WO2010057920A2 - Method for making up or caring for eyelashes or eyebrows using a polyalkene-based supramolecular polymer - Google Patents

Method for making up or caring for eyelashes or eyebrows using a polyalkene-based supramolecular polymer Download PDF

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Publication number
WO2010057920A2
WO2010057920A2 PCT/EP2009/065390 EP2009065390W WO2010057920A2 WO 2010057920 A2 WO2010057920 A2 WO 2010057920A2 EP 2009065390 W EP2009065390 W EP 2009065390W WO 2010057920 A2 WO2010057920 A2 WO 2010057920A2
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WO
WIPO (PCT)
Prior art keywords
composition
acid
polymer
chosen
oil
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Application number
PCT/EP2009/065390
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French (fr)
Other versions
WO2010057920A3 (en
Inventor
Stéphane Arditty
Nathalie Jager Lezer
Sandrine Chodorowski-Kimmes
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L'oreal
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Publication of WO2010057920A2 publication Critical patent/WO2010057920A2/en
Publication of WO2010057920A3 publication Critical patent/WO2010057920A3/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/064Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90Block copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/10Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006Rubber characterised by functional groups, e.g. telechelic diene polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30Characterized by the absence of a particular group of ingredients
    • A61K2800/31Anhydrous

Definitions

  • One subject of the present invention is a method for coating eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of a composition comprising at least one polyalkene-based supramolecular polymer.
  • the composition according to the invention may be in the form of a mascara.
  • the term "mascara” is understood to mean a composition intended to be applied to the eyelashes: it may be an eyelash makeup composition, an eyelash makeup base, a composition to be applied over a mascara, also known as a topcoat, or else a cosmetic composition for treating eyelashes.
  • the mascara is more particularly intended for human eyelashes, but also for false eyelashes .
  • eyelash makeup compositions are composed of at least one wax or of a mixture of waxes dispersed in an aqueous liquid phase or in an organic solvent phase.
  • Anhydrous mascaras or mascaras with a low content of water and/or water-soluble solvents which are known as "waterproof mascaras", formulated in the form of a dispersion of waxes in non-aqueous solvents, and which have good resistance to water and/or to sebum, are known in particular.
  • waterproof mascaras formulated in the form of a dispersion of waxes in non-aqueous solvents, and which have good resistance to water and/or to sebum
  • the makeup film obtained after application of these compositions is not sufficiently water-resistant, when bathing or showering for example, to tears or to sweat or else to sebum.
  • the mascara then has a tendency to run - appearance of rings under the eyes - or to disintegrate over time: grains are deposited and unattractive marks appear around the eyes .
  • a liposoluble film-forming polymer or a polymer in the form of a dispersion of particles in an organic solvent phase, at a higher content of film- forming polymer.
  • the presence of a high content of film- forming polymer is reflected by a pasty texture of the composition, which forms, after being deposited on the keratin fibres, a granular, non-uniform film that lacks slipperiness on application.
  • the objective of the present invention is therefore to provide a composition for making up or coating keratin fibres, especially eyelashes or eyebrows, which has good water resistance and/or sebum resistance properties, and also good rubbing resistance properties.
  • a polyalkene-based supramolecular polymer formulated in a continuous oily phase in the presence of a colorant, makes it possible to obtain a composition having a good water resistance and/or sebum resistance, and also a very good resistance to rubbing.
  • water resistance is understood according to the present application to mean the in vitro water resistance evaluated according to the following protocol:
  • composition is applied to 3 samples of straight Caucasian hair having 30 knots (60 eyelashes 1 cm in length) with a fringe length of 2 cm, by making 3 x 10 passes at 2 minute intervals with uptake of product between each series of 10 passes. Each sample is then dried at ambient temperature for a drying time of one hour.
  • the 3 made-up samples are immersed in a container containing water at 20 0 C for a given time (1 hour, 24 hours or 1 week) .
  • the 3 samples are then wiped back and forth 5 times on a square cloth of the Wypall L40 type from Kimberly Clark.
  • sebum resistance is understood according to the present application to mean the in vitro sebum resistance evaluated according to the same measurement protocol as for the water resistance described above, except that the 3 made-up samples are immersed in a container containing squalene (the squalene is present at 18% in the composition of sebum), instead of water.
  • rubbing resistance is understood according to the present application to mean the in vitro rubbing resistance evaluated according to the following protocol:
  • composition is applied to 3 samples of straight Caucasian hair having 30 knots (60 eyelashes 1 cm in length) with a fringe length of 2 cm, by making 3 x 10 passes at 2 minute intervals with uptake of product between each series of 10 passes. Each sample is then dried at ambient temperature for a drying time of one hour.
  • the made-up sample is then positioned perpendicularly above a sheet of paper and rubbed using a hard brush of the Keracils® type (30 passes) .
  • the quantity of grains thus formed, recovered on the sheet of paper, is evaluated.
  • a score between 0 and 6 is attributed to this quantity of grains; 0 being the score for which no grain is recovered on the sheet of paper and 6 the score for which a very large quantity of grains is recovered.
  • One subject of the present invention is therefore a method for making up or caring for eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of at least one layer of a cosmetic composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer, and at least one colorant.
