film after evaporation of the volatile materials present in said fatty phase.

[0011] For the purposes of the present invention, the term “solid or pasty fatty substance” means a solid compound or comprising a solid fraction at 25°C, such as butters, waxes, pasty compounds, and mixtures thereof. Pasty compounds are non-crystalline fatty compounds comprising a solid fraction and a liquid fraction at 25°C. For the purposes of the present invention, the term “liquid fatty body” means an oil.

[0012] In the following description, a water-soluble polymer, also called a water-soluble film-forming polymer, is a polymer which is soluble in an aqueous phase and which is capable of forming a film after evaporation of the volatile materials present in said aqueous phase.

[0013] The liposoluble polymer of the invention is a pullulan modified by a silicone group and / or a hydrocarbon group.

[0014] In one embodiment, the liposoluble polymer is a pullulan modified with a silicone group selected from trialkylsiloxysilylcarbamoyl pullulans.

[0015] For the purposes of the present invention, the term "alkyl" means a saturated, linear or branched, C1-C20, preferably C1-C2, and more preferably C1-C6, hydrocarbon aliphatic group. The term "branched" means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkyl chain. As alkyl groups, mention may be made, for example, of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and n-pentyl groups.

[0016] Thus, the liposoluble polymer of the invention is advantageously a pullulan modified by a silicone group selected from trialkylsiloxysilylcarbamoyl pullulans preferably carrying a C1-C6 alkyl group. In this embodiment, the liposoluble polymer is more preferably TRIMETHYLSILOXY-SILYLCARBAMOYL PULLULAN (INCI name), for example marketed by the company SHIN ETSU under the trade name TSPL-30-ID-F.

[0017] In another embodiment, the liposoluble polymer is a pullulan modified by a hydrocarbon group selected from pullulans modified by a C12-C18 hydrocarbon group. In this embodiment, the liposoluble polymer is more preferably MYRISTOYL PULLULAN (INCI name), marketed for example by the company KATAKURA.

[0018] In an advantageous embodiment, the liposoluble polymer selected from pullulans modified by at least one hydrophobic group represents from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, and more preferably from 0.5 to 12% by weight, relative to the total weight of the cosmetic composition.

[0019] The cosmetic composition of the invention also comprises at least one non-volatile oil and at least one volatile oil, the non-volatile oil representing at least 15% by weight relative to the total weight of the cosmetic composition.

[0020] These non-volatile and volatile oils can be of vegetable, mineral or synthetic origin. According to an alternative embodiment, oils of vegetable origin are preferred.

[0021] For the purposes of the present invention, the term "volatile oil" means an oil having lost 4% by weight or more, preferably 5% by weight or more, more preferably 8% by weight or more, and even more preferably 20% by weight or more, relative to the total weight of said oil, after 60 minutes in an enclosure at 33°C and 50% humidity, following the protocol described in the following paragraph. The high rate of volatile phase, and in particular of volatile oils, makes it possible to have a light composition, which is easily applied to the skin. The volatile oils participate in the positioning of the film on the skin during application, and when they evaporate, they leave the film adhering to the skin, with a sensation of bare skin, without a material effect, nor a mask effect on the skin.

[0022] Protocol for determining whether an oil is volatile:

[0023] 20 mg of the oil to be studied are weighed on a 5cm x 5cm PMMA plate at using a micropipette and a precision balance. This material is spread with the finger over the entire plate. The plate is then placed in a ventilated chamber thermostatically controlled at 33°C and 50% humidity. For each material, the test is carried out three times. The loss in mass during drying is measured after 60 minutes. The mass lost is expressed according to the following formula:

[0024] [Math.l] % lost “ —1—:—— x ISO in which:

[0025] mtx corresponds to the remaining mass at the measured time (t = 60 minutes), and

[0026] mt0 corresponds to the mass initially applied.

[0027] The volatile oil of the invention may be a hydrocarbon oil. The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms. These oils may optionally comprise oxygen atoms (for example in ester groups), nitrogen, sulfur and / or phosphorus, for example, in the form of hydroxyl or acid radicals.

[0028] The volatile oil of the invention may be a hydrocarbon oil selected from linear C8-C16 alkanes such as nonane, decane, undecane, tridecane, tetradecane, pentadecane, branched C8-C16 alkanes such as isododecane, isodecane, isohexadecane, and mixtures of these alkanes.

