WO2000027350A1 - Cosmetic composition without transfer comprising dispersed polymer particles an a polysaccharide rheological agent - Google Patents

Cosmetic composition without transfer comprising dispersed polymer particles an a polysaccharide rheological agent Download PDF

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Publication number
WO2000027350A1
WO2000027350A1 PCT/FR1999/002727 FR9902727W WO0027350A1 WO 2000027350 A1 WO2000027350 A1 WO 2000027350A1 FR 9902727 W FR9902727 W FR 9902727W WO 0027350 A1 WO0027350 A1 WO 0027350A1
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composition according
composition
polymer
block
chosen
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PCT/FR1999/002727
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French (fr)
Inventor
Valérie de la Poterie
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L'oreal
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Priority to BR9908218-7A priority Critical patent/BR9908218A/en
Priority to CA002304573A priority patent/CA2304573A1/en
Publication of WO2000027350A1 publication Critical patent/WO2000027350A1/en

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    • 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
    • A61K8/044—Suspensions
    • 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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • 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
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; 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
    • A61K8/817—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. 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
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • 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
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/614—By macromolecular compounds
    • 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
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

  • Cosmetic composition without transfer comprising a dispersion of polymer particles and a rheological agent of polysaccharide type
  • the present invention relates to a composition containing a polymer dispersible in an oily phase, intended in particular for the cosmetic, dermatological, pharmaceutical and hygienic fields. More specifically, the invention relates to a composition without transfer for the care and / or makeup of the skin both of the face and of the human body, of the lips, of the lower or upper eyelids, or even of the integuments such as the eyelashes, eyebrows, nails and hair.
  • This composition can be in particular in the form of a product cast in stick or in a cup such as lipsticks or lip balms, cast foundations, concealer products, eyeshadows or blushes, in the form of paste or more or less fluid cream such as foundations or fluid lipsticks, eye liners, mascaras, sun protection or skin coloring compositions or even body makeup.
  • a product cast in stick or in a cup such as lipsticks or lip balms, cast foundations, concealer products, eyeshadows or blushes, in the form of paste or more or less fluid cream such as foundations or fluid lipsticks, eye liners, mascaras, sun protection or skin coloring compositions or even body makeup.
  • Makeup or skin care or lip care products for human beings such as foundations or lipsticks generally contain fatty phases such as waxes and oils, pigments and / or fillers and possibly additives such as cosmetic or dermatological active ingredients. They can also contain so-called "pasty" products, of flexible consistency, making it possible to obtain pasta, colored or not, to be applied with a brush.
  • These compositions when applied to the skin or the lips, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact, the integuments and in particular a glass, a cup, a cigarette, a garment or the skin. This results in mediocre persistence of the applied film, requiring regular renewal of the application of the foundation or lipstick composition.
  • the appearance of these unacceptable traces, in particular on the blouse collars may exclude certain women from the use of this type of makeup.
  • compositions tend to migrate, that is to say to propagate inside the wrinkles and fine lines of the skin which surround the lips and the eyes, causing an unsightly effect.
  • compositions of mascara of the water-in-oil emulsion type having a long hold, a resistance to water and leaving no traces contain, among other things, a water-insoluble polymer, generally called a latex, associated with a surfactant of the alkyl or alkoxy dimethicone copolyol type, hydrocarbon oils, pigments and fillers as well as waxes.
  • a water-insoluble polymer generally called a latex
  • hydrocarbon oils, pigments and fillers as well as waxes.
  • the compositions based on silicone oils and silicone resins as well as those based on latex lead to matt colored films.
  • women are now looking for products, in particular lip gloss, that are shiny.
  • the transfer-free properties of the deposited films are not perfect. In particular, a pronounced pressure or friction leads to a reduction in the color of the deposit and to a redeposition on the support brought into contact with these films.
  • the Applicant has found, quite surprisingly, that the use of a polymer dispersible in an oily phase, associated with a particular rheological agent, in a cosmetic, dermatological, pharmaceutical or hygienic composition makes it possible to obtain a shiny film. , very good hold, not transferring little or not at all, not migrating, water resistant, while being very pleasant to apply and to wear throughout the day.
  • the film is particularly soft and flexible.
  • the present invention therefore relates to a composition for topical application, containing a liquid fatty phase and polymer particles dispersed in the liquid fatty phase and surface stabilized by a stabilizing agent, said fatty phase being, in addition, thickened by an agent. liposoluble rheological polysaccharide type.
  • This composition is in particular a cosmetic, dermatological, hygienic or pharmaceutical composition. It therefore contains ingredients compatible with the skin, mucous membranes and keratinous or dander fibers. It can be in the form of an anhydrous gel, an emulsion or an oil-in-water or water-in-oil dispersion or also in the form of a multiple emulsion.
  • the polymer is insoluble in the 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. It also allows the formation of a film-forming deposit in the form of an isolable, continuous and homogeneous film and / or is characterized by the entanglement of the polymer chains. Even with a wax obtained by polymerization, after melting in the fatty phase, recrystallization is obtained.
  • 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. Preferably the polymer used is film-forming. 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 the mucous membranes such as 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 surface-stabilized polymer particles present in the liquid fatty phase, the composition of the invention makes it possible to limit or even eliminate the transfer of the composition and in particular the transfer of the active agents and / or of the coloring matters and therefore maintain these active ingredients and / or coloring materials 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 in order to limit, or even eliminate, their transfer to a support with which the film is brought into contact.
  • 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 use in a composition for topical, cosmetic or hygienic application or for the manufacture of a composition for topical, dermatological or pharmaceutical application, of particles of at least one polymer dispersed in a fatty phase liquid and surface stabilized by a stabilizing agent, said fatty phase being thickened by a liposoluble rheological agent of polysaccharide type, to reduce, or even eliminate, the transfer of the film of composition deposited on the mucous membranes and / or the skin of human beings towards a support brought into contact with the film and / or maintain its gloss.
  • the subject of the invention is also a method of cosmetic care or of making up the lips, the integuments or 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 method for limiting, or even eliminating, the transfer of a makeup or care composition for the skin or the lips on a support different from the said skin and the said lips, containing a liquid fatty phase and at least one ingredient chosen from coloring matters and cosmetic, dermatological, hygienic and pharmaceutical active ingredients, consisting in introducing into the liquid fatty phase particles of polymer dispersible in the liquid fatty phase and stabilized at the surface by a stabilizing agent and at least one liposoluble rheological agent of polysaccharide type.
  • An advantage of using a dispersion of particles in a composition of the invention is that the particles remain in the state of elementary particles, without forming agglomerates, in the fatty phase, which would not be the case. with nanoscale mineral particles.
  • Another advantage of the polymer dispersion is the possibility of obtaining very fluid compositions (of the order of 130 centipoise), even in the presence of a high level of polymer.
  • composition according to the invention exhibits qualities of spreading and adhesion to the skin, the semi-mucous membranes 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. This is quite remarkable since the compositions of the prior art with high "no transfer" properties are very difficult to remove. In general, they are sold with a specific make-up removing product, which introduces an additional constraint for the user.
  • composition according to the invention therefore advantageously comprises one or more stable dispersions of generally spherical particles of one or more polymers, in a physiologically acceptable liquid fatty phase.
  • These dispersions can in particular be in the form of nanoparticles of polymers in stable dispersion in said fatty phase.
  • the nanoparticles are preferably between 5 and 600 nm in size, since above about 600 nm, the particle dispersions become much less stable.
  • 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 polymeric system (polymer more additive of the plasticizer type), and thus of passing from a hard polymer to a more or less soft polymer, allowing the mechanical properties of the composition to be adjusted according to the intended application.
  • Tg glass transition temperature
  • film-forming polymers preferably having a low Tg, less than or equal to the skin temperature, in particular less than 40 ° C. A dispersion is thus obtained which can improve when it is applied to a support, which is not the case when dispersions of mineral pigments according to the prior art are used.
  • 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 from -100 ° C to 300 ° C and better still from -10 ° to 50 ° 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 usually used in the field of application and in particular from the compounds capable of being solvents for the polymer.
  • film-forming polymers mention may be made of radical, acrylic or vinyl homopolymers or copolymers, preferably having a Tg less than or equal to 40 ° C and in particular ranging from - 10 ° to 30 ° C.
  • non-film-forming polymers mention may be made of radical, vinyl or acrylic homopolymers or copolymers, optionally crosslinked, preferably having a Tg greater than or equal to 40 ° C. and in particular ranging from 45 ° to 150 ° C.
  • 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, especially 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.
  • ⁇ , ⁇ -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 of C 1 -C 20 alkyl, preferably in C ⁇ -C 8 , ary (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 lauryl (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 alkyl (meth) acrylate, in particular of CC 4 alkyl. More preferably, it is possible to use methyl acrylates optionally copolymerized with acrylic acid.
  • amides of the acid monomers mention may be made of (meth) acrylamides, and in particular N-alkyl (meth) 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 methacrylamide, vinylamine, vinyipyridine, diallyldimethylammonium chloride.
  • the vinyl polymers can also result from the homopolymerization or from the copolymerization of at least one monomer chosen from vinyl esters and styrenic monomers.
  • these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.
  • vinyl esters that may be mentioned include vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.
  • styrenic monomers mention may be made of styrene and alpha-methyl styrene.
  • - olefins such as ethyiene, propylene, butylene, isoprene, butadiene.
  • the vinyl polymer can be crosslinked using a difunctional monomer, 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 liquid fatty phase of the composition may 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, hydrocarbon, fluorinated and / or silicone, alone or in mixture insofar as they form a homogeneous and stable mixture and where they are compatible with the intended use.
  • liquid fatty phase is meant any non-aqueous medium which is liquid at room temperature and atmospheric pressure.
  • This fatty phase may contain a volatile liquid fatty phase and / or a non-volatile fatty phase.
  • volatile fatty phase is meant any non-aqueous medium capable of evaporating from the skin or the lips in less than an hour.
  • This volatile phase comprises in particular oils having a vapor pressure, at ambient temperature (25 ° C) and atmospheric pressure (760mm Hg) ranging from 10 "3 to 300mm Hg (0J3 Pa to 40,000 Pa).
  • the liquid fatty phase total of the composition can represent from 5% to 97.90% of the total weight of the composition and preferably from 20 to 85%.
  • the non-volatile part can represent from 0 to 80% of the total weight of the composition and better still from 1 at 50%.
  • liquid fatty phase which can be used in the invention, mention may therefore be made of hydrocarbon oils such as paraffin or petrolatum oil, mink, turtle, soybean oil, perhydrosqualene, sweet almond, calophyllum, palm, grapeseed, sesame, corn, parlam, arara, rapeseed, sunflower, cotton, apricot, castor, avocado, jojoba, olive or germ of cereals; esters of lanolic acid, oleic acid, iauric acid, stearic acid; fatty esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononate, 2-ethyl-hexyl palmitate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl-dodecyl myri
  • one or more volatile oils can be used at room temperature. These volatile oils are favorable for obtaining a film with total "transfer-free" properties. After evaporation of these oils, a flexible film-forming deposit is obtained, which is not sticky on the skin or the mucous membranes, respectively according to the movements of the skin or the lips, to which the composition is applied. These volatile oils also facilitate the application of the composition to the skin, the mucous membranes and the integuments. They can be hydrocarbon or silicone optionally comprising 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 siionics having from 2 to 7 silicon atoms, these siicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms as well as C 8 isoparaffins -C ⁇ 6 . These volatile oils represent in particular from 20 to 97.90% of the total weight of the composition, and better still from 30 to 75%.
  • volatile oil used in the invention we may notably mention the octaméthylcy- clotétrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane or isoparaffins C 8 -C 16 such as 'Isopar', the PERMETYLs and in particular isododecane.
  • octaméthylcy- clotétrasiloxane decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane or isoparaffins C 8 -C 16 such as 'Isopar', the PERMETYLs and in particular is
  • liquid fatty phase is chosen from the group comprising:
  • liquid fatty phases having a global solubility parameter according to the HANSEN solubility space less than or equal to 17 (MPa) 1 2
  • vegetable oils formed by esters of fatty acids and of polyols in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or long-chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR 'in which R represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R' represents a hydrocarbon chain born with 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate.
  • silicone oils such as polydimethylsiioxanes and poiymethylphenylsiloxanes, 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, the hydrocarbon chain not comprising a group of substitution.
  • monoalcohols according to the invention mention may be made of oleic alcohol, decanol, dodecanol, octadecanol and linoleic alcohol.
  • non-aqueous medium one can also use those described in document FR-A-2 710 646 of LV.M.H.
  • 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 produced 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 with a stabilizer. .
  • a mixture is therefore prepared comprising the initial monomers and a radical initiator. This mixture is dissolved in a solvent called, in the remainder of this description, "synthetic solvent".
  • the polymerization can be carried out in an organic organic solvent (synthesis solvent) then add the non-volatile oil (which must be miscible with said synthesis solvent) and selectively distill the synthesis solvent .
  • organic organic solvent synthesis solvent
  • 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 dissolved there, 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. Stabilizing
  • 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.
  • 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.
  • graft copolymers having for example an insoluble skeleton of polyacrylic type with solubied 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-siloxane block may in particular be a polydimethylsiloxane or alternatively a poly (C 2 - C ⁇ 8 ) methyl siioxane alkyl; the polyether block can be a poly C 2 -C 18 alkylene, in particular polyoxyethylene and / or polyoxypropylene.
  • dimethicone copolyol or alkyl (C 2 -C 18 ) dimethicone copolyol such as those sold under the name "DOW CORNING 3225C” by the company DOW CORNING, lauryl methicones such as those sold under the 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 ethylenic bonds which may be conjugated , such as ethylene or dienes such as butadiene and isoprene, and at least one block of a vinyl and better styrenic polymer.
  • the ethylenic monomer contains several optionally conjugated ethylenic bonds
  • the residual ethylenic unsaturations after the polymerization are generally hydrogenated.
  • the polymerization of isoprene leads, after h hydrogenation, to the formation of ethylene-propylene block
  • the polymerization of butadiene leads, after hydrogenation, to the formation of ethylene-butylene block.
  • block copolymers these, in particular of the "diblock” or “triblock” type of the polystyrene / polyisoprene (SI), polysyrene / polybutadiene (SB) type such as those sold under the name of "LUVITOL HSB” by BASF, of the polystyrene / copoly type ( ethylene-propyiene) (SEP) such as those sold under the name of “KRATON” by Shell Chemical Co or also of the polystyrene / copoly (ethylene-butylene) type (SEB).
  • SI polystyrene / polyisoprene
  • SB polysyrene / polybutadiene
  • SEP polystyrene / copoly type
  • KRATON polystyrene / copoly (ethylene-butylene) type
  • the Kraton G1650 (SEBS), the Kraton G1651 (SEBS), the Kraton G1652 (SEBS), the Kraton G1657X (SEBS), the Kraton G1701X (SEP), the Kraton G1702X (SEP), the Kraton can be used.
  • G1726X SEB
  • Kraton D-1101 SBS
  • Kraton D-1102 SBS
  • Kraton D-1107 SIS
  • the 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 OS84383 from Lubrizol (styrene / methacrylate copolymer).
  • grafted or 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
  • grafted or 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 8 polykylene (especially polyethylene and / or polyoxypropylene), mention may be made of bi- or tri-sequenced polyoxyethylene / polybutadiene or polyoxyethylene / polyisobutylene copolymers.
  • a polyether such as a C 2 -C 8 polykylene (especially polyethylene and / or polyoxypropylene)
  • 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 envisaged synthesis solvent.
  • copolymers based on alkyl acrylates or methacrylates derived from CrC 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 methacrylate copolymer.
  • the synthetic solvent is apolar
  • a grafted polymer or a block polymer it is then preferred to use, as stabilizer, either a grafted polymer or a block polymer, so as to have better interfacial activity.
  • the sequences or grafts which are insoluble in the synthesis solvent provide more voluminous coverage on the surface of the particles.
  • 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 radical polymer or of a polyether or of a polyester such as polyoxypropylenated and / or oxyethylenated blocks.
  • the stabilizing agent is preferably chosen from the group consisting of: - (a) grafted or block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or of a polyether or of a polyester,
  • 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 of a polyester, or mixtures thereof.
  • diblock polymers are used as the stabilizing agent.
  • Rheological agent it is possible to use one or more liposoluble rheological agents in the composition of the invention.
  • This or these rheological agents are liposoluble agents capable of thickening and / or gelling the composition. They are in particular present in an amount effective to increase the viscosity of the composition until a gel is obtained, namely a product which does not flow under its own weight, or even in stick form.
  • the amount of rheological agent is a function of the viscosity sought, and of the form sought for the final composition.
  • the ratio by weight of the quantity of solvent and / or of oil to the quantity of thickener is chosen, for example, from the range from 5 to 1000.
  • the composition according to the invention can contain, for example, an amount of alkyl ether of polysaccharide ranging from 0.05 to 20% of the total weight of the composition, and preferably from 0% to 10% by weight and better still from 0.5% to 6% by weight.
