Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/042—Gels
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
  • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
  • A61Q1/06—Lipsticks
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes

Definitions

• Cosmetic composition comprising a dispersion of polymer particles and a dispersion of pigments
• the present invention relates to a composition containing a polymer dispersible in an oily phase, intended in particular for the cosmetic field. More specifically, the invention relates to a composition for caring for and / or making up and / or treating keratin materials such as the skin of the face as well as of the human body, including the scalp, the integuments such as the eyelashes, eyebrows, nails and hair but also lips, lower or upper eyelids of humans.
• This composition leads in particular to a shiny, homogeneous and non-sticky deposit on the keratin materials and / or the lips.
• compositions for making up or caring for the skin or the lips of human beings such as foundations or lipsticks generally contain fatty phases such as waxes and oils, pigments and / or fillers and optionally additives such as cosmetic or dermatological active ingredients. They can also contain so-called "pasty" products, of flexible consistency, making it possible to obtain pastes, colored or not, to be applied with a brush.
• compositions tend to migrate, that is to say to propagate over time inside the wrinkles and fine lines of the skin which surround in particular the lips and the eyes, causing an unsightly effect.
• This migration is often cited by women as a major defect in conventional lipsticks.
• migration is meant an overflow of the composition and in particular of the color, outside the initial trace of the makeup.
• it exhibits poor resistance over time and in particular to color.
• This poor behavior is characterized by a change in color (toning, paling) generally as a result of an interaction with the sebum and sweat secreted by the skin in the case of foundation and make-up or of an interaction with saliva. in the case of lipsticks.
• This poor behavior requires the user to make-up very often, which can be a waste of time.
• compositions containing a siloxysilicate resin (with three-dimensional network), a volatile silicone oil with a cyclic silicone chain and powdery charges Although having improved hold properties have the disadvantage of leaving on the lips, after evaporation of the silicone oils, a film which becomes uncomfortable over time (feeling of drying and tightness), eliminating a certain number of women of this type of lipstick.
• compositions based on silicone oils and silicone resins lead to matt colored films.
• women are now looking for products, in particular lip gloss, that are shiny.
• composition is in solid form because it then has an inhomogeneous appearance in terms of color. In particular, white streaks are observed.
• composition is a makeup product. Indeed, the makeup obtained is inhomogeneous and unsightly, accentuating the defects of the support and in particular of the skin, which is quite the opposite of what consumers are looking for.
• the subject of the invention is precisely a composition for caring for and / or making up and / or treating keratin materials such as the skin and / or integuments but also the lips and the face, making it possible to remedy the various drawbacks mentioned above.
• the composition of the invention makes it possible to obtain a non-sticky deposit, of good coverage having a more or less shiny appearance, adapted to the desire of the consumer, not migrating and of good behavior, not drying out the skin or lips to which it is applied, both during application and over time. It also has good stability properties and, when it is in the form of a stick, a limitation in color heterogeneity. It thus allows a homogeneous and aesthetic makeup.
• the invention applies not only to lip makeup products but also to lip care and / or treatment products such as balms, skin, including the scalp, such as daily care and protection creams.
• lip care and / or treatment products such as balms, skin, including the scalp, such as daily care and protection creams.
• of the facial skin to make-up products for the skin, both of the face and of the human body, such as foundations, in particular cast in stick or in a cup, concealer products and ephemeral tattoo products, body hygiene products such as deodorants, in particular sticks, and eye makeup products, such as eyeliners, in particular in the form of a pencil, and mascaras, in particular in the form of bread.
• the applicant has " found, quite surprisingly, that the use of a polymer dispersible in an oily phase, associated with a colloidal dispersion of particularly colored solid particles, in a composition in particular cosmetic, made it possible to obtain a glossy film, very good hold, of uniform color, non-migrating, water-resistant, while being very pleasant to apply and to wear throughout the day.
• the film is in particular flexible, flexible and
• the present invention therefore relates to a composition for application to keratin materials, comprising a physiologically acceptable medium containing at least one liquid fatty phase, a colloidal dispersion of particles solid at room temperature and a dispersion of polymer particles stabilized on the surface. in said liquid fatty phase by a stabilizer.
• liquid fatty phase in the sense of the request, is meant any non-aqueous medium liquid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg), corn- applied with one or more fatty substances liquid at room temperature, also called oils.
• This fatty phase is macroscopically homogeneous (that is to say homogeneous when naked).
• This fatty phase may contain a volatile liquid fatty phase and / or a non-volatile fatty phase.
• non-volatile fatty phase any medium capable of remaining on the skin or the lips for several hours.
• a nonvolatile fatty phase has in particular a vapor pressure at ambient temperature and atmospheric pressure, non-zero less than 0.02 mm Hg and better still less than 10 "3 mm Hg.
• volatile fatty phase any non-aqueous medium capable of evaporating from the skin or the lips, in less than an hour at room temperature and atmospheric pressure.
• This volatile phase notably comprises oils having a vapor pressure, at ambient temperature (25 ° C) and atmospheric pressure (760mm Hg) ranging from 10 '3 to 300 mm Hg (0.3 Pa to 40,000 Pa), particular ranging from 0.02 to 300 mm Hg (2.66 Pa to 40,000 Pa).