[0029] In a preferred embodiment, the alkanes used in the context of the invention can be obtained from bio-sourced raw materials. The alkanes of the invention can thus be obtained from vegetable oils, from conventional chemical processes, such as those derived from synthetic biology obtained from sugar. Examples that may be mentioned are processes for producing alkanes linear or branched from palm oil, palm kernel oil or coconut oil to produce mixtures of alkanes comprising at least 12 carbon atoms (for example C1-C13 or C15-C19). A process is also known for the manufacture of bio-sourced isododecane by enzymatic fermentation from a glucose-rich sugar syrup. These processes make it possible to obtain mixtures of linear and / or branched alkanes whose relative volatility gives them particularly interesting properties in the field of makeup products, and in particular foundations, which are applied to the skin.

[0030] In one embodiment, the volatile oil of the invention consists of at least two distinct linear alkanes, each in C8-C16, and differing from each other by at least two carbon atoms. The presence of these two distinct linear alkanes, each in C8-C16, and differing from each other by at least two carbon atoms, makes it possible to adjust and optimize the volatility of the composition, which allows good placement of the cosmetic composition once the makeup film is applied to the skin and controlled evaporation of the linear alkanes in C8-C16, to obtain the desired hold.

[0031] According to a particular embodiment of the invention, the volatile oil of the invention consists of at least two distinct linear alkanes, each C8-C16, and differing from each other by at least two carbon atoms, chosen from the group consisting of nonane, docane, undecane, dodecane, tridecane and tetradecane, pentadecane, hexadecane, mixtures of C9-C13 alkanes, mixtures of C9-C12 alkanes, mixtures of C10-C12 alkanes, mixtures of C11-C13 alkanes, mixtures of C12-C14 alkanes, and mixtures thereof.

[0032] In particular, the following C9-C14 alkanes and mixtures of alkanes will be mentioned: - Cl 1-C13, such as a mixture of undecane and tridecane, marketed by BASF Care Créations under the trade name Cetiol® Ultimate, - C9-C12, C10-C12, C12-C14, such as those marketed by BIOSYNTHIS under the name VEGELIGHT® SILK (INCI name: C9-12 ALKANE), VEGELIGHT® 1214LC, - n-dodecane (C12) and n-tetradecane (C14), notably sold by Sasol under the references PARAFOL® 12-97 and PARAFOL® 14-97 respectively, and - their mixtures.

[0033] When the volatile oil consists of linear C8-C16 alkanes, the content of C8-C16 alkanes preferably represents from 15 to 25% by weight, preferably from 16 to 22%, by weight relative to the total weight of the cosmetic composition.

[0034] According to a particular embodiment of the invention, the volatile oil consists of a mixture of C9-C12 alkanes and a mixture of C11-C13 alkanes. In this embodiment, the content of C9-C12 alkanes preferably represents from 10 to 20% by weight relative to the total weight of the cosmetic composition, and the content of C9-C12 alkanes C1-C13 preferably represents from 5 to 10% by weight relative to the total weight of the cosmetic composition. In this embodiment, the volatile oil of the invention preferably comprises a total content of linear C9-C12 alkanes greater than the total content of linear C1-C13 alkanes, in particular a total content of linear C9-C12 alkanes ranging from 1 to 3 times the total content by weight of linear C1-C13 alkanes, relative to the total weight of linear C9-C13 alkanes.

[0035] The volatile oil is advantageously a volatile hydrocarbon oil whose weight loss measured by following the protocol described above, after 60 minutes in an enclosure at 33°C and 50% humidity, is greater than or equal to 60%, and preferably greater than or equal to 80%, relative to the total weight of said oil. Particularly advantageously, the volatile oil is isododecane.

[0036] In an advantageous embodiment, the volatile oil represents less than 25% by weight, preferably 5 to 20% by weight, and more preferably 10 to 15% by weight, relative to the total weight of the cosmetic composition.

[0037] For the purposes of the present invention, the term "non-volatile oil" means an oil which does not meet the definition of "volatile oil" within the meaning of the invention, as indicated above. In other words, the term "non-volatile oil" means an oil which has lost less than 4% by weight, relative to the total weight of said oil, after 60 minutes in an enclosure at 33°C and 50% humidity, following the protocol described above.