  • the rheological agent according to the invention is a polysaccharide aikylether formed of units comprising at least two different osidic rings, each unit comprising at least one hydroxyl group substituted by a saturated hydrocarbon-based alkyl chain.
  • hydrocarbon-based alkyl chain is understood to mean a linear or branched chain, comprising from 1 to 24, preferably from 1 to 10, better still from 1 to 6 and more especially from 1 to 3 atoms. of carbon.
  • the alkyl chain is chosen from saturated chains and in particular methyl, ethyl, ethenyl, n-propyl, propenyl, isopropyl, n-butyl, isobutyl, tertiobutyl, n-pentyl.
  • alkyl ethers can be manufactured as described in documents EP-A-281,360, EP-A-708,114, EP-A-281360.
  • the alkyl ether of polysaccharide has a molecular weight medium by weight greater than 100,000, and preferably greater than 200,000. This molecular weight can range up to 1 million.
  • This aikyl ether may contain from one to six and better still from two to four hydroxyl groups per unit, substituted by a saturated or unsaturated hydrocarbon alkyl chain.
  • the osidic cycles are in particular chosen from mannose, galactose, glucose, furanose, rhamnose, arabinose.
  • the polysaccharide alkyl ether is an aikyl ether of a gum and more particularly of a generally nonionic gum, that is to say comprising little or no ionic group.
  • suitable gums there may be mentioned, for example, guar gum, the motif of which comprises a galactose and a mannose, locust bean gum, the motif of which comprises a galactose and a mannose, karaya gum, which is a complex mixture of rhamnose, galactose. and galacic acid turonic, the tragacanth which is a complex mixture of arabinose, galactose and galacturonic acid.
  • the polysaccharide alkyl ether is a guar gum derivative.
  • the alkyl ether is an alkyl galactomannan with a C 1 to C 6 and better C 1 to C 3 alkyl chain and more particularly ethyl guar having a degree of substitution of 2 to 3 and in particular approximately 2.5 to 2 , 8, as described in documents RD 95378007 (October 1995) and EP-A-708114.
  • This gum is in particular that sold by the company Aqualon under the names N-HANCE-AG 200® and N-HANCE AG 50®.
  • This liposoluble rheological agent or agents allow the composition to thicken, while retaining a shiny appearance to the composition as well as to the film deposited on the lips and / or the body. This is clear from the table (I) mentioned later.
  • 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.
  • the composition of the invention may advantageously comprise one or more coloring matters containing one or more pulverulent compounds and / or one or more liposoluble or water-soluble dyes, for example at a rate of 0 to 70% of the total weight of the composition and in particular of 0 , 01 to 70%.
  • the pulverulent compounds can be chosen from pigments and / or nacres and / or fillers usually used in cosmetic or dermatological compositions.
  • the pulverulent compounds represent from 0 to 50% and in particular from OJ to 50% of the total weight of the composition and better still from 1 to 40%.
  • the transfer-free properties increase as the amount of pulverulent compounds decreases. Indeed, to date the transfer-free properties of the compositions of the prior art have increased with the amount of pulverulent compounds. Conversely, their discomfort, shine and dryness on the skin or mucous membranes increased. Furthermore, the property of non-transfer increases with the amount of polymer dispersed in the liquid fatty phase.
  • the polymer can represent in active material up to 60% (in active or dry material) of the total weight of the composition. By using above 12% by weight of polymer active material and non-volatile oil in the composition and up to 60%, a film is obtained without total transfer. Between 2% and 12% the effect without transfer is significant without however being total. We can therefore adapt the properties without transfer at will, which was not possible with the compositions without transfer of the prior art, without affecting the comfort of the film deposited.
  • the pigments can be white or colored, mineral and / or organic, interference or not.
  • mineral pigments mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue.
  • organic pigments there may be mentioned carbon black, pigments of type D & C, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.
  • the pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
  • the fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, nylon powders (Orgasol from Atochem), poly- ⁇ -alanine and polyethylene, Teflon, lauroyl-lysine, starch, nitride.
  • boron powders of tetrafluoroethylene polymers, hollow microspheres such as Expancel (Nobel Industrie), polytrap (Dow Corning) and microbeads of silicone resin (Toshiba Tospearls, for example), precipitated calcium carbonate , magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
  • organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
  • the liposoluble dyes are for example Sudan red, DC Red 17, DC Green 6, ⁇ -carotene, soybean oil, Sudan brown, DC Yeliow, 11, DC Violet 2, DC orange 5 , quinoline yellow. They can represent from 0 to 20% and in particular 0.01 to 20% of the weight of the composition and better still from 0J to 6%.
  • the water-soluble dyes are, for example, beet juice, methylene blue and can represent up to 6% of the total weight of the composition.
  • composition of the invention may, in addition, contain one or more cosmetic or dermatological active agents 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 active agents are used in the usual amount for humans and in particular at concentrations of 0 to 20% and in particular from 0.001 to 20% of the total weight of the composition.
  • the polymer of the composition of the invention allows the formation of a film on the skin, the lips and / or the mucous membranes, 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 suitable for the desired dosage form.
  • liquid fatty phase in which the polymer is stabilized can be chosen from waxes, oils, gums and / or pasty fatty substances of vegetable origin, animal, mineral or synthetic, or even siiconized, and mixtures thereof.
  • 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, fiber waxes cork or sugar cane, paraffin waxes, lignite, microcrystalline waxes, lanolin wax, Montan wax, ozokerites, polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, 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, fiber waxes cork or sugar cane, paraffin waxes, lignite, microcrystalline waxes, lanolin wax, Montan wax, ozokerites, polyethylene waxe
  • 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.
  • Meneta oil As liquid wax at room temperature, mention may be made of Jojoba oil.
  • the waxes can be present at a rate of 0-50% by weight in the composition and better still from 5 to 20%, in order not to decrease too much the gloss of the composition and of the film deposited on the lips and / or the skin.
  • the composition may also comprise any additive usually used in such compositions, such as thickeners other than the rheological agent of polysaccharide type, antioxidants, perfumes, preservatives, surfactants, liposoluble polymers such as polyalkylenes, in particular polybutene, polyacrylates and silicone polymers compatible with the fatty phase as well as polyvinylpyrolidone derivatives.
  • 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 poured eyeshadow, lipstick, base or lip care balm, concealer product. They can also be in the form of a flexible paste, of dynamic viscosity at 25 ° C of the order of 1 to 40 Pa.s or else of gel, of more or less fluid cream. They can then consist of foundations or lipsticks, sun products or skin coloring.
  • 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 presented 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 an aqueous phase using 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.
  • Example 1 of polymer dispersion
  • a dispersion of polymethyl methacrylate crosslinked with ethylene glycol dimethacrylate is prepared in isododecane, according to the method of Example 2 of document EP-A-749 746, replacing ISOPAR L by isododecane.
  • a dispersion of polymethyl methacrylate particles surface stabilized in isododecane is thus obtained by a polystyrene / copoly (ethylene-propylene) block copolymer sold under the name KRATON G1701 (Shell), having a dry matter content of 19.7% by weight and an average particle size of 135 nm (polydispersity: 0.05) and a Tg of 100 ° C. This copolymer is non-film-forming at room temperature.
  • a dispersion of uncrosslinked copolymer of methyl acrylate and acrylic acid in a 95/5 ratio is prepared in isododecane, according to the method of example 1 of document EP-A-749 746, replacing heptane with isododecane.
  • a dispersion of poly (methyl acrylate / acrylic acid) particles is thus obtained, stabilized at the surface in isododecane by a polystyrene / copoly (ethylene-propylene) block copolymer sold under the name of KRATON G1701 (Shell). , having a dry matter content of 19% by weight and an average particle size of 165 nm (polydispersity: 0.05) and a Tg of 13 ° C.
  • This copolymer is film-forming.
  • a dispersion of uncrosslinked copolymer of methyl acrylate and acrylic acid in a 95/5 ratio is prepared in isododecane, according to the method of example 1 of document EP-A-749 746, replacing heptane with isododecane.
  • This copolymer is film-forming.
  • the gelling agents of the composition according to the invention ensure a high gloss of the compositions, which is not the case with the gelling agents.
  • classics such as waxes, Bentone 34 from Rheox, KSG X-21-5432 sold by the company Shin Etsu which is an organopolysiloxane crosslinked to 27% in active material in polymethyltrifluoropropyl dimethylsiloxane.
  • Shin Etsu which is an organopolysiloxane crosslinked to 27% in active material in polymethyltrifluoropropyl dimethylsiloxane.
  • the composition containing no gelling agent or pigments has a gloss of 84%.
  • a lip lacquer is prepared in fluid form having the following composition:
  • This lip lacquer is very shiny, without total transfer and non-migrating. It is obtained according to the following operating method: dissolve the Kraton in the polymer dispersion under hot conditions (approximately 50 ° C.) for 2 hours then add the pigments previously ground in the oils.
  • This lacquer has been tested by experts using an applicator with a foam tip.
  • This hairspray stretches well over the lips; the film is glossy / satin; its transfer is weak; it does not migrate into fine lines and wrinkles around the lips. The contours are sharp. Comfort is good when applied.
  • Example 5 Lipstick Without Transfer A lipstick is prepared in fluid form having the following composition:
  • N-Hance AG 200 (Hercules) 1.50%.
  • PVP / eicosene copolymer 0.44%
  • This lipstick is prepared as before. It comes in a fluid, shiny, soft application form, without transfer and non-migrating.
  • a foundation in fluid form is prepared having your following composition:
  • octyldodecanol 3.00% This foundation is prepared as above. It comes in a fluid form, easy to spread and has good properties without transfer.

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Abstract

The invention concerns a composition, in particular cosmetic, dermatological, hygienic or pharmaceutical, for skin care and/or make up and/or skin appendages and/or lips, in the form of a flowing product or a gel comprising dispersed polymer particles surface-stabilised in a liquid fatty phase by a stabilising agent, said fatty phase being further thickened by a liposoluble polysaccharide rheological agent. Depending on the amount of polymer, it is possible to produce on the skin, skin appendages or lips a soft, shiny film having remarkable non-transferring properties, while being highly comfortable. The invention also concerns a method for care or make up of the skin, skin appendages and lips using said composition.

Description

Composition cosmétique sans transfert comprenant une dispersion de particules de polymère et un agent rhéologique de type polysaccharide Cosmetic composition without transfer comprising a dispersion of polymer particles and a rheological agent of polysaccharide type
La présente invention a trait à une composition contenant un polymère dispersible dans une phase grasse, destinée en particulier aux domaines cosmétique, dermatologique, pharmaceutique et hygiénique. Plus spécialement, l'invention se rapporte à une composition sans transfert pour le soin et/ou le maquillage de la peau aussi bien du visage que du corps humain, des lèvres, des paupières inférieure ou supérieure, ou encore des phanères comme les cils, les sourcils, les ongles et les cheveux.The present invention relates to a composition containing a polymer dispersible in an oily phase, intended in particular for the cosmetic, dermatological, pharmaceutical and hygienic fields. More specifically, the invention relates to a composition without transfer for the care and / or makeup of the skin both of the face and of the human body, of the lips, of the lower or upper eyelids, or even of the integuments such as the eyelashes, eyebrows, nails and hair.
Cette composition peut se présenter notamment sous forme de produit coulé en stick ou en coupelle comme les rouges ou baumes à lèvres, les fonds de teint coulés, les produits anti-cernes, les fards à paupières ou à joues, sous forme de pâte ou de crème plus ou moins fluide comme les fonds de teint ou rouges à lèvres fluides, les eyes liners, les mascaras, les compositions de protection solaire ou de coloration de la peau ou encore de maquillage du corps.This composition can be in particular in the form of a product cast in stick or in a cup such as lipsticks or lip balms, cast foundations, concealer products, eyeshadows or blushes, in the form of paste or more or less fluid cream such as foundations or fluid lipsticks, eye liners, mascaras, sun protection or skin coloring compositions or even body makeup.
Les produits de maquillage ou de soin de la peau ou des lèvres des êtres humains comme les fonds de teint ou les rouges à lèvres contiennent généralement des phases grasses telles que des cires et des huiles, des pigments et/ou charges et éventuellement des additifs comme des actifs cosmétiques ou dermatologiques. Elles peuvent aussi contenir des produits dits "pâteux", de consistance souple, permettant d'obtenir des pâtes, colorées ou non, à appliquer au pinceau. Ces compositions, lorsqu'elles sont appliquées sur la peau ou les lèvres, présentent l'inconvénient de transférer, c'est-à-dire de se déposer au moins en partie, en laissant des traces, sur certains supports avec lesquels elles peuvent être mises en contact, les phanères et notamment un verre, une tasse, une cigarette, un vêtement ou la peau. Il s'ensuit une persistance médiocre du film appliqué, nécessitant de renouveler régulièrement l'application de la composition de fond de teint ou de rouge à lèvres. Par ailleurs, l'apparition de ces traces inacceptables notamment sur les cols de chemisier peut écarter certaines femmes de l'utilisation de ce type de maquillage.Makeup or skin care or lip care products for human beings such as foundations or lipsticks generally contain fatty phases such as waxes and oils, pigments and / or fillers and possibly additives such as cosmetic or dermatological active ingredients. They can also contain so-called "pasty" products, of flexible consistency, making it possible to obtain pasta, colored or not, to be applied with a brush. These compositions, when applied to the skin or the lips, have the drawback of transferring, that is to say of depositing at least in part, leaving traces, on certain supports with which they can be brought into contact, the integuments and in particular a glass, a cup, a cigarette, a garment or the skin. This results in mediocre persistence of the applied film, requiring regular renewal of the application of the foundation or lipstick composition. Furthermore, the appearance of these unacceptable traces, in particular on the blouse collars, may exclude certain women from the use of this type of makeup.
De plus, ces compositions ont tendance à migrer, c'est-à-dire à se propager à l'intérieur des rides et des ridules de la peau qui entourent les lèvres et les yeux, entraînant un effet inesthétique.In addition, these compositions tend to migrate, that is to say to propagate inside the wrinkles and fine lines of the skin which surround the lips and the eyes, causing an unsightly effect.
Dans la demande JP-A-61 -65809 la société Shiseido a décrit des compositions de rouge à lèvres "sans transfert" contenant une résine siloxysilicate (à réseau tridimensionnel), une huile de silicone volatile à chaîne silicone cyclique et des charges pulvérulentes. Par ailleurs, la société Noevier à décrit dans le document JP-A-62-61911 des compositions de rouge à lèvres, d'eye liner et de fonds de teint "sans transfert" comportant une ou plusieurs silicones volatiles associées à une ou plusieurs cires hydrocarbonées. Ces compositions, bien que présentant des propriétés de "sans transfert" améliorées ont l'inconvénient de laisser sur les lèvres, après évaporation des huiles de silicone, un film qui devient inconfortable au cours du temps (sensation de dessèchement et de tiraillement), écartant un certain nombre de femmes de ce type de rouge à lèvres. Plus récemment, la société Procter & Gamble a envisagé dans sa demande de brevet WO-A-96/36323 des compositions de mascara de type émulsion eau-dans-huile présentant une longue tenue, une résistance à l'eau et ne laissant pas de traces. Ces compositions contiennent, entre autre, un polymère insoluble dans l'eau, appelé généralement un latex, associé à un tensioactif du type alkyle ou alcoxy diméthicone copolyol, des huiles hydrocarbonées, des pigments et charges ainsi que des cires. Les compositions à base d'huiles de silicones et de résines siliconées ainsi que celles à base de latex conduisent à des films colorés mats. Or, la femme est aujourd'hui à la recherche de produits notamment de coloration des lèvres, brillants. De plus, les propriétés de sans transfert des films déposés ne sont pas parfaites. En particulier, une pression ou un frottement prononcé, conduit à une diminution de la couleur du dépôt et à un redépôt sur le support mis en contact avec ces films.In application JP-A-61 -65809, the company Shiseido has described "non-transfer" lipstick compositions containing a siloxysilicate resin (with a three-dimensional network), a volatile silicone oil with a cyclic silicone chain and pulverulent fillers. Furthermore, the company Noevier described in document JP-A-62-61911 compositions of lipstick, eyeliner and "no transfer" foundation comprising one or more volatile silicones associated with one or more waxes hydrocarbons. These compositions, although having improved "no transfer" properties, have the drawback of leaving on the lips, after evaporation of the silicone oils, a film which becomes uncomfortable over time (feeling of drying and tightness), spreading a number of women of this type of lipstick. More recently, the company Procter & Gamble envisaged in its patent application WO-A-96/36323 compositions of mascara of the water-in-oil emulsion type having a long hold, a resistance to water and leaving no traces. These compositions contain, among other things, a water-insoluble polymer, generally called a latex, associated with a surfactant of the alkyl or alkoxy dimethicone copolyol type, hydrocarbon oils, pigments and fillers as well as waxes. The compositions based on silicone oils and silicone resins as well as those based on latex lead to matt colored films. However, women are now looking for products, in particular lip gloss, that are shiny. In addition, the transfer-free properties of the deposited films are not perfect. In particular, a pronounced pressure or friction leads to a reduction in the color of the deposit and to a redeposition on the support brought into contact with these films.