• This composition is in particular a cosmetic, dermatological, hygienic or pharmaceutical composition. It therefore contains ingredients compatible with the skin, lips and integuments such as keratin fibers. It can be in the form of an anhydrous gel, an oil-in-water or water-in-oil emulsion or dispersion or also in the form of a multiple emulsion. It can be in the form of a paste, a more or less rigid solid, cream, ointment. Preferably, it is in anhydrous form, and more especially in the form of an anhydrous gel, in particular poured in a stick or in a dish.
• this composition is stable over time and at temperature.
• no segregation of the dispersed solid particles nor any phase shift is observed, even after 2 months at ambient temperature and atmospheric pressure and at 45 ° C.
• its appearance to the naked eye is homogeneous and free from white streaks.
• the polymer is a solid insoluble in (a fatty phase even at its softening temperature, unlike a wax even of polymeric origin which is soluble in the fatty phase at its melting temperature. furthermore, allows the formation of a deposit which is in particular continuous and homogeneous film-forming and / or is characterized by the entanglement of the polymer chains.With the same wax obtained by polymerization, recrystallization is obtained after melting in the fatty phase. This recrystallization is in particular responsible for the loss of the gloss of the composition.
• the polymer in dispersion used in the present invention can be of any kind. It is thus possible to use a radical polymer, a polycondensate, or even a polymer of natural origin and their mixtures. This polymer can be chosen by a person skilled in the art according to its properties and according to the subsequent application desired for the composition.
• the polymer used is film-forming, that is to say capable of forming, alone or in combination with a plasticizing agent, an isolable film. It is however possible to use a non-film-forming polymer.
• non-film-forming polymer means a polymer which is not capable of forming, on its own, an isolable film.
• This polymer makes it possible, in association with a non-volatile compound of the oil type, to form a continuous and homogeneous deposit on the skin and / or the lips.
• the composition contains at least one ingredient chosen from cosmetic, dermatological, hygienic and pharmaceutical active ingredients, coloring matters and their mixtures. Thanks to the dispersion of polymer particles stabilized on the surface present in the liquid fatty phase, the composition of the invention makes it possible to maintain these active agents and / or coloring matters where they have been deposited.
• the quantity of polymer in dispersion must be sufficient to form on the skin and / or the lips and / or the keratin fibers a film capable of trapping the coloring matters and or the cosmetic or dermatological active agents and / or the oils. with a view to limiting their migration and increasing the hold of the composition.
• the amount of polymer is a function of the amount of coloring matter and / or active ingredients and / or oils, contained in the composition. In practice, the amount of polymer can be greater than 2% by weight (in active material), relative to the total weight of the composition.
• Another subject of the invention is the cosmetic use in a composition for application to the skin, the hares and the integuments and more particularly cosmetic, hygienic or the use for the manufacture of a dermatological or pharmaceutical composition for application to the skin, the lips and the integuments, of particles of at least one polymer dispersed in a liquid fatty phase and stabilized on the surface by a stabilizing agent and of a colloidal dispersion of solid particles at room temperature, in particular colored to limit the migration of the composition and / or increase its resistance over time and / or obtain a homogeneous make-up and / or maintain the gloss of said composition.
• the subject of the invention is also a method of cosmetic care or of making up keratin materials and in particular of the lips, integuments or of the skin, consisting in applying to the lips, the integuments or the skin respectively, a cosmetic composition as defined above.
• the subject of the invention is also a cosmetic method for limiting the migration of a makeup or care composition for the skin or the lips and / or increasing the resistance over time of this composition and / or its stability, containing a phase liquid fat and at least one ingredient chosen from coloring matters in the form of solid particles at room temperature, colored, consisting in introducing into the liquid fatty phase particles of polymer dispersible in the liquid fatty phase and surface stabilized by an agent stabilizing and introducing into said liquid fatty phase said colored particles in the form of a colloidal dispersion.
• a subject of the invention is also a process for the manufacture of a stable composition for application to keratin materials, comprising introducing into a physiologically acceptable liquid medium a) a dispersion of polymer particles stabilized at the surface in a phase fatty liquid by a stabilizer, b) a colloidal dispersion of particles welded at room temperature, chosen from pigments, nacres and (es fillers and their mixtures and to mix said medium supplemented with said dispersions a) and b).
• the dispersion of polymer particles stabilized on the surface by a stabilizer and the colloidal dispersion of solid particles are prepared separately and beforehand, before their introduction into the composition.
• Another subject of the invention is the use of a colloidal dispersion of solid particles at room temperature, chosen from pigments, nacres, fillers and their mixtures in a composition for application to keratin materials, containing a dispersion of polymer particles stabilized on the surface in a liquid fatty phase with a stabilizer, to stabilize said composition and / or give it a homogeneous appearance.
• An advantage of the use of a polymer particle dispersion in a compo- "sition of the invention is that these particles remain in the form of elementary particles, without forming agglomerates in the fatty phase.