[0038] The non-volatile oil of the invention can be selected from: - silicone oils, and preferably selected from linear silicone oils, such as dimethicone, in particular dimethicone 5cS (25°C), and aromatic silicone oils such as phenyl trimethicone, trimethyl pentaphenyl trisiloxane, and mixtures thereof, - dialkyl ethers of the following formula R1-O-R2, RI and R2 representing C4-C20, preferably C6-C12, alkyl chains, identical or different, linear or branched, saturated or unsaturated, - linear or branched alkanes comprising at least 17 carbon atoms, such as squalane, liquid paraffin, petroleum jelly, polybutene, polyisobutene, hydrogenated polyisobutene, hydrogenated polydecene, olefin oligomers, and mixtures thereof, - carbonates of formula R3-OC(=O)-O-R4, R3 and R4 being C4-C20, preferably C6-C12, alkyl chains, identical or different, linear or branched, saturated or unsaturated, - esters, and preferably mono-, di-, or triesters of C6-C20 carboxylic acids and C4-C20 alcohols, preferably C6-C12, identical or different, linear or branched, saturated or unsaturated, and preferably fatty acid esters of propylene glycol such as propylene glycol dicaprylate and propylene glycol dicaprate; fatty acid alkyl esters such as ethylhexyl palmitate, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, coco caprylates / caprates and isononyl isononanoate; carbonic acid esters such as dicaprylyl carbonate; fatty acid esters of polyglycerols, such as polyglyceryl-2 triisostearate, polyglyceryl-2 tetraisostearate and polyglyceryl-10 decaisostearate; tri-fatty acid esters of glycerin such as glyceryl triethylhexanoate, glyceryl tribehenate, glyceryl tri(caprylate / caprate) and triheptanoin (also known as triglyceride oils); benzoic acid derivatives such as dii-sostearyl malate and alkyl benzoate; salicylic acid derivatives such as homosalates and ethylhexyl salicylate;cinnamic acid derivatives such as octyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, cinnoxate, ethylhexyl methoxycinnamate, diisopropyl methylcinnamate, glyceryl hexanoate-ethyl-dimethoxy cinnamate and di-(2-ethylhexyl)-4'-methoxybenzalmalonate, and mixtures thereof; - fatty alcohols advantageously comprising a C12-C26 chain, linear or branched, saturated or unsaturated, preferably octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol, - higher fatty acids such as oleic acid, linoleic acid, linolenic acid, and - mixtures thereof.

[0039] For the purposes of the invention, the term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

[0040] The non-volatile oil is advantageously selected from dimethicone, in particular dimethicone 5cS (25°C), phenyl trimethicone, trimethyl pentaphenyl trisiloxane, capric / caprylic triglyceride, dicaprylyl ether, dicaprylyl carbonate, coconut caprylates / caprates, triheptanoin, ethylhexyl salicylate, and mixtures thereof.

[0041] The non-volatile oil represents at least 15% by weight, preferably from 15 to 30% by weight, more preferably from 15 to 25% by weight, and even more preferably from 15 to 20% by weight, relative to the total weight of the cosmetic composition.

[0042] In one embodiment, the volatile oil / non-volatile oil weight ratio varies from 1 / 5 to 4 / 5, and preferably from 2 / 3 to 3 / 4.

[0043] In a preferred embodiment, the cosmetic composition of the invention further comprises at least one water-soluble polymer.

[0044] In the following description, a water-soluble polymer, also called a water-soluble film-forming polymer, is a polymer that is soluble in an aqueous phase, and which is capable of forming a film after evaporation of the volatile materials present in said aqueous phase.

[0045] The water-soluble polymer of the invention is preferably a polysaccharide, more preferably selected from CHITOSAN, PULLULAN, HYDROXYPROPYL STARCH, TAPIOCA STARCH, their derivatives, and their mixtures.

[0046] The chitosan (INCI name: CHITOSAN) that can be used in the context of the invention can be a fully or partially deacetylated chitin. The molecular mass of the chitosan used can vary from 1,000 to approximately 5,000,000 g.mol1, preferably from 5,000 to 700,000 g.mol', and more preferably from 10,000 to 100,000 g.mol'. The degree of deacetylation of the chitosan can preferably vary from 50 to 99%. The chitosan of the invention is advantageously selected from chitosan of fungal origin (CHITOSAN FUNGAL) or crustacean origin, for example from crabs, lobsters, squid or shrimp. In a particularly preferred embodiment, the chitosan of the invention is fungal chitosan (CHITOSAN FUNGAL).

[0047] The pullulan (INCI name: PULLULAN) of the invention is a natural polysaccharide (ose polymer) consisting of maltotriose units (a glucose triholoside), also known as alpha-1,4-; alpha-1,6-glucan. The three glucose units that make up maltotriose are linked by an alpha-1,4-type osidic bond, while the maltotrioses are connected to each other by alpha-1,6-type osidic bonds. The pullulan of the invention is produced from starch by the fungus Aureobasidiumpullulans.