En outre, les documents EP-A-497144 et FR-A-2 357 244 décrivent des compositions dites "sans transfert", contenant un polymère bloc styrène-éthylène-propylène associé à des cires, des huiles légères ou volatiles et des pigments. Ces compositions présentent l'inconvénient d'être peu confortables, d'avoir des propriétés cosmétiques quelconques et d'être difficilement formulables. Par ailleurs, les propriétés "sans transfert" de ces compositions sont très moyennes. II subsiste donc le besoin d'une composition ne présentant pas les inconvénients ci- dessus et ayant notamment des propriétés de "sans transfert" total, même lors d'une pression ou d'un frottement prononcé, un aspect plus ou moins brillant, adapté au désir de la consommatrice, ne migrant pas, ne desséchant pas la peau ou les lèvres sur lesquelles elle est appliquée, aussi bien lors de l'application qu'au cours du temps.In addition, documents EP-A-497,144 and FR-A-2,357,244 describe so-called "transfer-free" compositions containing a styrene-ethylene-propylene block polymer combined with waxes, light or volatile oils and pigments. These compositions have the disadvantage of being uncomfortable, of having any cosmetic properties and of being difficult to formulate. Furthermore, the "no transfer" properties of these compositions are very average. There therefore remains a need for a composition which does not have the above drawbacks and which in particular has total "transfer-free" properties, even when it is strongly pressed or rubbed, with a more or less shiny appearance, suitable at the consumer's desire, does not migrate, does not dry out the skin or the lips to which it is applied, both during application and over time.
La demanderesse a constaté, de façon tout à fait surprenante, que l'utilisation d'un polymère dispersible dans une phase grasse, associé à un agent rhéologique particulier, dans une composition cosmétique, dermatologique, pharmaceutique ou hygiénique permettait d'obtenir un film brillant, de très bonne tenue, ne transférant peu ou pas du tout, ne migrant pas, résistant à l'eau, tout en étant très agréable à l'application et à porter tout au long de la journée. Le film est notamment souple et flexible.The Applicant has found, quite surprisingly, that the use of a polymer dispersible in an oily phase, associated with a particular rheological agent, in a cosmetic, dermatological, pharmaceutical or hygienic composition makes it possible to obtain a shiny film. , very good hold, not transferring little or not at all, not migrating, water resistant, while being very pleasant to apply and to wear throughout the day. The film is particularly soft and flexible.
La présente invention a donc pour objet une composition à application topique, contenant une phase grasse liquide et des particules de polymère dispersées dans la phase grasse liquide et stabilisées en surface par un agent stabilisant, ladite phase grasse étant, en outre, épaissie par un agent rhéologique liposoluble de type polysaccharide.The present invention therefore relates to a composition for topical application, containing a liquid fatty phase and polymer particles dispersed in the liquid fatty phase and surface stabilized by a stabilizing agent, said fatty phase being, in addition, thickened by an agent. liposoluble rheological polysaccharide type.
Cette composition est en particulier une composition cosmétique, dermatologique, hygiénique ou pharmaceutique. Elle contient donc des ingrédients compatibles avec la peau, les muqueuses et les fibres kératiniques ou phanères. Elle peut se présenter sous forme de gel anhydre, d'émulsion ou de dispersion huile-dans-eau ou eau-dans-huile ou encore sous forme d'émulsion multiple.This composition is in particular a cosmetic, dermatological, hygienic or pharmaceutical composition. It therefore contains ingredients compatible with the skin, mucous membranes and keratinous or dander fibers. It can be in the form of an anhydrous gel, an emulsion or an oil-in-water or water-in-oil dispersion or also in the form of a multiple emulsion.
Selon l'invention le polymère est insoluble dans la phase grasse même à sa température de ramollissement, à l'inverse d'une cire même d'origine polymerique qui est elle soluble dans la phase grasse à sa température de fusion. Il permet, en outre, la formation d'un dépôt fiimogène se présentant sous forme de film isolable, continu et homogène et/ou est caractérisé par l'enchevêtrement des chaînes polymériques. Avec une cire même obtenue par polymérisation on obtient, après fusion dans la phase grasse, une recristaliisa- tion.According to the invention, the polymer is insoluble in the 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. It also allows the formation of a film-forming deposit in the form of an isolable, continuous and homogeneous film and / or is characterized by the entanglement of the polymer chains. Even with a wax obtained by polymerization, after melting in the fatty phase, recrystallization is obtained.
Le polymère en dispersion utilisé dans la présente invention peut être de toute nature. On peut ainsi employer un polymère radicalaire, un polycondensat, voire un polymère d'origine naturelle et leurs mélanges. Ce polymère peut être choisi par l'homme du métier en fonction de ses propriétés et selon l'application ultérieure souhaitée pour la composition. De préférence le polymère utilisé est filmifiable. Il est toutefois possible d'utiliser un polymère non filmifiable. Par polymère non filmifiable, on entend un polymère non capable de former, seul, un film isolable. Ce polymère permet, en association avec un composé non volatil du type huile, de former un dépôt continue et homogène sur la peau et les muqueuses comme les lèvres.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. Preferably the polymer used is film-forming. It is however possible to use a non-film-forming polymer. The term “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 the mucous membranes such as the lips.
Avantageusement, la composition contient au moins un ingrédient choisi parmi les actifs cosmétiques, dermatologiques, hygiéniques et pharmaceutiques, les matières colorantes et leurs mélanges. Grâce à la dispersion de particules de polymère stabilisées en surface présente dans la phase grasse liquide, la composition de l'invention permet de limiter, voire supprimer le transfert de la composition et en particulier le transfert des actifs et/ou des matières colorantes et donc de maintenir ces actifs et/ou matières colorantes là où ils ont été déposés.Advantageously, 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 surface-stabilized polymer particles present in the liquid fatty phase, the composition of the invention makes it possible to limit or even eliminate the transfer of the composition and in particular the transfer of the active agents and / or of the coloring matters and therefore maintain these active ingredients and / or coloring materials where they have been deposited.
Selon l'invention, la quantité de polymère en dispersion doit être suffisante pour former sur la peau et/ou les lèvres et/ou les fibres kératiniques un film apte à piéger les matières colorantes et/ou les actifs cosmétiques ou dermatologiques et/ou les huiles en vue de limiter, voire supprimer, leur transfert sur un support avec lequel le film est mis en contact. La quantité de polymère est fonction de la quantité de matières colorantes et/ou d'actifs et/ou d'huiles, contenue dans la composition. En pratique, la quantité de polymère peut être supérieure à 2 % en poids (en matière active), par rapport au poids total de la composition.According to the invention, 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 in order to limit, or even eliminate, their transfer to a support with which the film is brought into contact. 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.
Un autre objet de l'invention est l'utilisation dans une composition à application topique, cosmétique ou hygiénique ou pour la fabrication d'une composition à application topique, dermatologique ou pharmaceutique, de particules d'au moins un polymère dispersées dans une phase grasse liquide et stabilisées en surface par un agent stabilisant, ladite phase grasse étant épaissie par un agent rhéologique liposoluble de type polysaccharide, pour diminuer, voire supprimer, le transfert du film de composition déposé sur les muqueuses et/ou la peau d'être humain vers un support mis en contact avec le film et/ou conserver sa brillance.Another subject of the invention is the use in a composition for topical, cosmetic or hygienic application or for the manufacture of a composition for topical, dermatological or pharmaceutical application, of particles of at least one polymer dispersed in a fatty phase liquid and surface stabilized by a stabilizing agent, said fatty phase being thickened by a liposoluble rheological agent of polysaccharide type, to reduce, or even eliminate, the transfer of the film of composition deposited on the mucous membranes and / or the skin of human beings towards a support brought into contact with the film and / or maintain its gloss.
L'invention a encore pour objet un procédé de soin cosmétique ou de maquillage des lèvres, des phanères ou de la peau, consistant à appliquer sur respectivement les lèvres, les phanères ou la peau une composition cosmétique telle définie précédemment.The subject of the invention is also a method of cosmetic care or of making up the lips, the integuments or the skin, consisting in applying to the lips, the integuments or the skin respectively, a cosmetic composition as defined above.
L'invention a encore pour objet un procédé pour limiter, voire supprimer, le transfert d'une composition de maquillage ou de soin de la peau ou des lèvres sur un support différent de la dite peau et desdites lèvres, contenant une phase grasse liquide et au moins un ingrédient choisi parmi les matières colorantes et les actifs cosmétiques, dermatologiques, hygiéniques et pharmaceutiques, consistant à introduire dans la phase grasse liquide des particules de polymère dispersibles dans la phase grasse liquide et stabilisables en surface par un agent stabilisant et au moins un agent rhéologique liposoluble de type polysaccharide. Un avantage de l'utilisation d'une dispersion de particules dans une composition de l'invention est que les particules restent à l'état de particules élémentaires, sans former d'agglomérats, dans la phase grasse, ce qui ne serait pas le cas avec des particules minérales de taille nanométrique. Un autre avantage de la dispersion de polymère est la possibilité d'obtenir des compositions très fluides (de l'ordre de 130 centipoises), même en présence d'un taux élevé de polymère.The subject of the invention is also a method for limiting, or even eliminating, the transfer of a makeup or care composition for the skin or the lips on a support different from the said skin and the said lips, containing a liquid fatty phase and at least one ingredient chosen from coloring matters and cosmetic, dermatological, hygienic and pharmaceutical active ingredients, consisting in introducing into the liquid fatty phase particles of polymer dispersible in the liquid fatty phase and stabilized at the surface by a stabilizing agent and at least one liposoluble rheological agent of polysaccharide type. An advantage of using a dispersion of particles in a composition of the invention is that the particles remain in the state of elementary particles, without forming agglomerates, in the fatty phase, which would not be the case. with nanoscale mineral particles. Another advantage of the polymer dispersion is the possibility of obtaining very fluid compositions (of the order of 130 centipoise), even in the presence of a high level of polymer.
Encore un autre avantage d'une telle dispersion est qu'il est possible de calibrer à volonté la taille des particules de polymère, et de moduler leur "polydispersité" en taille lors de la synthèse. Il est ainsi possible d'obtenir des particules de très petite taille, qui sont invisi- bles à l'œil nu lorsqu'elles sont dans la composition et lorsqu'elles sont appliquées sur la peau ou les lèvres. Ceci ne serait pas possible avec des pigments sous forme particu- laire, leur constitution ne permettant pas de moduler la taille moyenne des particules. On a de plus constaté que la composition selon l'invention, présente des qualités d'étalement et d'adhésion sur la peau, les semi-muqueuses ou les muqueuses, particulièrement intéressantes, ainsi qu'un toucher onctueux et agréable. Cette composition a, en outre, l'avantage de se démaquiller facilement notamment avec un lait démaquillant classique. Ceci est tout à fait remarquable puisque les compositions de l'art antérieur à pro- priétés "sans transfert" élevées sont très difficiles à démaquiller. En général, elles sont vendues avec un produit démaquillant spécifique, ce qui introduit une contrainte supplémentaire pour l'utilisatrice.Yet another advantage of such a 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 very small particles, which are invisible. bles with the naked eye when they are in the composition and when they are applied to the skin or the lips. This would not be possible with pigments in particulate form, their constitution not allowing the average particle size to be modulated. It has also been found that the composition according to the invention exhibits qualities of spreading and adhesion to the skin, the semi-mucous membranes 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. This is quite remarkable since the compositions of the prior art with high "no transfer" properties are very difficult to remove. In general, they are sold with a specific make-up removing product, which introduces an additional constraint for the user.
La composition selon l'invention comprend donc avantageusement une ou plusieurs dis- persions stables de particules généralement sphériques d'un ou plusieurs polymères, dans une phase grasse liquide physiologiquement acceptable. Ces dispersions peuvent notamment se présenter sous forme de nanoparticules de polymères en dispersion stable dans ladite phase grasse. Les nanoparticules sont de préférence d'une taille comprise entre 5 et 600 nm, étant donné qu'au-delà d'environ 600 nm, les dispersions de particules deviennent beaucoup moins stables.The composition according to the invention therefore advantageously comprises one or more stable dispersions of generally spherical particles of one or more polymers, in a physiologically acceptable liquid fatty phase. These dispersions can in particular be in the form of nanoparticles of polymers in stable dispersion in said fatty phase. The nanoparticles are preferably between 5 and 600 nm in size, since above about 600 nm, the particle dispersions become much less stable.
Encore un avantage de la dispersion de polymère de la composition. de l'invention est la possibilité de faire varier la température de transition vitreuse (Tg) du polymère ou du système polymerique (polymère plus additif du type plastifiant), et de passer ainsi d'un polymère dur à un polymère plus ou moins mou, permettant de régler les propriétés mécaniques de la composition en fonction de l'application envisagée.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 polymeric system (polymer more additive of the plasticizer type), and thus of passing from a hard polymer to a more or less soft polymer, allowing the mechanical properties of the composition to be adjusted according to the intended application.
Il est possible d'utiliser des polymères filmifiables, de préférence ayant une Tg basse, inférieure ou égale à la température de la peau notamment inférieure à 40°C. On obtient ainsi une dispersion qui peut fiimifier lorsqu'elle est appliquée sur un support, ce qui n'est pas le cas lorsqu'on utilise des dispersions de pigments minéraux selon l'art antérieur.It is possible to use film-forming polymers, preferably having a low Tg, less than or equal to the skin temperature, in particular less than 40 ° C. A dispersion is thus obtained which can improve when it is applied to a support, which is not the case when dispersions of mineral pigments according to the prior art are used.
Les polymères en dispersion utilisables dans la composition de l'invention ont de préférence un poids moléculaire de l'ordre de 2000 à 10 000 000 et une Tg de -100°C à 300°C et mieux de -10° à 50°C.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 from -100 ° C to 300 ° C and better still from -10 ° to 50 ° C .
Lorsque le polymère présente une température de transition vitreuse trop élevée pour l'application souhaitée, on peut lui associer un plastifiant de manière à abaisser cette température du mélange utilisé. Le plastifiant peut être choisi parmi les plastifiants usuel- lement utilisés dans le domaine d'application et notamment parmi les composés susceptibles d'être des solvants du polymère.When the polymer has a glass transition temperature too high for the desired application, 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 usually used in the field of application and in particular from the compounds capable of being solvents for the polymer.
Parmi les polymères filmifiables, on peut citer des homopolymères ou des copolymères radicalaires, acryliques ou vinyliques, de préférence ayant une Tg inférieure ou égale à 40°C et notamment allant de - 10° à 30°C.Among the film-forming polymers, mention may be made of radical, acrylic or vinyl homopolymers or copolymers, preferably having a Tg less than or equal to 40 ° C and in particular ranging from - 10 ° to 30 ° C.
Parmi les polymères non filmifiables, on peut citer des homopolymères ou copolymères radicalaires, vinyliques ou acryliques, éventuellement réticulés, ayant de préférence une Tg supérieure ou égale à 40°C et notamment allant de 45° à 150°C.Among the non-film-forming polymers, mention may be made of radical, vinyl or acrylic homopolymers or copolymers, optionally crosslinked, preferably having a Tg greater than or equal to 40 ° C. and in particular ranging from 45 ° to 150 ° C.
Par polymère radicalaire, on entend un polymère obtenu par polymérisation de monomères à insaturation notamment éthylénique, chaque monomère étant susceptible de s'ho- mopolymériser (à l'inverse des polycondensats). Les polymères radicalaires peuvent être notamment des polymères, ou des copolymères, vinyliques, notamment des polymères acryliques.By 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, especially acrylic polymers.
Les polymères vinyliques peuvent résulter de la polymérisation de monomères à insaturation éthylénique ayant au moins un groupement acide et/ou des esters de ces monomères acides et/ou des amides de ces acides.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.
Comme monomère porteur de groupement acide, on peut utiliser des acides carboxyli- ques insaturés α,β-éthyléniques tes que l'acide acrylique, l'acide méthacrylique, l'acide crotonique, l'acide maleique, l'acide itaconique. On utilise de préférence l'acide (méth)acrylique et l'acide crotonique, et plus préférentiellement l'acide (méth)acrylique.As monomer carrying an acid group, α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid can be used. Preferably (meth) acrylic acid and crotonic acid are used, and more preferably (meth) acrylic acid.
Les esters de monomères acides sont avantageusement choisis parmi les esters de l'acide (méth)acrylique (encore appelé les (méth)acrylates), comme les (méth)acrylates d'alkyle, en particulier d'alkyie en CrC20, de préférence en Cι-C8, les (méth)acrylates d'aryie, en particulier d'aryle en C6-C10, les (méth)acrylates d'hydroxyalkyle, en particulier d'hydroxyalkyle en C2-C6. Comme (méth)acrylates d'alkyle, on peut citer le (méth)acrylate de méthyle, d'éthyle, de butyle, d'isobutyle, d'éthyl-2 hexyle et le lauryle. Comme (méth)acrylates d'hydroxyalkyle, on peut citer le (méth)acrylate d'hydroxyéthyle, le (méth)acrylate de 2-hydroxypropyle. Comme (méth)acrylates d'aryle, on peut citer l'acry- late de benzyle ou de phényle.The esters of acidic monomers are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), such as alkyl (meth) acrylates, in particular of C 1 -C 20 alkyl, preferably in Cι-C 8 , ary (meth) acrylates, in particular C 6 -C 10 aryl, hydroxyalkyl (meth) acrylates, in particular C 2 -C 6 hydroxyalkyl. As alkyl (meth) acrylates, mention may be made of methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth) acrylate. As hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. As aryl (meth) acrylates, mention may be made of benzyl or phenyl acrylate.