• Another advantage of the polymer dispersion is the possibility of obtaining very fluid compositions (of the order of 130 centipoises), even in the presence of a high level of polymer.
• Yet another advantage of such a polymer dispersion is that it is possible to calibrate the size of the polymer particles at will, and to modulate their "polydispersity" in size during the synthesis. It is thus possible to obtain particles of very small size, which are invisible to the naked eye when they are in the composition and when they are applied to the skin or the lips.
• composition according to the invention exhibits qualities of spreading and adhesion to the skin, the lips, the eyelashes or the mucous membranes, which are particularly advantageous, as well as a smooth and pleasant touch.
• This composition also has the advantage of removing makeup easily, in particular with a conventional cleansing milk.
• composition according to the invention therefore advantageously comprises one or more stable dispersions of particles of generally spherical polymers of one or more polymers, in a physiologically acceptable liquid fatty phase.
• These dispersions are generally called NAD (Non-Aqueous Dispersion) of polymer by opposition to latexes which are aqueous dispersions of polymer.
• These dispersions can in particular be in the form of nanoparticles of polymers in stable dispersion in said fatty phase.
• the nanoparticles are preferably of a size between 5 and 600 nm. It is however possible to obtain polymer particle sizes of up to 1 ⁇ m.
• Another advantage of the polymer dispersion of the composition of the invention is the possibility of varying the glass-transition temperature (Tg) of the polymer or of the polymer system (polymer more additive of the plasticizer type), and thus to pass d a hard polymer to a more or less soft polymer, making it possible to adjust the mechanical properties of the composition as a function of the intended application and in particular of the film deposited.
• Tg glass-transition temperature
• the dispersion polymers which can be used in the composition of the invention preferably have a molecular weight of the order of 2000 to 10 000 000 and a Tg of -100 ° C to 300 ° C and better still of -50 ° to 50 ° C , preferably from -10 ° C to 100 ° C.
• a plasticizer can be associated with it so as to lower this temperature of the mixture used.
• the plasticizer can be chosen from the plasticizers commonly used in the field of application and in particular from the compounds capable of being solvents for the polymer. It is possible to use film-forming polymers, preferably having a low Tg, less than or equal to the skin temperature and in particular less than or equal to 40 ° C. A dispersion is thus obtained which can film when applied to a support, which is not the case when dispersions of mineral pigments according to the prior art are used.
• film-forming polymers mention may be made of radical, acrylic or vinyl homopolymers or copolymers, preferably having a Tg of less than or equal to 40 ° C and in particular ranging from - 10 ° to 30 ° C, used alone or as a mixture.
• radical, vinyl or acrylic homopolymers or copolymers optionally crosslinked, preferably having a Tg greater than 40 ° C and in particular ranging from 45 ° to 150 ° C, used alone or as a mixture.
• radical polymer is meant a polymer obtained by polymerization of unsaturated monomers, in particular ethylenic, each monomer being capable of homopolymerizing (unlike polycondensates).
• the radical polymers can be in particular vinyl polymers or copolymers, in particular acrylic polymers.
• the vinyl polymers can result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acid monomers and / or amides of these acids.
• monomer carrying an acid group ⁇ , ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid can be used.
• (meth) acrylic acid and crotonic acid are used, and more preferably (meth) acrylic acid.
• esters of acidic monomers are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), such as alkyl (meth) acrylates, in particular C 1 -C 20 alkyl, of preferably in Cj-Cg, aryl (meth) acrylates, in particular C 6 -C 10 aryl, hydroxyalkyl (meth) acrylates, in particular C 2 -C 6 hydroxyalkyl.
• alkyl (meth) acrylates mention may be made of methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryie (meth) acrylate.
• hydroxyalkyl (meth) acrylates mention may be made of hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
• aryl (meth) acrylates mention may be made of benzyl or phenyl acrylate.
• esters of (meth) acrylic acid are alkyl (meth) acrylates.
• radical polymer use is preferably made of copolymers of (meth) acrylic acid and of (meth) acrylate, in particular C 1 -C alkyl. More preferably, methyl acrylates may be used, optionally copolymerized with acrylic acid.
• amides of the acid monomers mention may be made of (meth) acrylamides, and in particular N-alkyl (nneth) acrylamides, in particular of C 2 -C 12 alkyl such as N-ethyl acrylamide, Nt-butyl acrylamide , N-octyl acrylamide; N-dialkyl (CC 4 ) (meth) acrylamides.
• the vinyl polymers can also result from the polymerization of ethylenically unsaturated monomers having at least one amino group, in free form or else partially or totally neutralized, or even partially or totally quaternized.
• Such monomers can be, for example, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl ethacrylamide, vinylamine, vinylpyridine, d.allyldimethylammonium chloride.
• the vinyl polymers can also result from the homopolymerization or from the copolyerization of at least one monomer chosen from vinyl esters and styrene monomers.
• these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.
• vinyl esters include vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.
• styrene monomers mention may be made of styrene and aipha-methyl styrene.
• - olefins such as ethylene, propylene, butylene, isoprene, butadiene.
• the vinyl polymer can be crosslinked using one or more difunctional monomers, in particular comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate or diallyl phthalate.