[0048] The hydroxypropyl starch (INCI name: HYDROXYPROPYL STARCH) of the invention advantageously has a weight-average molecular weight greater than 106 Da, and advantageously from 106 to 109 Da. The weight-average molecular weight can be determined by HPSEC-MALLS (high-performance size exclusion chromatography coupled in-line with multi-angle laser light scattering detection). The hydroxypropyl starch of the invention is marketed for example by the company ROQUETTE.

[0049] The tapioca starch (INCI name: TAPIOCA STARCH) of the invention comes from the roots of bitter cassava and consists of starch.

[0050] The derivatives of the water-soluble polymers of the invention may be CHITOSAN PCA, CHITOSAN LACTATE, N-CARBOXYBUTYL CHITOSAN and HYDROXYPROPYL CHITOSAN (HPCS).

[0051] In an advantageous embodiment, the water-soluble polymer selected from chitosan (CHITOSAN), pullulan (PULLULAN), hydroxypropyl starch (HYDROXYPROPYL STARCH), tapioca starch (TAPIOCA STARCH), their derivatives, and their mixtures, represents from 0.01 to 7% by weight, preferably from 0.05 to 5% by weight, and more preferably from 0.1 to 3% by weight, relative to the total weight of the composition.

[0052] In a preferred embodiment, the cosmetic composition of the invention comprises: - TRIMETHYLSILOXYSILYLCARBAMOYL PULLULAN, as a fat-soluble polymer, and - chitosan (CHITOSAN), pullulan (PULLULAN), their derivatives, or their mixtures, as a water-soluble polymer.

[0053] In another preferred embodiment, the cosmetic composition of the invention comprises:

[0054] - MYRISTOYL PULLULAN, as a liposoluble polymer, and - chitosan (CHITOSAN), hydroxypropyl starch (HYDROXYPROPYL STARCH), pullulan (PULLULAN), their derivatives, or their mixtures, as a water-soluble polymer.

[0055] The cosmetic composition of the invention may also comprise at least one UV filter, preferably selected from liposoluble organic UV filters, hydrophilic organic UV filters, mineral UV filters, and mixtures thereof.

[0056] By "hydrophilic organic UV filter" is meant any organic compound absorbing ultraviolet (UV) radiation in the wavelength range from 280 nm to 400 nm which can be dissolved in the aqueous phase of the cosmetic composition of the invention, or which can be dispersed therein in colloidal form or in semi-cellular form.

[0057] By "liposoluble organic UV filter" is meant any organic compound absorbing UV radiation in the wavelength range from 280 nm to 400 nm which can be dissolved in the molecular state in an oil, or be dispersed in an oil in colloidal form or in micellar form.

[0058] In an advantageous embodiment, the organic UV filter represents from 0.05 to 10% by weight, preferably from 0.1 to 8% by weight, and more preferably from 0.5 to 5% by weight, relative to the total weight of the cosmetic composition.

[0059] The cosmetic composition of the invention may also comprise at least one surfactant such as conventional ionic, non-ionic, amphoteric, zwit-terionic surfactants. The surfactant may be an alkylated derivative of polyglycerol, an alkylated polyethylene glycol, an alkylated derivative of sorbitan, a metal salt of fatty acids, a silicone surfactant. In a preferred embodiment, the surfactant of the invention is preferably an alkylated polyethylene glycol, a polyglycerol ester, or their mixture, more preferably selected from POLYGLYCERYL-3 DIISOSTEARATE, POLYGLYCERYL-3 POLYRICINOLEATE, CETYL PEG / PPG-10 / 1 DL METHICONE AND HEXADECENE AND PENTAERYTHRITYL TETRA- DI-T-BUTYL HYDROXYHYDROCINNAMATE (marketed by EVONIK under the trade name ABIL® EM180), PEG-9 POLYDIMETHYLSI-LOXYETHYL DIMETHICONE (marketed by SHIN-ETSU under the trade name KF-6028), LAURYL PEG-9 POLYDIMETHYLSILOXYETHYL-DIMETHICONE AND TOCOPHEROL (marketed by SHIN-ETSU under the trade name KF-6038), and mixtures thereof. In a more preferred embodiment, the surfactant of the invention is a polyglycerol ester, and more preferably selected from POLYGLYCERYL-3 DIISOSTEARATE, POLY-GLYCERYL-3 POLYRICINOLEATE, and mixtures thereof.

[0060] In an advantageous embodiment, the surfactant represents from 0.1 to 5%, preferably from 0.5 to 4%, and more preferably from 1 to 3% by weight, relative to the total weight of the cosmetic composition.