Les esters de l'acide (méth)acrylique particulièrement préférés sont les (méth)acrylates d'alkyle.Particularly preferred esters of (meth) acrylic acid are alkyl (meth) acrylates.
Comme polymère radicalaire, on utilise de préférence les copolymère d'acide (méth)acrylique et de (méth)acrylate d'alkyle, notamment d'alkyie en C C4. Plus préférentiellement, on peut utiliser les acrylates de méthyle éventuellement copolymérisés avec l'acide acrylique.As radical polymer, use is preferably made of copolymers of (meth) acrylic acid and of alkyl (meth) acrylate, in particular of CC 4 alkyl. More preferably, it is possible to use methyl acrylates optionally copolymerized with acrylic acid.
Comme amides des monomères acides, on peut citer les (méth)acrylamides, et notamment les N-alkyl (méth)acrylamides, en particulier d'alkyl en C2-C12 tels que le N-éthyl acrylamide, le N-t-butyl acrylamide, le N-octyl acrylamide ; les N- dialkyl (C C4) (méth)acrylamides.As amides of the acid monomers, mention may be made of (meth) acrylamides, and in particular N-alkyl (meth) 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.
Les polymères vinyliques peuvent également résulter de la polymérisation de monomères à insaturation éthylénique ayant au moins un groupe aminé, sous forme libre ou bien partiellement ou totalement neutralisée, ou bien encore partiellement ou totalement quatemi- sée. De tels monomères peuvent être par exemple le (méth)acrylate de diméthylaminoé- thyle, le methacrylamide de diméthylaminoethyl, la vinylamine, la vinyipyridine, le chlorure de diallyldiméthylammonium.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 methacrylamide, vinylamine, vinyipyridine, diallyldimethylammonium chloride.
Les polymères vinyliques peuvent également résulter de l'homopolymérisation ou de la copolymérisation d'au moins un monomère choisi parmi les esters vinyliques et les mo- nomères styreniques. En particulier, ces monomères peuvent être polymérisés avec des monomères acides et/ou leurs esters et/ou leurs amides, tels que ceux mentionnés précédemment. Comme exemple d'esters vinyliques, on peut citer l'acétate de vinyle, le pro- pionate de vinyle, le néodécanoate de- vinyle, le pivalate de vinyle, le benzoate de vinyle et le t-butyl benzoate de vinyle. Comme monomères styreniques, on peut citer le styrène et l'alpha-méthyl styrène.The vinyl polymers can also result from the homopolymerization or from the copolymerization of at least one monomer chosen from vinyl esters and styrenic monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above. Examples of vinyl esters that may be mentioned include vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. As styrenic monomers, mention may be made of styrene and alpha-methyl styrene.
La liste des monomères donnée n'est pas limitative et il est possible d'utiliser tout monomère connu de l'homme du métier entrant dans les catégories de monomères acryliques et vinyliques (y compris les monomères modifiés par une chaîne siliconée). Comme autres monomères vinyliques, on peut encore citer :The list of monomers given is not exhaustive and it is possible to use any monomer known to a person skilled in the art falling within the categories of acrylic and vinyl monomers (including the monomers modified by a silicone chain). As other vinyl monomers, mention may also be made of:
- la N-vinyipyrrolidone, la vinylcaprolactame, les vinyl N-alkyl(CrC6) pyrroles, les vinyl- oxazoles, les vinyl-thiazoles, les vinylpyrimidines, les vinylimidazoles,- N-vinyipyrrolidone, vinylcaprolactam, vinyl N-alkyl (CrC 6 ) pyrroles, vinyl oxazoles, vinyl thiazoles, vinylpyrimidines, vinylimidazoles,
- les oléfines tels que l'éthyiène, le propylène, le butylène, l'isoprène, le butadiène.- olefins such as ethyiene, propylene, butylene, isoprene, butadiene.
Le polymère vinylique peut être réticulé à l'aide de monomère difonctionnel, notamment comprenant au moins deux insaturations éthyléniques, tel que le diméthacrylate d'éthy- lène glycol ou le phtalate de diallyle.The vinyl polymer can be crosslinked using a difunctional monomer, in particular comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate or diallyl phthalate.
De façon non limitative, les polymères en dispersion de l'invention peuvent être choisis parmi, les polymères ou copolymères suivants : polyuréthannes, polyuréthannes- acryliques, polyurées, polyurée-poiyuréthannes, polyester-polyuréthannes, polyéther- polyuréthannes, polyesters, polyesters amides, polyesters à chaîne grasse, alkydes ; po- lymères ou copolymères acryliques et/ou vinyliques ; copolymères acryliques-silicone ; polyacrylamides ; polymères siiiconés comme les polyuréthannes ou acryliques siiiconés, polymères fluorés et leurs mélanges.Without limitation, 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.
La phase grasse liquide de la composition peut être constituée de toute huile cosméti- quement ou dermatologiquement acceptable, et de façon générale physiologiquement acceptable, notamment choisie parmi les huiles d'origine minérale, animale, végétale ou synthétique, carbonées, hydrocarbonées, fiuorées et/ou siliconées, seules ou en mélange dans la mesure où elles forment un mélange homogène et stable et où elles sont compatibles avec l'utilisation envisagée.The liquid fatty phase of the composition may 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, hydrocarbon, fluorinated and / or silicone, alone or in mixture insofar as they form a homogeneous and stable mixture and where they are compatible with the intended use.
Par "phase grasse liquide", on entend tout milieu non aqueux liquide à température ambiante et pression atmosphérique. Cette phase grasse peut contenir une phase grasse liquide volatile et/ou une phase grasse non volatile. Par "phase grasse volatile", on entend tout milieu non aqueux susceptible de s'évaporer de la peau ou des lèvres, en moins d'une heure. Cette phase volatile comporte notamment des huiles ayant une pression de vapeur, à température ambiante (25°C) et pression atmosphérique (760mm Hg) allant de 10"3 à 300mm de Hg (0J3 Pa à 40 000 Pa). La phase grasse liquide totale de la composition peut représenter de 5 % à 97,90 % du poids total de la composition et de préférence de 20 à 85 %. La partie non volatile peut représenter de 0 à 80 % du poids total de la composition et mieux de 1 à 50%.By "liquid fatty phase" is meant any non-aqueous medium which is liquid at room temperature and atmospheric pressure. This fatty phase may contain a volatile liquid fatty phase and / or a non-volatile fatty phase. By "volatile fatty phase" is meant any non-aqueous medium capable of evaporating from the skin or the lips in less than an hour. This volatile phase comprises in particular oils having a vapor pressure, at ambient temperature (25 ° C) and atmospheric pressure (760mm Hg) ranging from 10 "3 to 300mm Hg (0J3 Pa to 40,000 Pa). The liquid fatty phase total of the composition can represent from 5% to 97.90% of the total weight of the composition and preferably from 20 to 85%. The non-volatile part can represent from 0 to 80% of the total weight of the composition and better still from 1 at 50%.
Comme phase grasse liquide utilisable dans l'invention, on peut ainsi citer les huiles hy- drocarbonees telles que l'huile de paraffine ou de vaseline, l'huile de vison, de tortue, de soja, le perhydrosqualène, l'huile d'amande douce, de calophyllum, de palme, de pépins de raisin, de sésame, de maïs, de parléam, d'arara, de colza, de tournesol, de coton, d'abricot, de ricin, d'avocat, de jojoba, d'olive ou de germes de céréales ; des esters d'acide lanolique, d'acide oléique, d'acide iaurique, d'acide stéarique ; les esters gras tels que le myristate d'isopropyle, le palmitate d'isopropyle, le stéarate de butyle, le laurate d'hexyle, l'adipate de diisopropyle, l'isononate d'isononyle, le palmitate de 2-éthyl-hexyle, le laurate de 2-hexyl-décyle, le palmitate de 2-octyl-décyle, le myristate ou le lactate de 2- octyl-dodécyle, le succinate de 2-diéthyl-hexyle, le malate de diisostéaryle, le triisostéa- rate de glycérine ou de diglycérine ; les acides gras supérieurs tels que l'acide myristique, l'acide palmitique, l'acide stéarique, l'acide béhénique, l'acide oléique, l'acide linoiéique, l'acide linolénique ou l'acide isostéarique ; les alcools gras supérieurs tels que le cétanol, l'alcool stéarylique ou l'alcool oléique, l'alcool linoiéique ou linolénique, l'alcool isostéarique ou l'octyl dodécanol ; les huiles siliconées telles que les polydiméthylsiloxanes (PDMS), éventuellement phénylées telles que les phényltriméthicones ou éventuellement substitués par des groupements aliphatiques et/ou aromatiques, éventuellement fluorés, ou par des groupements fonctionnels tels que des groupements hydroxyle, thiol et/ou aminé ; les polysiloxanes modifiés par des acides gras, des alcools gras ou des po- lyoxyaikylènes, les siiiconés fluorées, les huiles perfluorées.As liquid fatty phase which can be used in the invention, mention may therefore be made of hydrocarbon oils such as paraffin or petrolatum oil, mink, turtle, soybean oil, perhydrosqualene, sweet almond, calophyllum, palm, grapeseed, sesame, corn, parlam, arara, rapeseed, sunflower, cotton, apricot, castor, avocado, jojoba, olive or germ of cereals; esters of lanolic acid, oleic acid, iauric acid, stearic acid; fatty esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononate, 2-ethyl-hexyl palmitate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl-dodecyl myristate or lactate, 2-diethyl-hexyl succinate, diisostearyl malate, glycerin triisostearate or diglycerin; higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoiic acid, linolenic acid or isostearic acid; higher fatty alcohols such as cetanol, stearyl alcohol or oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyl dodecanol; silicone oils such as polydimethylsiloxanes (PDMS), optionally phenylated such as phenyltrimethicones or optionally substituted by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amino groups; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones, perfluorinated oils.
Avantageusement, on peut utiliser une ou plusieurs huiles volatiles à température ambiante. Ces huiles volatiles sont favorables à l'obtention d'un film à propriétés "sans transfert" total. Après évaporation de ces huiles, on obtient un dépôt filmogène souple, non collant sur la peau ou les muqueuses, suivant respectivement le mouvements de la peau ou des lèvres, sur lesquelles la composition est appliquée. Ces huiles volatiles facilitent, en outre, l'application de la composition sur la peau, les muqueuses et les phanères. Elles peuvent être hydrocarbonées ou siliconées comportant éventuellement des groupements alkyle ou alkoxy, pendants ou en bout de chaîne siliconée. Comme huile volatile utilisable dans l'invention, on peut citer les siiiconés linéaires ou cycliques ayant de 2 à 7 atomes de silicium, ces siiiconés comportant éventuellement des groupes alkyle ou alkoxy ayant de 1 à 10 atomes de carbone ainsi que les isoparaffines en C8-Cι6. Ces huiles volatiles représentent notamment de 20 à 97,90 % du poids total de la composition, et mieux de 30 à 75 %.Advantageously, one or more volatile oils can be used at room temperature. These volatile oils are favorable for obtaining a film with total "transfer-free" properties. After evaporation of these oils, a flexible film-forming deposit is obtained, which is not sticky on the skin or the mucous membranes, respectively according to the movements of the skin or the lips, to which the composition is applied. These volatile oils also facilitate the application of the composition to the skin, the mucous membranes and the integuments. They can be hydrocarbon or silicone optionally comprising alkyl or alkoxy groups, pendant or at the end of the silicone chain. As volatile oil which can be used in the invention, mention may be made of linear or cyclic siionics having from 2 to 7 silicon atoms, these siicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms as well as C 8 isoparaffins -Cι 6 . These volatile oils represent in particular from 20 to 97.90% of the total weight of the composition, and better still from 30 to 75%.
Comme huile volatile utilisable dans l'invention, on peut citer notamment l'octaméthylcy- clotétrasiloxane, le décaméthylcyclopentasiloxane, l'hexadécaméthylcyclohexasiloxane, l'heptaméthylhexyltrisiloxane, l'heptaméthyloctyltrisiloxane ou les isoparaffines en C8-C16 telles que les 'ISOPARs', les PERMETYLs et notamment l'isododécane.As volatile oil used in the invention, we may notably mention the octaméthylcy- clotétrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane or isoparaffins C 8 -C 16 such as 'Isopar', the PERMETYLs and in particular isododecane.
Dans un mode particulier de réalisation de l'invention, on choisit le phase grasse liquide dans le groupe comprenant :In a particular embodiment of the invention, the liquid fatty phase is chosen from the group comprising:
- les composés liquides non aqueux ayant un paramètre de solubilité global selon l'espace de solubilité de HANSEN inférieur à 17 (MPa)1/2, - ou les monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de HANSEN inférieur ou égal à 20 (MPa)1 2,- non-aqueous liquid compounds having a global solubility parameter according to the HANSEN solubility space of less than 17 (MPa) 1/2 , - or monoalcohols having a global solubility parameter according to the lower HANSEN solubility space or equal to 20 (MPa) 1 2 ,
- ou leurs mélanges.- or their mixtures.
Le paramètre de solubilité global δ global selon l'espace de solubilité de HANSEN est dé- fini dans l'article "Solubility parameter values" de Eric A. Grulke de l'ouvrage "Polymer Handbook" 3ème édition, Chapitre VII, pages 519-559 par la relation : δ = ( dD 2+ dp2 + dH 2)1/2 , dans laquelle : - dD caractérise les forces de dispersion de LONDON issues de la formation de dipôles induits lors des chocs moléculaires,The total overall solubility parameter δ according to the Hansen solubility space is de- fined in the article "Solubility parameter values" by Eric A. Grulke of the book "Polymer Handbook" 3rd edition, Chapter VII, pages 519 -559 by the relation: δ = (d D 2 + dp 2 + d H 2 ) 1/2 , in which: - d D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks,
- dp caractérise les forces d'interactions de DEBYE entre dipôles permanents,- dp characterizes the DEBYE interaction forces between permanent dipoles,
- dH caractérise les forces d'interactions spécifiques (type liaisons hydrogène, acide/base, donneur/accepteur, etc.). La définition des solvants dans l'espace de solubilité tridimen- sionnel selon HANSEN est donnée dans l'article de C. M. HANSEN : "The three dimen- sional solubility parameters" J. Paint Technoi. 39, 105 (1967).- d H characterizes the specific interaction forces (such as hydrogen bonds, acid / base, donor / acceptor, etc.). The definition of solvents in the three-dimensional solubility space according to HANSEN is given in the article by CM HANSEN: "The three dimensional solubility parameters" J. Paint Technoi. 39, 105 (1967).
Parmi les phases grasses liquides ayant un paramètre de solubilité global selon l'espace de solubilité de HANSEN, inférieur ou égal à 17 (MPa)1 2, on peut citer des huiles végéta- les formées par des esters d'acides gras et de polyols, en particulier les triglycérides, telles que l'huile de tournesol, de sésame ou de colza, ou les esters dérivés d'acides ou d'alcools à longue chaîne (c'est à dire ayant de 6 à 20 atomes de carbone), notamment les esters de formule RCOOR' dans laquelle R représente le reste d'un acide gras supérieur comportant de 7 à 19 atomes de carbone et R' représente une chaîne hydrocarbo- née comportant de 3 à 20 atomes de carbone, tels que les palmitates, les adipates et les benzoates, notamment l'adipate de diisopropyle. On peut également citer les hydrocarbures et notamment des huiles de paraffine, de vaseline, ou le polyisobutylène hydrogéné, l'isododécane, ou encore les 'ISOPARs', isoparaffines volatiles. On peut encore citer les huiles de silicone telles que les polydiméthylsiioxanes et les poiyméthylphénylsiloxanes, éventuellement substitués par des groupements aliphatiques et/ou aromatiques, éventuellement fluorés, ou par des groupements fonctionnels tels que des groupements hy- droxyle, thiol et/ou aminé, et les huiles siliconées volatiles, notamment cycliques. On peut également citer les solvants, seuls ou en mélange, choisis parmi (i) les esters linéaires, ramifiés ou cycliques, ayant plus de 6 atomes de carbone, (ii) les éthers ayant plus de 6 atomes de carbone, (iii) les cétones ayant plus de 6 atomes de carbone. Par monoalcools ayant un paramètre de solubilité global selon l'espace de solubilité de HANSEN inférieur ou égal à 20 (MPa)1/2, on entend les alcools gras aliphatiques ayant au moins 6 atomes de carbone, la chaîne hydrocarbonée ne comportant pas de groupement de substitution. Comme monoalcools selon l'invention, on peut citer l'alcool oléique, le décanol, le dodé- canol, l'octadécanol et l'alcool linoiéique.Among the liquid fatty phases having a global solubility parameter according to the HANSEN solubility space, less than or equal to 17 (MPa) 1 2 , mention may be made of vegetable oils formed by esters of fatty acids and of polyols , in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or long-chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR 'in which R represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R' represents a hydrocarbon chain born with 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate. Mention may also be made of hydrocarbons and in particular oils of paraffin, of petrolatum, or hydrogenated polyisobutylene, isododecane, or also 'ISOPARs', volatile isoparaffins. Mention may also be made of silicone oils such as polydimethylsiioxanes and poiymethylphenylsiloxanes, 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. Mention may also be made of the 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. By 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, the hydrocarbon chain not comprising a group of substitution. As monoalcohols according to the invention, mention may be made of oleic alcohol, decanol, dodecanol, octadecanol and linoleic alcohol.