• the dispersion polymers of the invention can be chosen from the following polymers or copolymers: polyurethanes, polyurethanes-acrylics, polyureas, polyurea-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyesters, polyester amides, polyesters fatty chain, alkyds; acrylic and / or vinyl polymers or copolymers; acrylic-silicone copolymers; polyacrylamides; silicone polymers such as polyurethanes or silicone acrylics, fluoropolymers and mixtures thereof.
• the polymer (s) in oily dispersion can represent (in dry matter or active material) from 0.1 to 60% of the weight of the composition, preferably from 2 to 40% and better still from 4 to 25%.
• the amount of dry matter in the dispersion represents the total amount of polymer + stabilizer.
• the liquid fatty phase of the composition can consist of any cosmetically or dermatologically acceptable oil, and generally physiologically acceptable oil, in particular chosen from oils of mineral, animal, vegetable or synthetic origin, carbonaceous, hydrocarbonaceous, fluorinated and / or silicone-based, alone or as a mixture insofar as they form a homogeneous and macroscopically stable mixture and where they are compatible with the intended use.
• hydrocarbon-based oil is meant oils mainly containing carbon atoms and hydrogen atoms and in particular alkyl or alkenyl chains such as alkanes or alkenes but also oils with alkyl or alkenyl chains comprising one or more ether groups , ester or carboxylic acid.
• the total liquid fatty phase of the composition may represent from 5% to 99.40% of the total weight of the composition and preferably from 20 to 85%. Advantageously, it represents at least 30% of the total weight of the composition. Preferably, this fatty phase contains at least one non-volatile oil (namely several non-volatile oils).
• the non-volatile part can represent from 0 to 80% of the total weight of the composition and better still from 1 to 50%.
• hydrocarbon oils of mineral or synthetic origin such as linear or branched hydrocarbons, volatile or not, such as paraffin oil or its derivatives, petrolatum oil, polydecenes, hydrogenated polyisobutene such as parlameam, squalane; oils of animal origin such as mink, turtle oil, perhydrosqualene; oils of vegetable origin; hydrocarbons with a high triglyceride content made up of fatty acid and glycerol esters, the fatty acids of which can have various chain lengths, the latter possibly being linear or branched, saturated or unsaturated, such as sweet almond oil, calophyllum, palm, grapeseed, sesame, arara, rapeseed, sunflower, cotton, apricot, castor, alfalfa, squash, blackcurrant, macadamia, rosebush muscat, hazelnut, avocado, jojoba, olive or germ of cereals (corn,
• one or more volatile solvents can be used at room temperature such as volatile cosmetic oils. These volatile solvents are favorable for obtaining a deposit of good performance. After evaporation of these solvents, a flexible film-forming deposit is obtained, which does not stick to the skin or the lips. These volatile solvents also facilitate the application of the composition to the skin, the lips and the integuments. They can be hydrocarbon or silicone and optionally comprise alkyl or alkoxy groups, pendant or at the end of the silicone chain.
• volatile oil which can be used in the invention, mention may be made of linear or cyclic silicone oils having a viscosity at room temperature of less than 8 cSt and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
• volatile silicone oil which can be used in the invention, mention may in particular be made of octamethylcyclo-tetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyldisethyloxane tranethylamethane, octamethylane tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
• volatile solvent used in the invention include volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures and in particular branched alkanes, C 8 -C 16 isoalkanes (also called isoparaffins) C 8 -C ⁇ 6 , isododecane, isodecane, isohexadecane and for example the oils sold under the trade names of isopars 'or Permyls', the branched esters of C 8 -C 18 such as neo isano pentanoate -hexyl and their mixtures.
• volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures and in particular branched alkanes, C 8 -C 16 isoalkanes (also called isoparaffins) C 8 -C ⁇ 6 , isododecane, isodecane, isohexadecane and for example the oils sold under the trade names of isopars 'or Permyls'
• liquid fatty phase is chosen from the group comprising:
• oils of vegetable origin formed by fatty acid esters and polyols, especially triglycerides, such as sunflower oil, sesame oil or rapeseed *, or esters derived from acids or long-chain alcohols (ie having from 6 to 20 carbon carbon), including the esters of formula R 1 COOR 2 in which R represents the residue of a higher fatty acid containing from 7 to 40 carbon atoms and R 2 represents a hydrocarbon chain comprising from 3 to 40 carbon atoms, such as palmitates , adipates and benzoates, in particular diisopropyl adipate.
• silicone oils such as polydimethylsiloxanes and polymethylphenylsiloxanes, optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups, and volatile silicone oils, in particular cyclic oils.
• solvents alone or as a mixture, chosen from (i) linear, branched or cyclic esters, having more than 6 carbon atoms, (ii) ethers having more than 6 carbon atoms, (iii) ketones having more than 6 carbon atoms.
• monoalcohols having a global solubility parameter according to the HANSEN solubility space of less than or equal to 20 (MPa) 1 ′ 2 is meant aliphatic fatty alcohols having at least 6 carbon atoms, fa hydrocarbon chain not comprising a group of substitution.