[0061] The cosmetic composition of the invention also comprises water, preferably in an amount ranging from 5 to 60% by weight, more preferably from 10 to 50% by weight, and even more preferably from 15 to 40% by weight, relative to the total weight of the cosmetic composition.

[0062] According to one embodiment, the cosmetic composition of the invention may further comprise at least one cosmetic active agent. The cosmetic active agent may in particular be advantageously chosen from a moisturizing agent, an anti-wrinkle agent, an antioxidant agent, a whitening agent, a depigmenting agent. In one of its aspects, the cosmetic composition of the invention may contain at least one cosmetic active agent in a proportion ranging from 0.01 to 5% by weight, relative to the total weight of the cosmetic composition.

[0063] According to one embodiment, the cosmetic composition of the invention may further comprise cosmetic ingredients such as solid fillers, preservatives, perfumes, coloring materials.

[0064] The coloring materials (or coloring agents) are advantageously chosen from pigments and nacres. The particles constituting the pigments and nacres preferably have a diameter not exceeding 200 μm, and even more preferably not exceeding 150 μm.

[0065] By "pigments" is meant white or colored particles, mineral or organic, coated or not, insoluble in an aqueous phase, intended to color and / or opacify the composition containing them. Among the pigments that can be used in the cosmetic composition of the invention, mention may be made of titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, carbon black, and mixtures thereof. It may also be a pigment having a structure that may be, for example, of the sericite / iron oxide type. brown / titanium dioxide / silica. It may also be pigments having a structure which may be, for example, of the silica microsphere type containing iron oxide. Advantageously, the pigments of the invention are iron oxides and / or titanium dioxides.

[0066] By "nacres" is meant colored particles of any shape, iridescent or not, in particular produced by certain molluscs in their shell or synthesized, and which have a color effect by optical interference. Among the nacres that can be used in the film-forming composition of the invention, mention may be made of white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic coloring materials.Examples of mother-of-pearls include natural mica coated with titanium dioxide, iron oxide, natural pigment, or bismuth oxychloride. Mother-of-pearls may more specifically have a yellow, pink, red, bronze, orange, brown, gold, and / or coppery color or reflection. Advantageously, mother-of-pearls are micas coated with titanium dioxide or iron oxide, as well as bismuth oxychloride.

[0067] The coloring matter may be treated with an organic agent which is deposited on the surface of the coloring matter by solvent evaporation, chemical reaction, or creation of covalent bonds between the organic agent and the coloring matter. Advantageously, the organic agent is a silicone or an amino acid. The coloring matter is preferably a pigment coated with a layer of silicone, more preferably with a layer of methicone, dimethicone (also called polydimethylsiloxane (PDMS)), hydrogenated dimethicone, a dimethicone-methicone copolymer, an acrylate-dimethicone copolymer, and even more preferably with a layer of dimethicone. Particularly advantageously, the coloring matter is a pigment chosen from iron oxides and / or titanium dioxides, coated in a layer of dimethicone.

[0068] According to an advantageous embodiment of the invention, the cosmetic composition of the invention is a foundation composition, a care cream or a care base, and preferably a foundation composition.

[0069] Another subject of the invention relates to a process for preparing a cosmetic composition according to the invention, comprising the following steps: (i) preparation of a mixture comprising at least one liposoluble polymer selected from pullulans modified by at least one hydrophobic group, and at least one non-volatile oil and at least one volatile oil, and optionally at least one water-soluble polymer selected from chitosan (CHITOSAN), pullulan (PULLULAN), hydroxypropyl starch (HYDROXYPROPYL STARCH), tapioca starch (TAPIOCA STARCH), their derivatives, and their mixtures, and at least one UV filter, and (ii) dispersion of the mixture obtained in step (i) in an aqueous phase optionally comprising one or more cosmetic active ingredients and / or excipients.

[0070] The liposoluble polymer, the volatile oil, the non-volatile oil, the optional water-soluble polymer, and the optional UV filter, mixed during step (i) of the process of the invention are as defined according to the invention.

[0071] Another subject of the invention relates to a method for making up and / or caring for the skin and / or protecting the skin against UV rays, comprising a step of applying a composition according to the invention to at least one part of the body and / or the face.

[0072] In addition to the preceding provisions, the invention also comprises other provisions which will emerge from the additional description which follows, which relates to the preparation of film-forming compositions according to the invention and of a comparative composition.

[0073] Examples:

[0074] In the examples, and unless otherwise indicated, all percentages are given as percentages by weight, the ingredients designated by their INCI name, and the temperature indicated in degrees Celsius.

[0075] Example 1:

[0076] A foundation composition 1 according to the invention corresponding to the formula of Table 1 was prepared.