Comme milieu non aqueux, on peut aussi utiliser ceux décrits dans le document FR-A-2 710 646 dθ LV.M.H.As non-aqueous medium, one can also use those described in document FR-A-2 710 646 of LV.M.H.
Le choix du milieu non aqueux est effectué par l'homme du métier en fonction de la nature des monomères constituant le polymère et/ou de la nature du stabilisant, comme indiqué ci-après. La dispersion de polymère peut être fabriquée comme décrit dans le document EP-A- 749747. La polymérisation peut être effectuée en dispersion, c'est-à-dire par précipitation du polymère en cours de formation, avec protection des particules formées avec un stabilisant. On prépare donc un mélange comprenant les monomères initiaux ainsi qu'un amorceur radicalaire. Ce mélange est dissous dans un solvant appelé, dans la suite de la présente description, "solvant de synthèse". Lorsque la phase grasse est une huile non volatile, on peut effectuer la polymérisation dans un solvant organique apoiaire (solvant de synthèse) puis ajouter l'huile non volatile (qui doit être miscible avec ledit solvant de synthèse) et distiller sélectivement le solvant de synthèse.The choice of 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 produced 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 with a stabilizer. . A mixture is therefore prepared comprising the initial monomers and a radical initiator. This mixture is dissolved in a solvent called, in the remainder of this description, "synthetic solvent". When the fatty phase is a non-volatile oil, the polymerization can be carried out in an organic organic solvent (synthesis solvent) then add the non-volatile oil (which must be miscible with said synthesis solvent) and selectively distill the synthesis solvent .
On choisit donc un solvant de synthèse tel que les monomères initiaux, et l'amorceur radicalaire, y sont solubies, et les particules de polymère obtenu y sont insolubles afin qu'elles y précipitent lors de leur formation. En particulier, on peut choisir le solvant de synthèse parmi les alcanes tels que l'heptane, l'isododécane ou le cyclohexane.We therefore choose a synthetic solvent such as the initial monomers, and the radical initiator, are dissolved therein, and the polymer particles obtained are insoluble therein so that they precipitate there during their formation. In particular, the synthesis solvent can be chosen from alkanes such as heptane, isododecane or cyclohexane.
Lorsque la phase grasse choisie est une huile volatile, on peut directement effectuer la polymérisation dans ladite huile qui joue donc également le rôle de solvant de synthèse. Les monomères doivent également y être solubies, ainsi que l'amorceur radicalaire, et le polymère obtenu doit y être insoluble.When the fatty phase chosen is a volatile oil, the polymerization can be carried out directly in said oil which therefore also plays the role of synthetic solvent. The monomers must also be dissolved there, as well as the radical initiator, and the polymer obtained must be insoluble therein.
Les monomères sont de préférence présents dans le solvant de synthèse, avant polymérisation, à raison de 5-20% en poids du mélange réactionnel. La totalité des monomères peut être présente dans le solvant avant le début de la réaction, ou une partie des mono- mères peut être ajoutée au fur et à mesure de l'évolution de la réaction de polymérisation.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.
L'amorceur radicalaire peut être notamment l'azo-bis-isobutyronitrile ou le tertiobutylpe- roxy-2-éthyl hexanoate. StabilisantThe radical initiator can in particular be azo-bis-isobutyronitrile or tert-butylpyroxy-2-ethyl hexanoate. Stabilizing
Les particules de polymère sont stabilisées en surface, au fur et à mesure de la polymérisation, grâce à un stabilisant qui peut être un polymère séquence, un polymère greffé, et/ou un polymère statistique, seul ou en mélange. La stabilisation peut être effectuée par tout moyen connu, et en particulier par ajout direct du polymère séquence, polymère greffé et/ou polymère statistique, lors de la polymérisation.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.
Le stabilisant est de préférence également présent dans le mélange avant polymérisation. Toutefois, il est également possible de l'ajouter en continu, notamment lorsqu'on ajoute également les monomères en continu.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.
On peut utiliser 2-30% en poids de stabilisant par rapport au mélange initial de monomères, et de préférence 5-20% en poids. Lorsqu'on utilise un polymère greffé et/ou séquence en tant que stabilisant, on choisit le solvant de synthèse de telle manière qu'au moins une partie des greffons ou séquences dudit polymère-stabilisant soit soluble dans ledit solvant, l'autre partie des greffons ou séquences n'y étant pas soluble. Le polymère-stabilisant utilisé lors de la polymérisation doit être soluble, ou dispersible, dans le solvant de synthèse. De plus, on choisit de préfé- rence un stabilisant dont les séquences ou greffons insolubles présentent une certaine affinité pour le polymère formé lors de la polymérisation.2-30% by weight of stabilizer relative to the initial mixture of monomers can be used, and preferably 5-20% by weight. When a grafted and / or block polymer is used as stabilizer, 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. In addition, a stabilizer is preferably chosen whose insoluble blocks or grafts have a certain affinity for the polymer formed during the polymerization.
Parmi les polymères greffés, on peut citer les polymères siiiconés greffés avec une chaîne hydrocarbonée ; les polymères hydrocarbonés greffés avec une chaîne siliconée.Among the grafted polymers, mention may be made of silicone polymers grafted with a hydrocarbon chain; hydrocarbon polymers grafted with a silicone chain.
Conviennent également les copolymères greffés ayant par exemple un squelette insoluble de type polyacrylique avec des greffons solubies de type acide poly-12- (hydroxystéarique). Ainsi on peut utiliser des copolymères blocs greffés ou séquences comprenant au moins un bloc de type polyorganosiloxane et au moins un bloc d'un polymère radicalaire, comme les copolymères greffés de type acrylique/silicone qui peuvent être employés notamment lorsque le milieu non aqueux est silicone. On peut aussi utiliser des copolymères blocs greffés ou séquences comprenant au moins un bloc de type polyorganosiloxane et au moins d'un polyéther. Le bloc polyorganopoly- siloxane peut être notamment un polydiméthylsiloxane ou bien encore un poly alkyl(C2- Cι8) méthyl siioxane ; le bloc polyéther peut être un poly alkylène en C2-C18, en particulier polyoxyéthylène et/ou polyoxypropylène. En particulier, on peut utiliser les diméthicones copolyol ou des alkyl (C2-C18) diméthicones copolyol tels que ceux vendu sous la dénomination "DOW CORNING 3225C" par la société DOW CORNING, les lauryl méthicones tels que ceux vendu sous la dénomination "DOW CORNING Q2-5200 par la société "DOW CORNING". Comme copolymères blocs greffés ou séquences, on peut citer aussi ceux comprenant au moins un bloc résultant de la polymérisation d'au moins un monomère éthylénique, à une ou plusieurs liaisons éthyléniques éventuellement conjuguées, comme l'éthylène ou les diènes tels que le butadiène et l'isoprène, et d'au moins un bloc d'un polymère vinyli- que et mieux styrénique. Lorsque le monomère éthylénique comporte plusieurs liaisons éthyléniques éventuellement conjuguées, les insaturations éthyléniques résiduelles après la polymérisation sont généralement hydrogénées. Ainsi, de façon connue, la polymérisation de l'isoprène conduit, après hydrogénation, à la formation de bloc éthyiène- propylène, et la polymérisation de butadiène conduit, après hydrogénation, à la formation de bloc éthylène-butylène. Parmi ces polymères, on peut citer les copolymères séquen- ces, notamment de type "dibloc" ou "tribloc" du type polystyrène/polyisoprène (SI), polys- tyrène/polybutadiène (SB) tels que ceux vendus sous le nom de 'LUVITOL HSB' par BASF, du type polystyrène/copoly(éthylène-propyiène) (SEP) tels que ceux vendus sous le nom de 'KRATON' par Shell Chemical Co ou encore du type polysty- rène/copoly(éthylène-butylène) (SEB). En particulier, on peut utiliser le Kraton G1650 (SEBS), le Kraton G1651 (SEBS), le Kraton G1652 (SEBS), le Kraton G1657X (SEBS), le Kraton G1701X (SEP), le Kraton G1702X (SEP), le Kraton G1726X (SEB), le Kraton D- 1101 (SBS), le Kraton D-1102 (SBS), le Kraton D-1107 (SIS). Les polymères sont généralement appelés des copolymères de diènes hydrogénés ou non.Also suitable are graft copolymers having for example an insoluble skeleton of polyacrylic type with solubied grafts of poly-12- (hydroxystearic) acid type. Thus, 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. . It is also possible to use graft or block copolymers comprising at least one block of the polyorganosiloxane type and at least one polyether. The polyorganopoly-siloxane block may in particular be a polydimethylsiloxane or alternatively a poly (C 2 - Cι 8 ) methyl siioxane alkyl; the polyether block can be a poly C 2 -C 18 alkylene, in particular polyoxyethylene and / or polyoxypropylene. In particular, it is possible to use dimethicone copolyol or alkyl (C 2 -C 18 ) dimethicone copolyol such as those sold under the name "DOW CORNING 3225C" by the company DOW CORNING, lauryl methicones such as those sold under the name " DOW CORNING Q2-5200 by the company "DOW CORNING" As 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 ethylenic bonds which may be conjugated , such as ethylene or dienes such as butadiene and isoprene, and at least one block of a vinyl and better styrenic polymer. When the ethylenic monomer contains several optionally conjugated ethylenic bonds, the residual ethylenic unsaturations after the polymerization are generally hydrogenated. Thus, in a known manner, the polymerization of isoprene leads, after h hydrogenation, to the formation of ethylene-propylene block, and the polymerization of butadiene leads, after hydrogenation, to the formation of ethylene-butylene block. Among these polymers, mention may be made of block copolymers these, in particular of the "diblock" or "triblock" type of the polystyrene / polyisoprene (SI), polysyrene / polybutadiene (SB) type such as those sold under the name of "LUVITOL HSB" by BASF, of the polystyrene / copoly type ( ethylene-propyiene) (SEP) such as those sold under the name of “KRATON” by Shell Chemical Co or also of the polystyrene / copoly (ethylene-butylene) type (SEB). In particular, the Kraton G1650 (SEBS), the Kraton G1651 (SEBS), the Kraton G1652 (SEBS), the Kraton G1657X (SEBS), the Kraton G1701X (SEP), the Kraton G1702X (SEP), the Kraton can be used. G1726X (SEB), Kraton D-1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS). The polymers are generally called copolymers of hydrogenated or non-hydrogenated dienes.
On peut aussi utiliser les Gelled Permethyl 99A-750, 99A-753-59 et 99A-753-58 (mélange de tribloc et de polymère en étoile), Versagel 5960 de chez Penreco (tribloc + polymère en étoile) ; OS129880, OS129881 et OS84383 de chez Lubrizol (copolymère sty- rène/méthacrylate).One can also use 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 OS84383 from Lubrizol (styrene / methacrylate copolymer).
Comme copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation d'au moins un monomère éthylénique à une ou plusieurs liaisons éthyléniques et d'au moins un bloc d'un polymère acrylique, on peut citer les copolymères bi- ou triséquencés poly(méthylacrylate de méthyle)/polyisobutylène ou les copolymères greffés à squelette poly(méthylacrylate de méthyle) et à greffons polyisobutylène.As grafted or 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, mention may be made of bi- or triblock copolymers poly (methyl methyl acrylate) / polyisobutylene or graft copolymers with poly (methyl methyl acrylate) backbone and with polyisobutylene grafts.
Comme copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation d'au moins un monomère éthylénique à une ou plusieurs liaisons éthyléniques et d'au moins un bloc d'un polyéther tel qu'un polylkylène en C2-Cι8 (poly- éthyléné et ou polyoxypropyléné notamment), on peut citer les copolymères bi- ou triséquencés polyoxyéthylène/polybutadiène ou polyoxyéthylène/polyisobutylène.As grafted or 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 8 polykylene (especially polyethylene and / or polyoxypropylene), mention may be made of bi- or tri-sequenced polyoxyethylene / polybutadiene or polyoxyethylene / polyisobutylene copolymers.
Lorsqu'on utilise un polymère statistique en tant que stabilisant, on le choisit de manière à ce qu'il possède une quantité suffisante de groupements le rendant soluble dans le sol- vant de synthèse envisagé.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 envisaged synthesis solvent.
On peut ainsi employer des copolymères à base d'acrylates ou de méthacrylates d'alkyle issus d'alcools en CrC4, et d'acrylates ou de méthacrylates d'alkyle issus d'alcools en C8- C30. On peut en particulier citer le copolymère méthacrylate de stéaryle/méthacrylate de méthyle.It is thus possible to use copolymers based on alkyl acrylates or methacrylates derived from CrC 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 methacrylate copolymer.
Lorsque le solvant de synthèse est apolaire, il est préférable de choisir en tant que stabilisant, un polymère apportant une couverture des particules la plus complète possible, plusieurs chaînes de poiymères-stabilisants venant alors s'adsorber sur une particule de po- lymère obtenu par polymérisation.When the synthetic solvent is apolar, it is preferable to choose, as stabilizer, a polymer providing the most complete coverage of the particles possible, several chains of polymer-stabilizers then being adsorbed on a polymer particle obtained by polymerization.
Dans ce cas, on préfère alors utiliser comme stabilisant, soit un polymère greffé, soit un polymère séquence, de manière à avoir une meilleure activité interfaciale. En effet, les séquences ou greffons insolubles dans le solvant de synthèse apportent une couverture plus volumineuse à la surface des particules.In this case, it is then preferred to use, as stabilizer, either a grafted polymer or a block polymer, so as to have better interfacial activity. In fact, the sequences or grafts which are insoluble in the synthesis solvent provide more voluminous coverage on the surface of the particles.
Lorsque le solvant de synthèse liquide comprend au moins une huile de silicone, l'agent stabilisant est de préférence choisi dans le groupe constitué -par les copolymères blocs greffés ou séquences comprenant au moins un bloc de type polyorganosiloxane et au moins un bloc d'un polymère radicalaire ou d'un polyéther ou d'un polyester comme les blocs polyoxypropyléné et/ou oxyéthyléné.When the liquid synthetic solvent comprises at least one silicone oil, 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 radical polymer or of a polyether or of a polyester such as polyoxypropylenated and / or oxyethylenated blocks.
Lorsque le phase grasse liquide ne comprend pas d'huile de silicone, l'agent stabilisant est de préférence choisi dans le groupe constitué par : - (a) les copolymères blocs greffés ou séquences comprenant au moins un bloc de type polyorganosiloxane et au moins un bloc d'un polymère radicalaire ou d'un polyéther ou d'un polyester,When the liquid fatty phase does not comprise silicone oil, the stabilizing agent is preferably chosen from the group consisting of: - (a) grafted or block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or of a polyether or of a polyester,
- (b) les copolymères d'acrylates ou de méthacrylates d'alkyle issus d'alcools en C C4, et d'acrylates ou de méthacrylates d'alkyle issus d'alcools en C8-C30,(b) copolymers of alkyl acrylates or methacrylates derived from CC 4 alcohols, and alkyl acrylates or methacrylates derived from C 8 -C 30 alcohols,
- (c) les copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation d'au moins un monomère éthylénique, à liaisons éthyléniques conjuguées, et au moins un bloc d'un polymère vinylique ou acrylique ou d'un polyéther ou d'un po- lyester, ou leurs mélanges.- (c) 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 of a polyester, or mixtures thereof.
De préférence, on utilise des polymères dibloc comme agent stabilisant.Preferably, diblock polymers are used as the stabilizing agent.