• oleic alcohol decanol, dodecanol, octadecanol and linoleic alcohol.
• non-aqueous medium it is also possible to use those described in document FR-A-2 710 646 by LVMH
• non-aqueous medium is made by a person skilled in the art depending on the nature of the monomers constituting the polymer and / or the nature of the stabilizer, as indicated below.
• the polymer dispersion can be manufactured as described in document EP-A-749747.
• the polymerization can be carried out in dispersion, that is to say by precipitation of the polymer during formation, with protection of the particles formed by stabilizer.
• a mixture is therefore prepared comprising the initial monomers and a radical initiator.
• This mixture is dissolved in a solvent called, in (following (a present description, "synthesis solvent”.
• synthesis solvent a solvent that is a non-volatile oil
• the polymerization can be carried out in an apolar organic solvent (synthesis solvent) then add the non-volatile oil (which must be miscible with said synthesis solvent) and selectively distil the synthesis solvent.
• a synthetic solvent such as the initial monomers and the radical initiator are therefore chosen to be soluble therein, and the polymer particles obtained therein are insoluble so that they precipitate thereon during their formation.
• the synthesis solvent can be chosen from alkanes such as heptane, isododecane or cyclohexane.
• the polymerization can be carried out directly in said oil which therefore also plays the role of synthetic solvent.
• the monomers must also be soluble therein, as well as the radical initiator, and the polymer obtained must be insoluble therein.
• the monomers are preferably present in the synthesis solvent, before polymerization, in an amount of 5-20% by weight of the reaction mixture). All of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added as the polymerization reaction proceeds.
• the radical initiator can in particular be azo-bis-isobutyronitrile or tert-butylpyroxy-2-ethyl hexanoate.
• the polymer particles are surface stabilized, as the polymerization progresses, thanks to a stabilizer which can be a block polymer, a graft polymer, and / or a random polymer, alone or as a mixture.
• Stabilization can be carried out by any known means, and in particular by direct addition of the block polymer, graft polymer and / or random polymer, during the polymerization.
• the stabilizer is preferably also present in the mixture before polymerization. However, it is also possible to add it continuously, in particular when the monomers are also added continuously.
• 2-30% by weight of stabilizer relative to the initial mixture of monomers can be used, and preferably 5-20% by weight.
• the synthetic solvent is chosen in such a way that at least part of the grafts or blocks of said polymer stabilizer is soluble in said solvent, the other part of the grafts or sequences not being soluble therein.
• the polymer stabilizer used during the polymerization must be soluble, or dispersible, in the synthetic solvent.
• a stabilizer is preferably chosen whose insoluble blocks or grafts have a certain affinity for the polymer formed during the polymerization.
• grafted polymers mention may be made of silicone polymers grafted with a hydrocarbon chain; hydrocarbon polymers grafted with a silicone chain. Also suitable are graft copolymers having, for example, an insoluble skeleton of polyacrylic type with soluble grafts of poly-12- (hydroxystearic) acid type.
• graft or block block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer can be used, such as graft copolymers of acrylic / silicone type which can be used in particular when the non-aqueous medium is silicone.
• graft or block copolymers comprising at least one block of the polyorganosiloxane type and at least one polyether.
• the polyorganopoly-siioxane block can in particular be a polydimethylsiloxane or alternatively a poly (C 2 -C 18 ) alkyl methyl siloxane; the polyether block may be a poly alkylene C z -C a, in particular polyoxyethylene and / or polyoxypropylene.
• copolyof dimethicones or of alkyl (C 2 ⁇ C 18 ) copolyol dimethicones such as those sold under the name “Dow Corning 3225C” by the company Dow Corning, lauryl methicones such as those sold under name “Dow Corning Q2-5200 by the company” Dow Corning ".
• graft or block block copolymers mention may also be made of those comprising at least one block resulting from the polymerization of at least one ethylenic monomer, with one or more optionally conjugated ethylenic bonds, such as ethylene or dienes such as butadiene and isoprene, and at least one block of a vinyl and better styrenic polymer.
• ethylenic monomer has more than one ethylenic bond that possibly combined, the residual ethylenic unsaturations after the polymerization are generally hydrogenated.
• block copolymers in particular of the "diblock” or “triblock” type of the polystyrene / polyisoprene (SI), polystyrene / polybutadiene (SB) type such as those sold under the name of "LUVITOL HSB" by BASF, of the polystyrene copoly (ethylene-propylene) type (SEP) such as those sold under the name 'Kraton' by Shell Chemical Co or also of the polystyrene / copoly (ethylene-butylene) (SEB) type.
• SI polystyrene / polyisoprene
• SB polystyrene / polybutadiene
• SEP polystyrene copoly (ethylene-propylene) type
• SEB polystyrene / copoly (ethylene-butylene)
• Kraton G1650 SEBS
• Kraton G1651 SEBS
• Kraton G1652 SEBS
• Kraton G1657X SEBS
• Kraton G1701X SEP
• Kraton G1702X SEP
• Kraton G1726X SEB
• Kraton CM 101 SBS
• SBS Kraton D-1102
• SBS Kraton D-107
• Polymers are generally called copolymers of hydrogenated or non-hydrogenated dienes.
• Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 mixture of triblock and star polymer
• Versagel 5960 from Penreco (triblock + star polymer)
• OS129880, OS129881 and ⁇ S84383 from Lubrizol (styrene / methacrylate copolymer).
• graft or block block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and of at least one block of an acrylic polymer
• graft or block block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and of at least one block of a polyether such as a C 2 -C 18 polykylene (polyethylenated and / or polyoxypropylenated in particular), mention may be made of two or three-block polyoxyethylene / polybutadiene or polyoxyethylene / polyisobutylene copolymers.
• a polyether such as a C 2 -C 18 polykylene
• a random polymer When a random polymer is used as a stabilizer, it is chosen so that it has a sufficient quantity of groups making it soluble in the intended synthetic solvent.
• copolymers based on alkyl acrylates or methacrylates derived from C 1 -C 4 alcohols and alkyl acrylates or methacrylates derived from C 8 -C 30 alcohols Mention may in particular be made of the stearyl methacrylate / methyl methacryate copolymer.
• the synthetic solvent is apolar
• the stabilizing agent is preferably chosen from the group consisting of grafted or block block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a polymer radical or of a polyether or of a polyester such as polyoxypropylenated and / or oxyethylenated blods.
• the stabilizing agent is preferably chosen from the group consisting of:
• grafted or block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer, with conjugated ethylenic bonds, and at least one block of a vinyl or acrylic polymer or of a polyether or polyester, or mixtures thereof.
• diblock polymers are used as the stabilizing agent.
• the dispersions of gelled polymers obtained according to the invention can then be used in a composition, in particular cosmetic, dermatological, pharmaceutical and / or hygienic, such as a composition for caring for or making up the skin or the lips, or even a hair composition. or a sunscreen composition or artificial coloring or tanning of the skin.
• a composition in particular cosmetic, dermatological, pharmaceutical and / or hygienic, such as a composition for caring for or making up the skin or the lips, or even a hair composition. or a sunscreen composition or artificial coloring or tanning of the skin.
• composition according to the invention also contains particles solid at room temperature, dispersed in the physiologically acceptable medium introduced into the composition in the form of a colloidal dispersion, also called "particulate paste”.
• colloidal dispersion or “particulate paste” is meant within the meaning of the invention a concentrated colloidal dispersion of particles coated or not in a continuous medium, surface stabilized using a dispersing agent.
• particles can be chosen from pigments, nacres, solid fillers and their mixtures.
• These particles can be of any shape, in particular of spherical or elongated shape like fibers. They are insoluble in the medium.
• the dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation.
• concentration of dispersant generally used to stabilize a colloidal dispersion is 0.3 to 5 mg / m 2 , preferably 0.5 to 4 mg / m 2 , of surface area of particles.
• This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can physically or chemically cling to the surface of the pigments.
• These dispersants also have at least one functional group which is compatible or soluble in the continuous medium.
• esters of 12-hydroxy stearic acid in particular and of acid are used.
• polyol such as glycerol, diglycerin
• poly (12-hydroxystearic) acid stearate with a molecular weight of approximately 750 g / mole such as that sold under the name of Solsperse 21,000 by the company Avecia
• CTFA polygyceryl-2 dipolyhydroxystearate
• the polydihydroxystearic acid and the esters of hydroxy12-stearic acid are preferably intended for a hydrocarbon or fluorinated medium, while the mixtures of dimethylsiloxane oxyethylene / oxypropyiene are preferably intended for a silicone medium.
• the colloidal dispersion is a suspension of particles of generally micron size ( ⁇ 10 ⁇ m) in a continuous medium.
• the volume fraction of particles in a concentrated dispersion is from 20% to 40%, preferably greater than 30%, which corresponds to a weight content of up to 70% depending on the density of the particles.
• the particles dispersed in the medium can consist of mineral or organic particles or their mixtures such as those described below.
• the continuous medium of the paste can be any and contain any solvent or liquid fatty substance and their mixtures.
• the liquid medium of the particulate paste is one of the liquid fatty substances or oils which it is desired to use in the composition, thus forming part of the liquid fatty phase.
• the "particulate paste" or colloidal dispersion is a "pigmentary paste” containing a colloidal dispersion of colored particles, coated or not, surface stabilized. These colored particles are pigments, nacres or a mixture of pigments and / or nacres.
• the colloidal dispersion represents from 0.5 to 60% by weight of the composition and better still from 2 to 40% and even better still from 2 to 30%.
• the pigments can be white or colored, mineral and / or organic, interference or not. Mention may be made, among the mineral pigments, of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red or chromium, manganese violet , ultramarine blue, chromium hydrate and ferric blue.
• the organic pigments mention may be made of carbon black, pigments of the organic lacquer type of barium, strontium, calcium or aluminum, including those subject to certification by the Food and Drug Administration (FDA) (example D&C or FD&C) and those exempt from FDA certification such as cochineal carmine lacquers.
• FDA Food and Drug Administration
• Pigments can represent from 0.1 to 50% in active matter and in particular 0.5 at 35% and better still from 2 to 25% of the total weight of the composition.