[0077] [Tables 1] Phases Ingredients % A METHYL TRIMETHICONE 13.7 A PHENYL TRIMETHICONE 6.5 A ETHYLHEXYL SALICYLATE 4.5 A PEG-9 POLYDIMETHYLSILOXYETHYL DL METHICONE 4.5 A TRIMETHYL PENTAPHENYL TRISILOXANE 3.8 A ISODODECANE 3.5 A DIMETHICONE 5cS (25°C) 3.1 A MYRISTOYL PULLULAN 2.0 A CETYL DIMETHICONE 1.5 A TITANIUM DIOXIDE 4.2 A TITANIUM DIOXIDE (AND) SODIUM MYRISTOL GLUTAMATE (AND) ALUMINUM HYDROXIDE 8.4 A IRON OXIDES SunPURO® 4.2 A CELLULOSE 0.5 A CETYL PEG / PPG-10 / 1 DIMETHICONE 0.5 A DISTEARDIMONIUM HECTORITE 0.4 A SODIUM MYRISTOYL GLUTAMATE 0.4 B ALCOHOL 96.2% VOL 10.0 B VEGETABLE GLYCEROL 5.0 B BUTYLENE GLYCOL 3.0 B PULLULAN 1.0 B CHLORPHENESIN 0.2 B PURIFIED WATER QSP 100

[0078] The composition was prepared according to the following method:

[0079] The ingredients of the fatty phase A including the pullulan derivative were weighed in a main beaker, then mixed using a VMLRAYNERY stirrer at room temperature (20°C). The mineral pigments were weighed into a cup, passed through a three-roll mill, and then dispersed in the main beaker using an ULTRA-TURRAX™ disperser. The compounds of aqueous phase B were weighed into a beaker, then dispersed with VMI-RAYNERY at room temperature (20°C). After obtaining a homogeneous mixture, phase B was dispersed in phase A at 800 rpm for 30 minutes.

[0080] Composition 1 comprises the following non-volatile oils: PHENYL TRL METHICONE, ETHYLHEXYL SALICYLATE, TRIMETHYL PENTAPHENYL TRISILOXANE and DIMETHICONE 5cS (25°C), which represent 17.85% by weight of the total weight of composition 1.

[0081] Evaluation of Non-Transfer Properties in Vivo

[0082] The in vivo Non-Transfer properties of the foundation composition prepared in Example 1 were evaluated according to the following test:

[0083] The in vivo Non-Transfer test was performed on four panelists.

[0084] The foundation composition was applied to the forearm on an area of 5x5 cm - 50 mg of foundation, then dried for 15 minutes. A tissue was then applied to the spread foundation composition by applying pressure with the hand (100 g).

[0085] Visual evaluation of the transfer on the handkerchief:

[0086] Evaluation criteria:

[0087] +++: no transfer

[0088] ++: very slight transfer

[0089] +: slight transfer

[0090] x: transfer on the handkerchief

[0091] Results of the in vivo Non-Transfer test:

[0092] [Tables2] Composition Liposoluble polymer Water-soluble polymer No In vivo transfer 1 MYRISTOYL PULLULAN: 2% PULLULAN: 1% ++ Example 2:

[0093] A foundation composition 2 according to the invention corresponding to the formula in Table 3 was prepared in the same way as in Example 1:

[0094] [Tables3] Phases Ingredients % A METHYL TRIMETHICONE 9.7 A PHENYL TRIMETHICONE 6.5 A ETHYLHEXYL SALICYLATE 4.5 A PEG-9 POLYDIMETHYLSILOXYETHYL DL METHICONE 4.5 A TRIMETHYL PENTAPHENYL TRISILOXANE 3.8 A ISODODECANE 8.3 A DIMETHICONE 5cS (25°C) 3.1 A MYRISTOYL PULLULAN 2.0 A CETYL DIMETHICONE 1.5 A TITANIUM DIOXIDE 4.5 A TITANIUM DIOXIDE (AND) SODIUM MYRISTOL GLUTAMATE (AND) ALUMINUM HYDROXIDE 13.0 A IRON OXIDES SunPURO® 4.2 A CELLULOSE 0.5 A CETYL PEG / PPG-10 / 1 DIMETHICONE 0.5 A DISTEARDIMONIUM HECTORITE 0.4 A SODIUM MYRISTOYL GLUTAMATE 0.4 B ALCOHOL 96.2% VOL 10.0 B VEGETABLE GLYCEROL 5.0 B CHLORPHENESIN 0.2 B PURIFIED WATER QSP 100

[0095] Composition 2 comprises the following non-volatile oils: PHENYL TRL METHICONE, ETHYLHEXYL SALICYLATE, TRIMETHYL PENTAPHENYL TRISILOXANE and DIMETHICONE 5cS (25°C), which represent 17.9% by weight of the total weight of composition 2.