Agent rhéologique Selon l'invention, il est possible d'utiliser un ou plusieurs agents rhéologiques liposolubles dans la composition de l'invention. Ce ou ces agents rhéologiques sont des agents liposolubles capables d'épaissir et/ou gélifier la composition. Il sont en particulier présents en une quantité efficace pour augmenter la viscosité de la composition jusqu'à l'obtention d'un gel, à savoir un produit ne s'écoulant pas sous son propre poids, voire même en stick. La quantité d'agent rhéologique est fonction de la viscosité recherchée, et de la forme recherchée pour la composition finale. En particulier le rapport en poids de la quantité de solvant et/ou d'huile sur la quantité d'épaississant est choisi par exemple dans la gamme allant de 5 à 1000. La composition selon l'invention peut contenir par exemple une quantité d'alkyléther de polysaccharide allant de 0,05 à 20 % du poids total de la composition, et de préférence de OJ % à 10 % en poids et mieux de 0,5 % à 6 % en poids.Rheological agent According to the invention, it is possible to use one or more liposoluble rheological agents in the composition of the invention. This or these rheological agents are liposoluble agents capable of thickening and / or gelling the composition. They are in particular present in an amount effective to increase the viscosity of the composition until a gel is obtained, namely a product which does not flow under its own weight, or even in stick form. The amount of rheological agent is a function of the viscosity sought, and of the form sought for the final composition. In particular, the ratio by weight of the quantity of solvent and / or of oil to the quantity of thickener is chosen, for example, from the range from 5 to 1000. The composition according to the invention can contain, for example, an amount of alkyl ether of polysaccharide ranging from 0.05 to 20% of the total weight of the composition, and preferably from 0% to 10% by weight and better still from 0.5% to 6% by weight.
L'agent rhéologique selon l'invention est un aikyléther de polysaccharide formé de motifs comportant au moins deux cycles osidiques différents, chaque motif comportant au moins un groupe hydroxyle substitué par une chaîne alkyle hydrocarbonée saturée.The rheological agent according to the invention is a polysaccharide aikylether formed of units comprising at least two different osidic rings, each unit comprising at least one hydroxyl group substituted by a saturated hydrocarbon-based alkyl chain.
Dans l'agent rhéologique de l'invention, on entend par « chaîne alkyle hydrocarbonée » une chaîne linéaire ou ramifiée, comportant de 1 à 24, de préférence de 1 à 10, mieux de 1 à 6 et plus spécialement de 1 à 3 atomes de carbone. En particulier, la chaîne alkyle est choisie parmi les chaînes saturées et notamment méthyle, éthyle, éthényle, n-propyle, propényle, isopropyle, n-butyle, isobutyle, tertiobutyle, n-pentyle. Ces alkyléthers peuvent être fabriqués comme décrits dans les documents EP-A-281 360, EP-A-708 114, EP-A- 281360. Selon un mode de réalisation préféré de l'invention, l'alkyléther de polysaccharide a un poids moléculaire moyen en poids supérieur à 100 000, et de préférence supérieur à 200 000. Ce poids moléculaire peut aller jusqu'à 1 million. Cet aikyléther peut comporter de un à six et mieux de deux à quatre groupes hydroxyle par motif, substitués par une chaîne alkyle hydrocarbonée saturée ou non.In the rheological agent of the invention, the term “hydrocarbon-based alkyl chain” is understood to mean a linear or branched chain, comprising from 1 to 24, preferably from 1 to 10, better still from 1 to 6 and more especially from 1 to 3 atoms. of carbon. In particular, the alkyl chain is chosen from saturated chains and in particular methyl, ethyl, ethenyl, n-propyl, propenyl, isopropyl, n-butyl, isobutyl, tertiobutyl, n-pentyl. These alkyl ethers can be manufactured as described in documents EP-A-281,360, EP-A-708,114, EP-A-281360. According to a preferred embodiment of the invention, the alkyl ether of polysaccharide has a molecular weight medium by weight greater than 100,000, and preferably greater than 200,000. This molecular weight can range up to 1 million. This aikyl ether may contain from one to six and better still from two to four hydroxyl groups per unit, substituted by a saturated or unsaturated hydrocarbon alkyl chain.
Les cycles osidiques sont notamment choisis parmi le mannose, le galactose, le glucose, le furanose, le rhamnose, l'arabinose.The osidic cycles are in particular chosen from mannose, galactose, glucose, furanose, rhamnose, arabinose.
Selon un mode préféré de réalisation de l'invention, l'alkyléther de polysaccharide est un aikyléther d'une gomme et plus particulièrement d'une gomme globalement non ionique, c'est-à-dire comportant peu ou pas de groupe ionique. Comme gommes appropriées, on peut citer par exemple la gomme de guar dont le motif comprend un galactose et un mannose, la gomme de caroube dont le motif comprend un galactose et un mannose, la gomme de karaya qui est un mélange complexe de rhamnose, galactose et acide galac- turonique, la gomme adragante qui est un mélange complexe d'arabinose, galactose et acide galacturonique.According to a preferred embodiment of the invention, the polysaccharide alkyl ether is an aikyl ether of a gum and more particularly of a generally nonionic gum, that is to say comprising little or no ionic group. As suitable gums, there may be mentioned, for example, guar gum, the motif of which comprises a galactose and a mannose, locust bean gum, the motif of which comprises a galactose and a mannose, karaya gum, which is a complex mixture of rhamnose, galactose. and galacic acid turonic, the tragacanth which is a complex mixture of arabinose, galactose and galacturonic acid.
Selon un mode de réalisation préféré de l'invention, l'alkyléther de polysaccharide est un dérivé de gomme de guar. Ainsi, avantageusement l'alkyéther est un galactomannane alkyle de chaîne alkyle en Ci à C6 et mieux en Ci à C3 et plus particulièrement le guar éthylé ayant un degré de substitution de 2 à 3 et notamment d'environ 2,5 à 2,8, tel que décrit dans les documents RD 95378007 (octobre 1995) et EP-A-708114. Cette gomme est en particulier celle vendue par la société Aqualon sous les noms N-HANCE-AG 200® et N-HANCE AG 50®.According to a preferred embodiment of the invention, the polysaccharide alkyl ether is a guar gum derivative. Thus, advantageously the alkyl ether is an alkyl galactomannan with a C 1 to C 6 and better C 1 to C 3 alkyl chain and more particularly ethyl guar having a degree of substitution of 2 to 3 and in particular approximately 2.5 to 2 , 8, as described in documents RD 95378007 (October 1995) and EP-A-708114. This gum is in particular that sold by the company Aqualon under the names N-HANCE-AG 200® and N-HANCE AG 50®.
Ce ou ces agents rhéologiques liposolubles permettent un épaississement de la composition, tout en conservant un aspect brillant à la composition ainsi qu'au film déposé sur les lèvres et/ou le corps. Ceci ressort clairement du tableau (I) mentionné ultérieurement.This liposoluble rheological agent or agents allow the composition to thicken, while retaining a shiny appearance to the composition as well as to the film deposited on the lips and / or the body. This is clear from the table (I) mentioned later.
Les dispersions de polymères gélifiées obtenues selon l'invention peuvent alors être utilisées dans une composition notamment cosmétique, dermatologique, pharmaceutique et/ou hygiénique, telle qu'une composition de soin ou de maquillage de la peau ou des lèvres, ou encore une composition capillaire ou une composition solaire ou de coloration ou de bronzage artificiel de la peau.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.
Suivant l'application, on pourra choisir d'utiliser des dispersions de polymères filmifiables ou non filmifiables, dans des huiles volatiles ou non volatiles. La composition de l'invention peut comprendre avantageusement une ou plusieurs matières colorantes contenant un ou plusieurs composés pulvérulents et/ou un ou plusieurs colorants liposolubles ou hydrosolubles, par exemple à raison de 0 à 70% du poids total de la composition et notamment de 0,01 à 70%. Les composés pulvérulents peuvent être choisis parmi les pigments et/ou les nacres et/ou les charges habituellement utilisés dans les compositions cosmétiques ou dermatologiques. Avantageusement, les composés pulvérulents représentent de 0 à 50 % et notamment de OJ à 50 % du poids total de la composition et mieux de 1 à 40 %. Plus la quantité de composés pulvérulents diminue, plus les qualités de sans transfert et de confort augmentent. Le fait que les propriétés de sans transfert augmentent au fur et à mesure que la quantité de composés pulvérulents diminue est tout à fait surprenant. En effet, jusqu'à ce jour les propriétés de sans transfert des compositions de l'art antérieur augmentaient avec la quantité de composés pulvérulents. Inversement, leurs inconforts, leurs brillance et leur sécheresse sur la peau ou muqueuses augmentaient. Par ailleurs, la propriété de sans transfert augmente avec la quantité de polymère disper- sibie dans la phase grasse liquide. En pratique, le polymère peut représenter en matière active jusqu'à 60 % (en matière active ou sèche) du poids total de la composition. En utilisant au-dessus de 12 % en poids de matière active de polymère et d'huile non volatile dans la composition et jusqu'à 60 %, on obtient un film sans transfert total. Entre 2 % et 12 % l'effet sans transfert est notable sans toutefois être total. On peut donc adapter les propriétés sans transfert à volonté, ce qui n'était pas possible avec les compositions sans transfert de l'art antérieur, sans nuire au confort du film déposé.Depending on the application, it will be possible to choose to use dispersions of film-forming or non-film-forming polymers in volatile or non-volatile oils. The composition of the invention may advantageously comprise one or more coloring matters containing one or more pulverulent compounds and / or one or more liposoluble or water-soluble dyes, for example at a rate of 0 to 70% of the total weight of the composition and in particular of 0 , 01 to 70%. The pulverulent compounds can be chosen from pigments and / or nacres and / or fillers usually used in cosmetic or dermatological compositions. Advantageously, the pulverulent compounds represent from 0 to 50% and in particular from OJ to 50% of the total weight of the composition and better still from 1 to 40%. The more the quantity of pulverulent compounds decreases, the more the qualities of non-transferability and comfort increase. It is quite surprising that the transfer-free properties increase as the amount of pulverulent compounds decreases. Indeed, to date the transfer-free properties of the compositions of the prior art have increased with the amount of pulverulent compounds. Conversely, their discomfort, shine and dryness on the skin or mucous membranes increased. Furthermore, the property of non-transfer increases with the amount of polymer dispersed in the liquid fatty phase. In practice, the polymer can represent in active material up to 60% (in active or dry material) of the total weight of the composition. By using above 12% by weight of polymer active material and non-volatile oil in the composition and up to 60%, a film is obtained without total transfer. Between 2% and 12% the effect without transfer is significant without however being total. We can therefore adapt the properties without transfer at will, which was not possible with the compositions without transfer of the prior art, without affecting the comfort of the film deposited.
Les pigments peuvent être blancs ou colorés, minéraux et/ou organiques, interférentiels ou non. On peut citer, parmi les pigments minéraux, le dioxyde de titane, éventuellement traité en surface, les oxydes de zirconium ou de cérium, ainsi que les oxydes de fer ou de chrome, le violet de manganèse, le bleu outremer, l'hydrate de chrome et le bleu ferrique. Parmi les pigments organiques, on peut citer le noir de carbone, les pigments de type D & C, et les laques à base de carmin de cochenille, de baryum, strontium, calcium, aluminium.The pigments can be white or colored, mineral and / or organic, interference or not. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue. Among the organic pigments, there may be mentioned carbon black, pigments of type D & C, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.
Les pigments nacrés peuvent être choisis parmi les pigments nacrés blancs tels que le mica recouvert de titane, ou d'oxychlorure de bismuth, les pigments nacrés colorés tels que le mica titane avec des oxydes de fer, le mica titane avec notamment du bleu ferrique ou de l'oxyde de chrome, le mica titane avec un pigment organique du type précité ainsi que les pigments nacrés à base d'oxychlorure de bismuth. Les charges peuvent être minérales ou organiques, lamellaires ou sphériques. On peut citer le talc, le mica, la silice, le kaolin, les poudres de Nylon (Orgasol de chez Atochem), de poly-β-alanine et de polyéthylène, le Téflon, la lauroyl-lysine, l'amidon, le nitrure de bore, les poudres de polymères de tétrafluoroéthylène, les microsphères creuses telles que l'Expancel (Nobel Industrie), le polytrap (Dow Corning) et les microbilles de résine de silicone (Tospearls de Toshiba, par exemple), le carbonate de calcium précipité, le carbonate et l'hydro-carbonate de magnésium, l'hydroxyapatite, les microsphères de silice creuses (SILICA BEADS de MAPRECOS), les microcapsules de verre ou de céramique, les savons métalliques dérivés d'acides organiques carboxyliques ayant de 8 à 22 atomes de carbone, de préférence de 12 à 18 atomes de carbone, par exemple le stéarate de zinc, de magnésium ou de lithium, le laurate de zinc, le myristate de magnésium.The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. The fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, nylon powders (Orgasol from Atochem), poly-β-alanine and polyethylene, Teflon, lauroyl-lysine, starch, nitride. boron, powders of tetrafluoroethylene polymers, hollow microspheres such as Expancel (Nobel Industrie), polytrap (Dow Corning) and microbeads of silicone resin (Toshiba Tospearls, for example), precipitated calcium carbonate , magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
Les colorants liposolubles sont par exemple le rouge Soudan, le DC Red 17, le DC Green 6, le β-carotène, l'huile de soja, le brun Soudan, le DC Yeliow, 11 , le DC Violet 2, le DC orange 5, le jaune quinoiéine. Ils peuvent représenter de 0 à 20 % et notamment 0,01 à 20 % du poids de la compositions et mieux de 0J à 6 %. Les colorants hydrosolubles sont par exemple le jus de betterave, le bleu de méthylène et peuvent représenter jusqu'à 6 % du poids total de la composition.The liposoluble dyes are for example Sudan red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan brown, DC Yeliow, 11, DC Violet 2, DC orange 5 , quinoline yellow. They can represent from 0 to 20% and in particular 0.01 to 20% of the weight of the composition and better still from 0J to 6%. The water-soluble dyes are, for example, beet juice, methylene blue and can represent up to 6% of the total weight of the composition.
La composition de l'invention peut, en outre, contenir un ou plusieurs actifs cosmétiques ou dermatologiques tels que ceux classiquement utilisés.The composition of the invention may, in addition, contain one or more cosmetic or dermatological active agents such as those conventionally used.
Comme actifs cosmétiques, dermatologiques, hygiéniques ou pharmaceutiques, utilisables dans la composition de l'invention, on peut citer les hydratants, vitamines, acides gras essentiels, sphingolipides, filtres solaires. Ces actifs sont utilisés en quantité habituelle pour l'homme et notamment à des concentrations de 0 à 20 % et notamment de 0,001 à 20 % du poids total de la composition.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 active agents are used in the usual amount for humans and in particular at concentrations of 0 to 20% and in particular from 0.001 to 20% of the total weight of the composition.
Le polymère de la composition de l'invention permet la formation d'un film sur la peau, les lèvres et/ou les muqueuses, formant un réseau piégeant les matières colorantes (y compris les charges) et/ou les actifs. Selon la quantité relative de matières colorantes, utilisée par rapport à la quantité de polymère stabilisé, utilisée, il est possible d'obtenir un film plus ou moins brillant et plus ou moins sans transfert.The polymer of the composition of the invention allows the formation of a film on the skin, the lips and / or the mucous membranes, forming a network trapping the coloring matters (including the fillers) and / or the active agents. Depending on the relative amount of coloring matter used relative to the amount of stabilized polymer used, it is possible to obtain a more or less glossy film and more or less without transfer.
La composition selon l'invention peut, de plus, comprendre, selon le type d'application envisagée, les constituants classiquement utilisés dans les domaines considérés, qui sont présents en une quantité appropriée à la forme galénique souhaitée.The 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 suitable for the desired dosage form.
En particulier, elle peut comprendre, outre, la phase grasse liquide dans laquelle le polymère est stabilisé des phases grasses-additionnelles qui peuvent être choisies parmi les cires, les huiles, les gommes et/ou les corps gras pâteux, d'origine végétale, animale, mi- nérale ou de synthèse, voire siiiconés, et leurs mélanges.In particular, it can comprise, in addition, the liquid fatty phase in which the polymer is stabilized fatty-additional phases which can be chosen from waxes, oils, gums and / or pasty fatty substances of vegetable origin, animal, mineral or synthetic, or even siiconized, and mixtures thereof.
Parmi les cires solides à température ambiante, susceptibles d'être présentes dans la composition selon l'invention, on peut citer les cires hydrocarbonées telles que la cire d'abeilles, la cire de Carnauba, de Candellila, d'Ouricoury, du Japon, les cires de fibres de liège ou de canne à sucre, les cires de paraffine, de lignite, les cires microcristallines, la cire de lanoline, la cire de Montan, les ozokérites, les cires de polyéthylène, les cires obtenues par synthèse de Fischer-Tropsch, les huiles hydrogénées, les esters gras et les glycérides concrets à 25°C. On peut également utiliser des cires de silicone, parmi lesquelles on peut citer les alkyl, alcoxy et/ou esters de polyméthylsiloxane. Les cires peuvent se présenter sous forme de dispersions stables de particules colloïdales de cire telles qu'elles peuvent être préparées selon des méthodes connues, telles que celles de "Microemulsions Theory and Practice", L. M. Prince Ed., Académie Press (1977), pages 21 -32. Comme cire liquide à température ambiante, on peut citer l'huile de Jojoba.Among the 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, fiber waxes cork or sugar cane, paraffin waxes, lignite, microcrystalline waxes, lanolin wax, Montan wax, ozokerites, polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, 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. 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. As liquid wax at room temperature, mention may be made of Jojoba oil.