• the pearlescent pigments can be chosen from 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. They can represent from 0 to 25% (in active material) of the total weight of the composition and better still from 0.1 to 15% (if present). Pigments with goniochromatic properties can thus be used.
• the fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, powders of Nylon® (Orgasol® from Atochem), of poly- ⁇ -alanine and of polyethylene, the powders of polymers of tetrafluoroethyiene (Teflon ®), lauroyl-lysine, starch, boron nitride, hollow microspheres such as Expancel® (Nobel industry), Polytrap® (Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba , for example), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metallic soaps derivatives of organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc,
• the fillers and the pearlescent pigments or not are non-polymeric.
• the colloidal dispersion of the solid particles is prepared beforehand by mixing the solid particles, the dispersant and the continuous medium of the dispersion, with a view to obtaining adsorption of the stabilizer on the solid particles. This dispersion is then mixed with the other constituents of the composition. This step of prior preparation of the dispersion of solid particles is necessary to solve the problem of the stability of the composition.
• the simple addition of a dispersant in the composition without its prior adsorption on the solid particles and in particular on the pigments, does not make it possible to solve the problem of destabilization of a composition containing a dispersion of polymer particles stabilized on the surface.
• the composition of the invention may, inter alia, contain dyes soluble in the physiological medium and in particular liposoluble or water-soluble dyes.
• the liposoluble dyes are for example Sudan red, D&C Red n ° 17, D&C Green n ° 6, ⁇ -carotene, (soybean oil, Sudan brown, D&C Yellow n ° 11, D&C Violet n ° 2, orange D&C n ° 5, quinoline yellow, bromoacids They can represent from 0 to 20% and in particular 0.01 to 20% of the weight of the composition and better still from 0.1 to 6% (if present).
• the water-soluble dyes are for example beet juice, methylene blue and can represent up to 6% of the total weight of the composition.
• the composition of the invention can, in addition, contain one or more cosmetic active agents or dermatological such as those conventionally used.
• moisturizers As cosmetic, dermatological, hygienic or pharmaceutical active agents which can be used in the composition of the invention, mention may be made of moisturizers, vitamins, essential fatty acids, sphingolipids, sun filters. These assets are used in the usual amount for those skilled in the art and especially at concentrations of 0 to 20% and especially from 0.001 to 15% by total weight of a composition.
• the polymer of the composition of the invention allows the formation of a film on the skin, the lips and / or the integuments, forming a network trapping the coloring matters (including the fillers) and / or the active agents.
• the coloring matters including the fillers
• composition according to the invention can, moreover, comprise, depending on the type of application envisaged, the constituents conventionally used in the fields under consideration, which are present in an amount appropriate to the desired dosage form.
• the liquid fatty phase in which the polymer particles are stabilized can comprise, in addition, the liquid fatty phase in which the polymer particles are stabilized, additional fatty phases which can be chosen from waxes, oils, gums and / or pasty fatty, hydrocarbon-based, silicone and / or fluorinated, of vegetable, animal, mineral or synthetic origin and their mixtures.
• waxes solid at room temperature which may be present in the composition according to the invention, mention may be made of hydrocarbon waxes such as beeswax, Carnauba, Candellila, Ouricoury, Japanese wax, cork or sugar cane fiber waxes, paraffin waxes, lignite waxes, microcrystalline waxes, lanolin wax, Montan wax, ozokerites, polyethylene waxes, waxes obtained by Fischer synthesis Tropsch, hydrogenated oils, fatty esters and concrete glycerides at 25 ° C. It is also possible to use silicone waxes, among which mention may be made of alkyl, alkoxy and / or polymethylsiloxane esters.
• hydrocarbon waxes such as beeswax, Carnauba, Candellila, Ouricoury, Japanese wax, cork or sugar cane fiber waxes, paraffin waxes, lignite waxes, microcrystalline waxes, lanolin wax, Montan wax, ozokerites, poly
• the waxes can be in the form of stable dispersions of colloidal particles of wax as they can be prepared according to known methods, such as those of "Microemulsions Theory and Practice", LM Prince Ed., Académie Press (1977), pages 21-32.
• the waxes used have a melting temperature at least equal to 45 ° C.
• the waxes can be present in an amount of 0-50% by weight in the composition and better still from 5 to 25%, in order not to decrease too much the gloss of the composition and of the film deposited on the lips and / or the skin.
• composition can also comprise any other additive usually used in such compositions, such as water, oil or aqueous thickeners, antioxidants, perfumes, preservatives, surfactants, oils essential, liposoluble polymers (PolyVinyIPyrrolidone / eicosene copolymer).
• additives such as water, oil or aqueous thickeners, antioxidants, perfumes, preservatives, surfactants, oils essential, liposoluble polymers (PolyVinyIPyrrolidone / eicosene copolymer).
• compositions according to the invention can be prepared in the usual manner by a person skilled in the art. They can be in the form of a cast product and for example in the form of a stick or stick, or in the form of a dish usable by direct contact or with a sponge. In particular, they find application as a poured foundation, blush or eyeshadow, lipstick, base or lip care balm, concealer product. They can also be in the form of a flexible paste or else a gel, a more or less fluid cream. They can then constitute foundations or lipsticks, sunscreen or skin coloring products.