[0096] The in vivo Non-Transfer properties of the foundation compositions prepared in Example 2 and the Comparative Example were evaluated according to the test described in Example 1.

[0097] Comparative example:

[0098] A comparative foundation composition was prepared in the same way as in Example 2, replacing the 2.0% by weight of MYRISTOYL PULLULAN with 5% by weight of Shin-Etsu KP-549 fat-soluble polymer (METHYL TRIMETHICONE (AND) ACRYLATES / DIMETHICONE COPOLYMER) (at 40% solids).

[0099] Results of the in vivo Non-Transfer test:

[0100] [Tables4] Composition Polymère liposoluble Non Transfert in vivo 2 MYRISTOYL PULLULAN ++ Comparative METHYL TRIMETHICONE (AND) ACRYLATES / DL METHICONE COPOLYMER X

Claims

Claims

1. Cosmetic composition in water-in-oil form characterized in that it comprises: - at least one liposoluble polymer selected from pullulans modified by at least one hydrophobic group, - at least one non-volatile oil, - at least one volatile oil, and the non-volatile oil representing at least 15% by weight relative to the total weight of the composition.

2. Composition according to claim 1, characterized in that the liposoluble polymer is a pullulan modified by a silicone group and / or a hydrocarbon group.

3. Composition according to claim 1 or claim 2, characterized in that the liposoluble polymer is a pullulan modified by a silicone group selected from trialkylsiloxysilyl-carbamoyl pullulans preferably carrying a C1-C6 alkyl group, said liposoluble polymer more preferably being TRIMETHYLSL LOXYSILYLCARBAMOYL PULLULAN.

4. Composition according to claim 1 or claim 2, characterized in that the liposoluble polymer is a pullulan modified by a hydrocarbon group selected from pullulans modified by a C12-C18 hydrocarbon group, said liposoluble polymer more preferably being MYRISTOYL PULLULAN.

5. Composition according to one of claims 1 to 4, characterized in that it further comprises at least one water-soluble polymer, preferably a polysaccharide, even more preferably selected from CHITOSAN, PULLULAN, HYDROXYPROPYL STARCH, TAPIOCA STARCH, their derivatives, and their mixtures.

6. Composition according to one of claims 1 to 5, characterized in that the non-volatile oil is an oil having lost less than 4% by weight, relative to the total weight of said oil, after 60 minutes in an enclosure at 33°C and 50% humidity.

7. Composition according to one of claims 1 to 6, characterized in that the non-volatile oil is selected from: - silicone oils, preferably selected from linear silicone oils, such as dimethicone, in particular dimethicone 5cS (25°C), and aromatic silicone oils such as phenyl tri- methicone, trimethyl pentaphenyl trisiloxane, and mixtures thereof, - dialkyl ethers of the following formula R1-O-R2, RI and R2 representing C4-C20, preferably C6-C12, alkyl chains, identical or different, linear or branched, saturated or unsaturated, - linear or branched alkanes comprising at least 17 carbon atoms, such as squalane, liquid paraffin, petrolatum, polybutene, polyisobutene, hydrogenated polyisobutene, hydrogenated polydecene, olefin oligomers, and mixtures thereof, - carbonates of formula R3-OC(=O)-O-R4, R3 and R4 being C4-C20, preferably C6-C12, alkyl chains, identical or different, linear or branched, saturated or unsaturated, - esters, and preferably mono-, di-, or triesters of C6-C20 carboxylic acids and C4-C20 alcohols, preferably C6-C12, identical or different, linear or branched, saturated or unsaturated, and preferably fatty acid esters of propylene glycol such as propylene glycol dicaprylate and propylene glycol dicaprate; fatty acid alkyl esters such as ethylhexyl palmitate, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, coco caprylates / caprates and isononyl isononanoate; carbonic acid esters such as dicaprylyl carbonate; polyglycerol fatty acid esters, such as polyglyceryl-2 triisostearate, polyglyceryl-2 tetraisostearate and polyglyceryl-10 decaisostearate;tri-fatty acid esters of glycerin such as glyceryl triethylhexanoate, glyceryl tribehenate, glyceryl tri(caprylate / caprate) and tri-heptanoin (also known as triglyceride oils); benzoic acid derivatives such as diisostearyl malate and alkyl benzoate; salicylic acid derivatives such as homosalates and ethylhexyl salicylate; cinnamic acid derivatives such as octyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, cinnoxate, ethylhexyl methoxycinnamate, diisopropyl methylcinnamate, glyceryl hexanoate-ethyl-dimethoxy cinnamate and di-(2-ethylhexyl)-4'-methoxybenzalmalonate, and mixtures thereof; - fatty alcohols advantageously comprising a C12-26 chain, linear or branched, saturated or unsaturated, preferably octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol, - higher fatty acids such as oleic acid, linoleic acid, linolenic acid, and - mixtures thereof, the non-volatile oil being more preferably selected from dimethicone, in particular dimethicone 5cS (25°C), phenyl tri-methicone, trimethyl pentaphenyl trisiloxane, capric / caprylic triglyceride, dicaprylyl ether, dicaprylyl carbonate, coconut caprylates / caprates, triheptanoin, ethylhexyl salicylate, and mixtures thereof.