Les cires peuvent être présentes à raison de 0-50% en poids dans la composition et mieux de 5 à 20 %, en vue de ne pas trop diminuer la brillance de la composition et du film déposé sur les lèvres et/ou la peau. La composition peut comprendre, en outre, tout additif usuellement utilisé dans de telles compositions, tel que des épaississants autres que l'agent rhéologique de type polysac- charidique, des antioxydants, des parfums, des conservateurs, des tensioactifs, des polymères liposolubles comme les polyalkylènes, notamment le polybutène, les polyacryla- tes et les polymères siiiconés compatibles avec la phase grasse ainsi que les dérivés de polyvinylpyrolidone. Bien entendu l'homme du métier veillera à choisir ce ou ces éventuels composés complémentaires, et/ou leur quantité, de manière telle que les propriétés avantageuses de la composition selon l'invention ne soient pas, ou substantiellement pas, altérées par l'adjonction envisagée. Dans un mode de réalisation particulier de l'invention, les compositions selon l'invention peuvent être préparées de manière usuelle par l'homme du métier. Elles peuvent se présenter sous forme d'un produit coulé et par exemple sous la forme d'un stick ou bâton, ou sous la forme de coupelle utilisable par contact direct ou à l'éponge. En particulier, elles trouvent une application en tant que fond de teint coulé, fard à joues ou à paupières cou- lé, rouge à lèvres, base ou baume de soin pour les lèvres, produit anti-cernes. Elles peuvent aussi se présenter sous forme d'une pâte souple, de viscosité dynamique à 25°C de l'ordre de 1 à 40 Pa.s ou encore de gel, de crème plus ou moins fluide. Elles peuvent alors constituées des fonds de teint ou des rouges à lèvres, des produits solaires ou de coloration de la peau.The waxes can be present at a rate of 0-50% by weight in the composition and better still from 5 to 20%, in order not to decrease too much the gloss of the composition and of the film deposited on the lips and / or the skin. The composition may also comprise any additive usually used in such compositions, such as thickeners other than the rheological agent of polysaccharide type, antioxidants, perfumes, preservatives, surfactants, liposoluble polymers such as polyalkylenes, in particular polybutene, polyacrylates and silicone polymers compatible with the fatty phase as well as polyvinylpyrolidone derivatives. Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the addition considered. In a particular embodiment of the invention, the 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 poured eyeshadow, lipstick, base or lip care balm, concealer product. They can also be in the form of a flexible paste, of dynamic viscosity at 25 ° C of the order of 1 to 40 Pa.s or else of gel, of more or less fluid cream. They can then consist of foundations or lipsticks, sun products or skin coloring.
Les compositions de l'invention sont avantageusement anhydres et peuvent contenir moins de 5 % d'eau par rapport au poids total de la composition. Elles peuvent alors se présenter notamment sous forme de gel huileux, de liquide huileux ou huile, de pâte ou de stick ou encore sous forme de dispersion vésiculaire contenant des lipides ioniques et/ou non ioniques. Elles peuvent aussi se présenter sous forme d'une emulsion simple ou multiple à phase continue huileuse ou aqueuse, de dispersion huileuse dans une phase aqueuse grâce à des vésicules contenant des lipides ioniques et/ou non ioniques. Ces formes galéniques sont préparées selon les méthodes usuelles des domaines considérés.The 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 presented 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 an aqueous phase using vesicles containing ionic and / or nonionic lipids. These dosage forms are prepared according to the usual methods of the fields considered.
Ces compositions à application topique peuvent constituer notamment une composition cosmétique, dermatologique, hygiénique ou pharmaceutique de protection, de traitement ou de soin pour le visage, pour le cou, pour les mains ou pour le corps (par exemple crème de soin, huile solaire, gel corporel), une composition de maquillage (par exemple gel de maquillage, crème, stick) ou une composition de bronzage artificiel ou de protection de la peau.These 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.
L'invention est illustrée plus en détail dans les exemples suivants. Les pourcentages sont des pourcentages en poids. Exemple 1 de dispersion de polymèreThe invention is illustrated in more detail in the following examples. The percentages are percentages by weight. Example 1 of polymer dispersion
On prépare une dispersion de polyméthacrylate de méthyle réticulé par du diméthacrylate d'éthylène glycol, dans de l'isododécane, selon la méthode de l'exemple 2 du document EP-A-749 746, en remplaçant L'ISOPAR L par de l'isododécane. On obtient ainsi une dispersion de particules de polyméthacrylate de méthyle stabilisées en surface dans de l'isododécane par un copolymère dibloc séquence polystyrène/copoly(éhylène-propylène) vendu sous le nom de KRATON G1701 (Shell), ayant un taux de matière sèche de 19,7% en poids et une taille moyenne des particules de 135 nm (polydispersité : 0,05) et une Tg de 100°C. Ce copolymère est non filmifiable à température ambiante.A dispersion of polymethyl methacrylate crosslinked with ethylene glycol dimethacrylate is prepared in isododecane, according to the method of Example 2 of document EP-A-749 746, replacing ISOPAR L by isododecane. A dispersion of polymethyl methacrylate particles surface stabilized in isododecane is thus obtained by a polystyrene / copoly (ethylene-propylene) block copolymer sold under the name KRATON G1701 (Shell), having a dry matter content of 19.7% by weight and an average particle size of 135 nm (polydispersity: 0.05) and a Tg of 100 ° C. This copolymer is non-film-forming at room temperature.
Exemple 2 de dispersion de polymèreExample 2 of polymer dispersion
On prépare une dispersion de copolymère non réticulé d'acrylate de méthyle et d'acide acrylique dans un rapport 95/5, dans de l'isododécane, selon la méthode de l'exemple 1 du document EP-A-749 746, en remplaçant l'heptane par de l'isododécane. On obtient ainsi une dispersion de particules de poly(acrylate de méthyle/acide acrylique) stabilisées en surface dans de l'isododécane par un copolymère dibloc séquence polysty- rène/copoly(éhylène-propylène) vendu sous le nom de KRATON G1701 (Shell), ayant un taux de matière sèche de 19% en poids et une taille moyenne des particules de 165 nm (polydispersité : 0,05) et une Tg de 13°C. Ce copolymère est filmifiable.A dispersion of uncrosslinked copolymer of methyl acrylate and acrylic acid in a 95/5 ratio is prepared in isododecane, according to the method of example 1 of document EP-A-749 746, replacing heptane with isododecane. A dispersion of poly (methyl acrylate / acrylic acid) particles is thus obtained, stabilized at the surface in isododecane by a polystyrene / copoly (ethylene-propylene) block copolymer sold under the name of KRATON G1701 (Shell). , having a dry matter content of 19% by weight and an average particle size of 165 nm (polydispersity: 0.05) and a Tg of 13 ° C. This copolymer is film-forming.
Exemple 3 de dispersion de polymèreExample 3 of polymer dispersion
On prépare une dispersion de copolymère non réticulé d'acrylate de méthyle et d'acide acrylique dans un rapport 95/5, dans de l'isododécane, selon la méthode de l'exemple 1 du document EP-A-749 746, en remplaçant l'heptane par de l'isododécane. On obtient ainsi une dispersion de particules de poly(acrylate de méthyle/acide acrylique) stabilisées en surface dans de l'isododécane par un copolymère dibloc séquence polysty- rène/côpoly(éhylène-propylène) vendu sous le nom de KRATON G1701 (Shell), ayant un taux de matière sèche de 22,25 % en poids et une taille moyenne des particules de 180 nm (polydispersité : 0,05) et une Tg de 20°C. Ce copolymère est filmifiable.A dispersion of uncrosslinked copolymer of methyl acrylate and acrylic acid in a 95/5 ratio is prepared in isododecane, according to the method of example 1 of document EP-A-749 746, replacing heptane with isododecane. This gives a dispersion of poly (methyl acrylate / acrylic acid) particles surface stabilized in isododecane with a polystyrene / cocol (ethylene-propylene) block copolymer sold under the name KRATON G1701 (Shell) , having a dry matter content of 22.25% by weight and an average particle size of 180 nm (polydispersity: 0.05) and a Tg of 20 ° C. This copolymer is film-forming.
Tests comparatifsComparative tests
Dans les dispersions des exemples 2 et 3, on a introduit des pigments, et un gélifiant selon l'invention et selon l'art antérieur. On a ensuite mesuré la viscosité à 25°C des com- positions obtenues, à l'aide d'un viscosimetre type Brookfield LV tournant à 100 tr/min et équipé d'un mobile LV4 ou LV3 selon la viscosité ainsi que la brillance à l'aide d'un bril- lancemètre type Byk Gardner.In the dispersions of Examples 2 and 3, pigments and a gelling agent according to the invention and according to the prior art were introduced. The viscosity at 25 ° C. of the compositions obtained was then measured, using a Brookfield LV type viscometer rotating at 100 rpm and equipped with an LV4 or LV3 mobile depending on the viscosity as well as the gloss at using a Byk Gardner type shine meter.
Les résultats sont donnés dans le tableau (I) ci-après.The results are given in table (I) below.
Figure imgf000017_0001
Figure imgf000017_0001
De ce tableau, il ressort clairement que les gélifiants de la composition selon l'invention assurent une brillance élevée des compositions, ce qui n'est pas le cas avec les gélifiants classiques comme les cires, la Bentone 34 de chez Rhéox, le KSG X-21-5432 vendu par la société Shin Etsu qui est un organopolysiloxane réticulé à 27 % en matière active dans du polyméthyltrifluoropropyl dimethylsiloxane. La composition ne contenant pas de gélifiant ni de pigments a une brillance de 84 %. From this table, it is clear that the gelling agents of the composition according to the invention ensure a high gloss of the compositions, which is not the case with the gelling agents. classics such as waxes, Bentone 34 from Rheox, KSG X-21-5432 sold by the company Shin Etsu which is an organopolysiloxane crosslinked to 27% in active material in polymethyltrifluoropropyl dimethylsiloxane. The composition containing no gelling agent or pigments has a gloss of 84%.
Exemple 4 : Laque à lèvresExample 4: Lip Lacquer
On prépare une laque à lèvres sous forme fluide ayant la composition suivante :A lip lacquer is prepared in fluid form having the following composition:
. polyisobutène hydrogéné 1 ,67 %. 1.67% hydrogenated polyisobutene
. copolymère de PVP/eicosène 0,96 % . aluminium laque de DC Red 27 1 ,14 %. 0.96% PVP / eicosene copolymer. aluminum lacquer from DC Red 27 1, 14%
. calcium laque de DC Red 7 2J0 %. DC Red 7 calcium lacquer 2J0%
. DC Red 36 0,54 %. DC Red 36 0.54%
. oxyde de fer noir 0,04 %. 0.04% black iron oxide
. oxyde de fer rouge 1 ,19 % . dispersion de l'exemple 1 qs 100 %. red iron oxide 1, 19%. dispersion of example 1 qs 100%
. N-Hance AG 200 (Hercules) * 3,00 %. N-Hance AG 200 (Hercules) * 3.00%
. phénylthméthicone (DC 556 de Dow Corning) 28,67 %. phenylthmethicone (DC 556 from Dow Corning) 28.67%
. octyldodécanol 0,72 % * Galactomannane à chaîne alkyle en C C5 . octyldodecanol 0.72% * Galactomannan with CC 5 alkyl chain
Cette laque à lèvres est très brillante, sans transfert total et non migrante. Elle est obtenue selon le mode opératoire suivant : solubiliser le Kraton dans la dispersion de polymère à chaud (environ 50°C) pendant 2h puis ajouter les pigments préalablement broyés dans les huiles.This lip lacquer is very shiny, without total transfer and non-migrating. It is obtained according to the following operating method: dissolve the Kraton in the polymer dispersion under hot conditions (approximately 50 ° C.) for 2 hours then add the pigments previously ground in the oils.
Cette laque a été testée par des experts en utilisant un applicateur avec un embout en mousse. Cette laque s'étire bien sur les lèvres ; le film est brillant/satiné ; son transfert est faible ; il ne migre pas dans les rides et ridules autour des lèvres. Les contours sont nets. Le confort est bon à l'application.This lacquer has been tested by experts using an applicator with a foam tip. This hairspray stretches well over the lips; the film is glossy / satin; its transfer is weak; it does not migrate into fine lines and wrinkles around the lips. The contours are sharp. Comfort is good when applied.
Exemple 5 : Rouge à lèvres sans transfert On prépare un rouge à lèvres sous forme fluide ayant la composition suivante :Example 5 Lipstick Without Transfer A lipstick is prepared in fluid form having the following composition:
. polyisobutène hydrogéné 0,77 %. 0.77% hydrogenated polyisobutene
. oxydes de fer 4,00 %. iron oxides 4.00%
. dispersion de l'exemple 2 qs 100 % o. dispersion of example 2 qs 100% o
. N-Hance AG 200 (Hercules) 1 ,50 % . copolymère de PVP/eicosène 0,44 %. N-Hance AG 200 (Hercules) 1.50%. PVP / eicosene copolymer 0.44%
. phényltriméthicone 0,76 %. phenyltrimethicone 0.76%
. octyldodécanol 0,33 %. octyldodecanol 0.33%
Ce rouge à lèvres est préparé comme précédemment. Il se présente sous forme fluide, brillant, doux à l'application, sans transfert et non migrant.This lipstick is prepared as before. It comes in a fluid, shiny, soft application form, without transfer and non-migrating.
Exemple 6 : Fond de teint fluideExample 6: Fluid foundation
On prépare un fond de teint sous forme fluide ayant ta composition suivante :A foundation in fluid form is prepared having your following composition:
. polyisobutène hydrogéné 7,00 % . oxyde de fer jaune 1 J 7 %. 7.00% hydrogenated polyisobutene. yellow iron oxide 1 J 7%
. oxyde de fer noir 0,26 %. 0.26% black iron oxide
. oxyde de fer brun 0,64 %. brown iron oxide 0.64%
. dioxyde de titane 7,93 %. titanium dioxide 7.93%
. dispersion de polymère de l'exemple 1 qsp 100 % . N-Hance AG 200 2,00 %. dispersion of polymer of Example 1 qs 100%. N-Hance AG 200 2.00%
. nylon-12 12,00 %. nylon-12 12.00%
. copolymère PVP/eicosène 4,00 %. PVP / eicosene copolymer 4.00%
. phényltriméthicone 7,00 %. phenyltrimethicone 7.00%
. octyldodécanol 3,00 % Ce fond de teint est préparé comme précédemment. Il se présente sous forme fluide, facile à étaler et a de bonnes propriété sans transfert. . octyldodecanol 3.00% This foundation is prepared as above. It comes in a fluid form, easy to spread and has good properties without transfer.

Claims

REVENDICATIONS
1. Composition à application topique contenant une phase grasse liquide et des particules de polymère dispersées dans la phase grasse liquide et stabilisées en surface par un agent stabilisant, ladite phase étant, en outre, épaissie par un agent rhéologique liposoluble de type polysaccharide.1. Composition for topical application containing a liquid fatty phase and polymer particles dispersed in the liquid fatty phase and surface stabilized by a stabilizing agent, said phase being, in addition, thickened by a liposoluble rheological agent of polysaccharide type.
2. Composition selon la revendication 1 , dans laquelle l'agent rhéologique est un aikyléther de polysaccharide formé de motifs comportant au moins deux cycles osidiques diffé- rents, chaque motif comportant au moins un groupe hydroxyle substitué par une chaîne alkyle hydrocarbonée saturée.2. Composition according to claim 1, in which the rheological agent is a polysaccharide aikylether formed of units comprising at least two different osidic rings, each unit comprising at least one hydroxyl group substituted by a saturated hydrocarbon-based alkyl chain.
3. Composition selon la revendication 2, caractérisée en ce que deux à quatre groupes hydroxyle par motif sont substitués par une chaîne alkyle hydrocarbonée saturée.3. Composition according to claim 2, characterized in that two to four hydroxyl groups per unit are substituted by a saturated hydrocarbon alkyl chain.
4. Composition selon l'une des revendications 2 à 3, caractérisée en ce que la chaîne alkyle hydrocarbonée saturée comporte de 1 à 24 atomes de carbone et, de préférence de 2 à 10 atomes de carbone. 4. Composition according to one of claims 2 to 3, characterized in that the saturated hydrocarbon alkyl chain contains from 1 to 24 carbon atoms and, preferably from 2 to 10 carbon atoms.
5. Composition selon l'une des revendications 2 à 4, caractérisée en ce que la chaîne alkyle est choisie dans le groupe formé par les radicaux méthyle, éthyle, n-propyle, isopro- pyle, n-butyle, isobutyle, tertiobutyle.5. Composition according to one of claims 2 to 4, characterized in that the alkyl chain is chosen from the group formed by the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl radicals.
6. Composition selon l'une des revendications 2 à 5, caractérisée en ce que les cycles osidiques sont choisis dans le groupe formé par le mannose, le galactose, le glucose, le furanose, le rhamnose, l'arabinose.6. Composition according to one of claims 2 to 5, characterized in that the osidic cycles are chosen from the group formed by mannose, galactose, glucose, furanose, rhamnose, arabinose.