• compositions of the invention are advantageously anhydrous and can contain less than 5% of water relative to the total weight of the composition. They can then be in particular in the form of an oily gel, an oily liquid or oil, a paste or a stick or also in the form of a vesicular dispersion containing ionic and / or nonionic lipids. They can also be in the form of a single or multiple emulsion with an oily or aqueous continuous phase, an oily dispersion in a phase aqueous thanks to vesicles containing ionic and / or nonionic lipids. These dosage forms are prepared according to the usual methods of the fields considered.
• compositions for topical application may especially constitute a cosmetic, dermatological, hygienic or pharmaceutical composition for protection, treatment or care for the face, for the neck, for the hands or for the body (for example care cream, sun oil, body gel), a makeup composition (for example makeup gel, cream, stick) or an artificial tanning or skin protection composition.
• a cosmetic, dermatological, hygienic or pharmaceutical composition for protection, treatment or care for the face, for the neck, for the hands or for the body for example care cream, sun oil, body gel
• a makeup composition for example makeup gel, cream, stick
• an artificial tanning or skin protection composition for topical application.
• composition according to the invention may be in the form of a dermatological composition or for caring for the skin and / or integuments or in the form of a composition for sun protection, for personal hygiene, in particular in the form of a deodorant. It is then presented in particular in non-colored form. It can then be used as a care base for the skin, the integuments or the lips (lip balms, protecting the lips from the cold and / or the sun and / or the wind, care cream for the skin, the nails or the hair. ).
• composition of the invention may also be in the form of a colored product in particular for making up the skin, optionally having care or treatment properties, and in particular a foundation, a blush, a blush or eyeshadow, concealer, eyeliner, body makeup; lip makeup such as a lipstick, a lip gloss or a lip pencil possibly having care or treatment properties; make-up of headlights such as nails, eyelashes in the form of mascara, eyebrows and hair.
• composition of the invention must be cosmetically or dermatologically acceptable, ie contain a physiologically acceptable medium which is non-toxic and capable of being applied to the skin, the integuments or the lips of the face of human beings.
• cosmetically acceptable is meant within the meaning of the invention a composition of pleasant appearance, odor and feel.
• the invention is illustrated in more detail in the following examples.
• the percentages are percentages by weight.
• a dispersion of polymethyl methacrylate crosslinked with ethylene glycol dimethacrylate is prepared in hydrogenated polyisobutene (containing 6-8 moles of isobutylene) sold under the name Parieam by the company Nippon Oil Fat, according to the method of the example. 2 of document EP-A-749 746, by replacing Isopar L with the Parieam.
• a dispersion of polymethyl methacrylate particles stabilized on the surface in Parieam is thus obtained by a polystyrene / copoly (ethylene-propylene) block copolymer sold under the name Kraton G1701 (Shell), having a dry matter content of 22- 25% by weight and a Tg of 100 ° C. This copolymer is not film-forming at room temperature.
• a dispersion of uncrosslinked copolymer of methyl acrylate and acrylic acid in an 85/15 ratio is prepared in Parieam, according to the method of example 1 of document EP-A-749 746, replacing the heptane by the Parieam.
• This copolymer is film-forming.
• This dispersion is prepared beforehand before it is mixed with the other constituents of the composition according to the invention.
• phase A In a pan, all the components of phase A are introduced (which are heated to 100 ° C. with magnetic stirring in order to obtain a homogeneous mixture.
• Phase B is then ground in a three-cylinder mill. This grinding is then added to phase A.
• the mixture is left under stirring for 1 hour and then poured into suitable lipstick molds.
• the mixture is left under stirring for 1 hour and then poured into suitable lipstick molds. freezer at -18 ° C for 30 minutes to obtain a lipstick stick.
• phase B grinding of pigment in the three-cylinder
• this formula looks like an inhomogeneous stick on the surface: presence of mottling on the stick.
• Phase B corresponding to the pigment paste, mixed with lanolin is then added.
• the pigment paste contains 8.66% of pigments, 0.58% of poly (12-hydroxystearic) acid stearate and 8.48% of Parieam .
• the color change is less pronounced than in the mixture of the counterexample.
• the mixture is left under stirring for one hour and then poured into suitable lipstick molds. The molds are then placed in the freezer at -18 ° C for 30 minutes.
• the lipstick stick obtained has no mottling and is uniform in color.
• phase A All the components of phase A are introduced into a pan, which is heated to 100 ° C. with magnetic stirring in order to obtain a homogeneous mixture.
• Phase B corresponding to the pigment paste, Parieam mixed, is then added.
• the pigment paste contains 8.66% of pigments, 0.58% of poly (12-hydroxystearic acid) stearate and 8.48% of Parieam.
• the stick obtained has no mottling and is uniform in color. Its application is easy: the deposit obtained is comfortable, homogeneous, shiny, non-migrating and of good performance, especially in color.

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• 2001
  • 2001-11-08 EP EP01985790A patent/EP1389999A1/de not_active Withdrawn
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