8. Composition according to one of claims 1 to 7, characterized in that the volatile oil is an oil having lost 4% by weight or more, preferably 5% by weight or more, more preferably 8% by weight or more, and even more preferably 20% by weight or more, relative to the total weight of said oil, after 60 minutes in an enclosure at 33°C and 50% humidity.

9. Composition according to one of claims 1 to 8, characterized in that the volatile oil is selected from hydrocarbon oils selected from linear C8-C16 alkanes such as nonane, decane, undecane, tridecane, tetradecane, pentadecane, branched C8-C16 alkanes such as isododecane, isodecane, isohexadecane, and mixtures of these alkanes, the volatile oil preferably being isododecane.

10. Composition according to one of claims 1 to 9, characterized in that it comprises at least one UV filter, preferably selected from liposoluble organic UV filters, hydrophilic organic UV filters, mineral UV filters, and mixtures thereof.

11. Composition according to one of claims 1 to 10, characterized in that it comprises at least one surfactant selected from conventional ionic, non-ionic, amphoteric, zwitterionic surfactants, preferably alkylated derivatives of polyglycerol, alkylated polyethylene glycols, alkylated derivatives of sorbitan, metal salts of fatty acids, silicone surfactants, and more preferably polyglycerol esters selected from POLYGLYCERYL-3 DIL SOSTEARATE, POLYGLYCERYL-3 POLYRICINOLEATE, and their mixture.

12. Composition according to one of claims 1 to 11, characterized in that the liposoluble polymer represents from 0.05 to 20% by weight, preferably from 0.1 to 15% by weight, and more preferably from 0.5 to 12% by weight, relative to the total weight of the composition.

13. Composition according to one of claims 1 to 12, characterized in that the water-soluble polymer represents from 0.01 to 7% by weight, preferably from 0.05 to 5% by weight, and more preferably from 0.1 to 3% by weight, relative to the total weight of the composition.

14. Composition according to one of claims 1 to 13, characterized in that the non-volatile oil represents from 15 to 30%, preferably from 15 to 25% by weight, and more preferably from 15 to 20%, relative to the total weight of the composition.

15. Composition according to one of claims 1 to 14, characterized in that the volatile oil represents less than 25% by weight, preferably 1 to 20% by weight, more preferably 5 to 15% by weight, and even more preferably 10 to 15% by weight, relative to the total weight of the composition.

16. Composition according to one of claims 1 to 15, characterized in that the surfactant represents from 0.1 to 5%, preferably from 0.5 to 4%, and more preferably from 1 to 3% by weight, relative to the total weight of the composition.

17. Composition according to one of claims 1 to 16, characterized in that it comprises water, preferably in an amount ranging from 5 to 60% by weight, preferably from 10 to 50% by weight, and more preferably from 15 to 40% by weight, relative to the total weight of the composition.

18. Composition according to one of claims 1 to 17, characterized in that it is a foundation composition, a care cream or a care base, and preferably a foundation composition.

19. Process for preparing a cosmetic composition according to one of claims 1 to 18, characterized in that it comprises the following steps: (i) preparation of a mixture comprising at least one liposoluble polymer, at least one non-volatile oil, at least one volatile oil, and optionally at least one water-soluble polymer and at least one UV filter, as defined according to one of claims 1 to 18, and (ii) dispersion of the mixture obtained in step (i) in an aqueous phase optionally comprising one or more cosmetic active ingredients and / or excipients.

20. Method for making up and / or caring for the skin, characterized in that it comprises a step of applying a composition according to one of the re- claims 1 to 18, on at least one part of the body and / or face.