7. Composition selon l'une des revendications 2 à 6, caractérisée en ce que l'alkyléther de polysaccharide est un aikyléther d'une gomme choisie parmi la gomme guar, la gomme de caroube, la gomme de karaya, la gomme adragante et leurs mélanges.7. Composition according to one of claims 2 to 6, characterized in that the polysaccharide alkyl ether is an aikyl ether of a gum chosen from guar gum, locust bean gum, karaya gum, tragacanth gum and their mixtures.
8. Composition selon l'une des revendications 2 à 7, caractérisée en ce que l'alkyléther de polysaccharide est un galactomannane alkyle de chaîne alkyle en Ci à C6 et mieux en8. Composition according to one of Claims 2 to 7, characterized in that the polysaccharide alkyl ether is an alkyl galactomannan alkyl chain in C 6 and better
9. Composition selon l'une des revendications 2 à 8, caractérisée en ce que l'alkyléther de polysaccharide est de la gomme de guar à chaîne éthyle avec un degré de substitution de 2 à 3. 9. Composition according to one of claims 2 to 8, characterized in that the polysaccharide alkyl ether is guar gum with an ethyl chain with a degree of substitution of 2 to 3.
10. Composition selon l'une des revendications 2 à 9, caractérisée en ce que l'alkyléther de polysaccharide a un poids moléculaire moyen en poids supérieur à 200 000.10. Composition according to one of claims 2 to 9, characterized in that the polysaccharide alkyl ether has a weight average molecular weight greater than 200,000.
11. Composition selon l'une des revendications précédentes, dans laquelle l'agent rhéologique représente de 0,05 à 20 % du poids total de la composition.11. Composition according to one of the preceding claims, in which the rheological agent represents from 0.05 to 20% of the total weight of the composition.
12. Composition selon l'une des revendications précédentes, dans laquelle l'agent rhéologique représente de 0,5 à 5 % du poids total de la composition.12. Composition according to one of the preceding claims, in which the rheological agent represents from 0.5 to 5% of the total weight of the composition.
13. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère en dispersion est filmifiable.13. Composition according to one of the preceding claims, characterized in that the polymer in dispersion is film-forming.
14. Composition selon l'une des revendications précédentes dans laquelle au moins un ingrédient choisi parmi les actifs cosmétiques, dermatologiques, hygiéniques ou pharmaceutiques et les matières colorantes est prévu. 14. Composition according to one of the preceding claims in which at least one ingredient chosen from cosmetic, dermatological, hygienic or pharmaceutical active agents and coloring matters is provided.
15. Composition selon l'une des revendications précédentes, dans laquelle le polymère en dispersion est choisi parmi les polymères radicalaires, les polycondensats, les polymères d'origine naturelle et leurs mélanges.15. Composition according to one of the preceding claims, in which the polymer in dispersion is chosen from radical polymers, polycondensates, polymers of natural origin and their mixtures.
16. Composition selon l'une des revendications précédentes, dans laquelle le polymère en dispersion est choisi parmi tes polyuréthannes, polyuréthannes-acryliques, polyurées, polyurée/polyuréthannes, polyester-polyuréthannes, polyéther-polyuréthannes, polyesters, polyesters amides, polyesters à chaîne grasse, alkydes ; polymères ou copolymères acryliques et/ou vinyliques ; copolymères acryiiques-silicone ; poiyacrylamides ; polymères siiiconés, polymères fluorés et leurs mélanges.16. Composition according to one of the preceding claims, in which the polymer in dispersion is chosen from polyurethanes, polyurethanes-acrylics, polyureas, polyureas / polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyesters, polyester amides, polyesters with a fatty chain. , alkyds; acrylic and / or vinyl polymers or copolymers; acrylic-silicone copolymers; poiyacrylamides; silicone polymers, fluoropolymers and mixtures thereof.
17. Composition selon l'une des revendications précédentes, dans laquelle la phase grasse liquide est constituée d'huiles d'origine minérale, animale, végétale ou synthéti- que, carbonées, hydrocarbonées, fluorées et/ou siliconées, seules ou en mélange.17. Composition according to one of the preceding claims, in which the liquid fatty phase consists of oils of mineral, animal, vegetable or synthetic origin, carbonaceous, hydrocarbon-based, fluorinated and / or silicone-based, alone or as a mixture.
18. Composition selon l'une des revendications précédentes, dans laquelle la phase grasse liquide est choisie parmi l'huile de paraffine ou de vaseline, l'huile de vison, de tortue, de soja, le perhydrosqualène, l'huile d'amande douce, de calophyllum, de palme, de parléam, de pépins de raisin, de sésame, de maïs, de colza, de tournesol, de coton, d'abricot, de ricin, d'avocat, de jojoba, d'olive ou de germes de céréales ; des esters d'acide lanoiique, d'acide oléique, d'acide iaurique, d'acide stéarique ; les esters gras tels que le myristate d'isopropyle, le palmitate d'isopropyle, le stéarate de butyle, le laurate d'hexyle, l'adipate de diisopropyle, l'isononate d'isononyle, le paimitate de 2-éthyl-hexyle, le laurate de 2-hexyl-décyle, le palmitate de 2-octyl-décyle, le myristate ou le lactate de 2- octyl-dodécyle, le succinate de 2-diéthyl-hexyle, le malate de diisostéaryle, le triisostéa- rate de glycérine ou de diglycérine ; les acides gras supérieurs tels que l'acide myristique, l'acide palmitique, l'acide stéarique, l'acide béhénique, l'acide oléique, l'acide linoiéique, l'acide linolénique ou l'acide isostéarique ; les alcools gras supérieurs tels que le cétanol, l'alcool stéarylique ou l'alcool oléique, l'alcool linoiéique ou linolénique, l'alcool isostéarique ou l'octyl dodécanol ; les huiles siliconées telles que les PDMS éventuellement phé- nylés tels que les phényltriméthicones ou éventuellement substitués par des groupements aliphatiques et/ou aromatiques, ou par des groupements fonctionnels tels que des groupements hydroxyle, thiol et/ou aminé ; les polysiloxanes modifiés par des acides gras, des alcools gras ou des polyoxyalkylènes, les siiiconés fluorées, les huiles perfluorées ; les huiles volatiles telles que l'octaméthylcyclotétrasiloxane, le décaméthylcyclopentasi- loxane, l'hexadéméthylcyclohexasiloxane, l'heptaméthylhexyltrisiloxane, l'heptaméthyloc- tylthsiloxane ou les isoparaffines en C8-C16, et l'isododécane. 18. Composition according to one of the preceding claims, in which the liquid fatty phase is chosen from paraffin or petrolatum oil, mink, turtle, soybean oil, perhydrosqualene, almond oil sweet, calophyllum, palm, parlam, grapeseed, sesame, corn, rapeseed, sunflower, cotton, apricot, castor, avocado, jojoba, olive or cereal sprouts; esters of lanoiic acid, oleic acid, iauric acid, stearic acid; fatty esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononate, 2-ethylhexyl paimitate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl-dodecyl myristate or lactate, 2-diethyl-hexyl succinate, diisostearyl malate, glycerin triisostearate or diglycerin; higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoiic acid, linolenic acid or isostearic acid; higher fatty alcohols such as cetanol, stearyl alcohol or oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyl dodecanol; silicone oils such as PDMS optionally phenylated such as phenyltrimethicones or optionally substituted by aliphatic and / or aromatic groups, or by functional groups such as hydroxyl, thiol and / or amino groups; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, fluorinated silicones, perfluorinated oils; volatile oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexademethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethylocytylthsiloxane or C 8 -C 16 isoparaffins, and isododecane.
19. Composition selon l'une des revendications précédentes, caractérisée en ce que la phase grasse contient au moins une huile volatile à température ambiante et pression atmosphérique.19. Composition according to one of the preceding claims, characterized in that the fatty phase contains at least one volatile oil at ambient temperature and atmospheric pressure.
20. Composition selon l'une des revendications précédentes, dans laquelle le stabilisant est choisi parmi les polymères séquences, les polymères greffés, les polymères statistiques et leurs mélanges.20. Composition according to one of the preceding claims, in which the stabilizer is chosen from block polymers, graft polymers, random polymers and their mixtures.
21. Composition selon l'une des revendications précédentes, dans laquelle le stabilisant est choisi parmi les polymères siiiconés greffés avec une chaîne hydrocarbonée ; les po- lymères hydrocarbonés greffés avec une chaîne siliconee ; les copolymères greffés ayant un squelette insoluble de type polyacryiique avec des greffons solubies de type acide poly-12(hydroxystéarique) ; les copolymères blocs greffés ou séquences comprenant au moins un bloc de type polyorganosiloxane et au moins un bloc d'un polymère radicalaire ; les copolymères blocs greffés ou séquences comprenant au moins un bloc de type po- lyorganosiloxane et au moins d'un polyéther ; les copolymères d'acrylates ou de méthacrylates d'alkyle en Cι-C4, ou d'acrylates ou de méthacrylates d'alkyie en C8-C30 ; les copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation de monomères éthyléniques comportant éventuellement des liaisons conjuguées et au moins un bloc d'un polymère vinylique ; les copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation de monomères éthyléniques comportant éventuellement des liaisons conjuguées et au moins un bloc d'un polymère acrylique ; les copolymères blocs greffés ou séquences comprenant au moins un bloc résultant de la polymérisation de diène et au moins un bloc d'un polyéther.21. Composition according to one of the preceding claims, in which the stabilizer is chosen from silicone polymers grafted with a hydrocarbon chain; hydrocarbon polymers grafted with a silicone chain; grafted copolymers having an insoluble backbone of polyacrylic type with solubied grafts of poly-12 acid (hydroxystearic); graft or block block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer; grafted or block copolymers comprising at least one block of the po- type lyorganosiloxane and at least one polyether; copolymers of Cι-C 4 alkyl acrylates or methacrylates, or C 8 -C 30 alkyl acrylates or methacrylates; graft or block block copolymers comprising at least one block resulting from the polymerization of ethylenic monomers optionally comprising conjugated bonds and at least one block of a vinyl polymer; graft or block block copolymers comprising at least one block resulting from the polymerization of ethylenic monomers optionally comprising conjugated bonds and at least one block of an acrylic polymer; grafted or block copolymers comprising at least one block resulting from the polymerization of diene and at least one block of a polyether.
22. Composition selon l'une des revendications précédentes, caractérisée en ce que le stabilisant est un polymère bloc greffé ou séquence, comprenant au moins un bloc résultant de la polymérisation de diène et au moins un bloc d'un polymère vinylique. 22. Composition according to one of the preceding claims, characterized in that the stabilizer is a graft or block block polymer, comprising at least one block resulting from the polymerization of diene and at least one block of a vinyl polymer.
23. Composition selon l'une des revendications précédentes, comprenant, en outre, au moins une phase grasse additionnelle choisie parmi les cires, les gommes et/ou les corps gras pâteux, d'origine végétale, animale, minérale, de synthèse, ou siliconee, et leurs mélanges. 23. Composition according to one of the preceding claims, further comprising at least one additional fatty phase chosen from waxes, gums and / or pasty fatty substances, of vegetable, animal, mineral, synthetic origin, or silicone, and mixtures thereof.
24. Composition selon l'une des revendications 14 à 23, caractérisée en ce que les matières colorantes comprennent au moins un composé pulvérulent choisi parmi les charges, les pigments, les nacres et leurs mélanges.24. Composition according to one of claims 14 to 23, characterized in that the coloring matters comprise at least one pulverulent compound chosen from fillers, pigments, nacres and their mixtures.
25. Composition selon la revendication 24, caractérisée en ce que le composé pulvérulent représente jusqu'à 50 % du poids total de la composition.25. Composition according to Claim 24, characterized in that the pulverulent compound represents up to 50% of the total weight of the composition.
26. Composition selon l'une des revendications 24 à 25, caractérisée en ce que le composé pulvérulent représente de 1 à 40 % du poids total de la composition. 26. Composition according to one of claims 24 to 25, characterized in that the pulverulent compound represents from 1 to 40% of the total weight of the composition.
27. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère en dispersion représente (en matière sèche) jusqu'à 60 % du poids total de la composition.27. Composition according to one of the preceding claims, characterized in that the polymer in dispersion represents (in dry matter) up to 60% of the total weight of the composition.
28. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère en dispersion représente (en matière sèche) de 12 à 60 % du poids total de la composition.28. Composition according to one of the preceding claims, characterized in that the polymer in dispersion represents (in dry matter) from 12 to 60% of the total weight of the composition.
29. Composition selon l'une des revendications précédentes, caractérisée en ce que la phase grasse liquide contient au moins une huile choisie parmi les isoparaffines en C8- C16, l'isododécane et les siiiconés linéaires ou cycliques ayant de 2 à 7 atomes de silicium, ces siiiconés comportant éventuellement des groupes alkyle ayant de 1 à 10 atomes de carbone, leurs mélanges.29. Composition according to one of the preceding claims, characterized in that the liquid fatty phase contains at least one oil chosen from C 8 - C 16 isoparaffins, isododecane and linear or cyclic siionics having from 2 to 7 atoms of silicon, these silicones optionally comprising alkyl groups having from 1 to 10 carbon atoms, their mixtures.
30. Composition selon l'une des revendications précédentes, se présentant sous forme d'un stick ou bâton, sous la forme d'une pâte souple de viscosité dynamique à 25°C de 1 à 40 Pa.s, sous forme de coupelle, de gel huileux, de liquide huileux, de dispersion vési- culaire contenant des lipides ioniques et/ou non ioniques, d'émulsion eau-dans-huile ou huile-dans-eau. 30. Composition according to one of the preceding claims, in the form of a stick or stick, in the form of a flexible paste of dynamic viscosity at 25 ° C. from 1 to 40 Pa.s, in the form of a cup, oily gel, oily liquid, vesicular dispersion containing ionic and / or nonionic lipids, water-in-oil or oil-in-water emulsion.
31. Composition selon l'une des revendications précédentes, se présentant sous forme anhydre.31. Composition according to one of the preceding claims, which is in anhydrous form.
32. Composition selon l'une des revendications précédentes, se présentant sous la forme d'un produit de soin et/ou de maquillage de la peau et/ou des lèvres. 32. Composition according to one of the preceding claims, which is in the form of a product for caring for and / or making up the skin and / or the lips.
33. Composition selon l'une des revendications précédentes, se présentant sous forme d'un fond de teint, d'un fard à joues ou à paupières, d'un rouge à lèvres, d'une base ou baume de soin pour les lèvres, d'un produit anti-cernes, d'un eye liner, d'un mascara.33. Composition according to one of the preceding claims, which is in the form of a foundation, a blusher or an eyeshadow, a lipstick, a base or lip care balm. , concealer, eye liner, mascara.
34. Utilisation dans ou pour la fabrication d'une composition à application topique, de particules d'au moins un polymère dispersées et stabilisées dans une phase grasse liquide et stabilisées en surface par un agent stabilisant, ladite phase grasse étant épaissie par un agent rhéologique liposoluble de type polysaccharide, pour diminuer, voire supprimer, le transfert du film de composition déposé sur la peau et/ou les lèvres d'être humain vers un support mis en contact avec le film et/ou conserver sa brillance.34. Use in or for the manufacture of a composition for topical application, of particles of at least one polymer dispersed and stabilized in a liquid fatty phase and surface-stabilized by a stabilizing agent, said fatty phase being thickened by a rheological agent liposoluble of polysaccharide type, to reduce, or even eliminate, the transfer of the film of composition deposited on the skin and / or the lips of a human being to a support brought into contact with the film and / or to retain its gloss.
35. Procédé de soin cosmétique ou de maquillage des lèvres ou de la peau, consistant à appliquer sur respectivement les lèvres ou la peau une composition cosmétique telle défi- nie aux revendications 1 à 33.35. A process for cosmetic care or for making up the lips or the skin, consisting in applying to the lips or the skin respectively a cosmetic composition as defined in claims 1 to 33.
36. Procédé pour limiter, voire supprimer, le transfert d'une composition de maquillage ou de soin de la peau ou des lèvres sur un support différent de la peau ou des lèvres, contenant une phase grasse liquide et au moins un ingrédient choisi parmi les actifs cosméti- ques, dermatologiques, hygiéniques et pharmaceutiques et les matières colorantes, consistant à introduire dans la phase grasse liquide un agent rhéologique liposoluble de type polysaccharide et liquide des particules de polymère dispersibles dans ladite phase grasse liquide et stabilisabies en surface par un agent stabilisant. 36. Method for limiting, or even eliminating, the transfer of a makeup or care composition for the skin or the lips on a support different from the skin or the lips, containing a liquid fatty phase and at least one ingredient chosen from cosmetic, dermatological, hygienic and pharmaceutical active agents and coloring matters, consisting in introducing into the liquid fatty phase a liposoluble rheological agent of polysaccharide and liquid type of particles of polymer dispersible in said liquid fatty phase and stabilized on the surface by a stabilizing agent .
PCT/FR1999/002727 1998-11-09 1999-11-08 Cosmetic composition without transfer comprising dispersed polymer particles an a polysaccharide rheological agent WO2000027350A1 (en)

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