  • Another subject of the present invention is an assembly for making up or caring for eyelashes or eyebrows comprising:
  • composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer and at least one colorant
  • said applicator comprising means that make it possible to smooth and/or separate the eyelashes or eyebrows, especially in the form of teeth, bristles or other reliefs .
  • compositions according to the invention are thus used for making up and/or caring for keratin fibres, in particular eyelashes, for example as mascaras.
  • the process for making up or coating eyelashes or eyebrows according to the invention consists, in particular, in applying an effective amount of a composition as described above, to the eyelashes or the eyebrows.
  • the applicator included in the makeup or care assembly according to the present invention comprises means that make it possible to smooth and/or separate the eyelashes or eyebrows, especially in the form of teeth, bristles or other reliefs.
  • the application means may be used to apply the composition to the eyelashes or the eyebrows.
  • the applicator may also be used for finishing the making-up process in one region of the eyelashes or of the eyebrows made up or loaded with product using another applicator.
  • the composition according to the invention may be withdrawn from a container by immersing the application member into this container.
  • the application part may comprise, optionally, a member for closing a container that contains the composition according to the invention.
  • the process of applying the composition according to the invention to the eyelashes or the eyebrows may also comprise the following steps: - forming a deposit of the cosmetic composition on the eyelashes or the eyebrows; and
  • the application member is arranged in order to apply a product to the eyelashes or the eyebrows, and may comprise, for example, a brush or a comb.
  • the brush may comprise a twisted core and bristles held between the turns of the core, or may be produced in yet another way.
  • the comb is, for example, produced from a single part by moulding of a plastic.
  • the application member may be magnetic.
  • the application member is mounted at the end of a wand, which wand may be flexible, which may contribute to improving the comfort during application.
  • the applicator may or may not comprise a reservoir that contains the composition.
  • the composition is, for example, contained in a container and the application member is, for example, loaded with composition by being introduced at least partially into this container.
  • the container may or may not comprise a wiping member.
  • the reservoir may be fastened in a removable or unremovable manner to the applicator.
  • the wall of the reservoir is used, for example, for gripping the applicator .
  • the assembly according to the invention may also comprise at least two different application members which may be selectively mounted on the applicator.
  • the packaging and application assembly comprises an applicator 2 and a container 3 that contains a reserve of a makeup product P, in this particular case a composition according to the invention, for example mascara.
  • a makeup product P in this particular case a composition according to the invention, for example mascara.
  • the container 3 is conventional in the example illustrated and comprises a body 5 equipped with an externally threaded neck 6. A wiping member 7 is fastened inside the neck 6.
  • the applicator 2 comprises an application member 10 constituted, in the example in question, of a mascara brush.
  • the application member 10 is mounted at the end of a wand 11, the other end of which is attached to a case 13 comprising an end part arranged so as to screw onto the neck 6 and thus seal the container 3 in a leaktight manner.
  • the brush 10 comprises, for example, bristles, the ends of which are arranged in helical layers.
  • the wand may be produced with a constant or variable cross section.
  • the wand 11 is flexible, a person skilled in the art being able to choose the dimensions of the wand as a function, for example, of the nature of the application member, of the product and of the treatment to be carried out.
  • the application member When the application member is configured in the form of a comb, the latter may be in accordance with what is described, in particular, in the publications US 2003-0089379-A1, US 6 655 390, US 6 814 084, US 6 675 814, US 6 581 610, US 6 546 937, US 6 539 950, US 6 412 496 or US 6 343 607, this list not being limiting.
  • the invention is not limited to one particular application member and the latter may especially be equipped with a means that makes it possible to heat the product and/or the eyelashes and/or the eyebrows during the application.
  • the application members may be of any type, especially with capillary slits or the like.
  • the application members may be made in various ways, especially by moulding, injection-moulding, staple fastening or twisting.
  • the application members may be intended for single use, where appropriate.
  • the application members may be fastened by any means to the application part, especially by bonding, welding, punching, click-fastening, screwing, with magnets, by friction, by attachment of Velcro® type, by gripping between jaws or the arms of pincers.
  • the application member may be driven in rotation, where appropriate, for example as described in patents US 4 937 326, US 4 922 934 and US 6 565 276.
  • the application of the product may be carried out, especially when the invention is implemented in order to apply a product to the eyelashes or the eyebrows, after having heated the product, for example by placing it in a microwave oven.
  • composition according to the invention may be packaged in a container delimiting at least one compartment which comprises said composition, said container being sealed by a sealing member.
  • the container may be associated with the applicator .
  • the applicator may be attached to the container, as described, for example, in patent FR 2 761 959.
  • the applicator is attached to a wand which, itself, is attached to the sealing member.
  • the sealing member may be coupled to the container by screwing.
  • the coupling between the sealing member and the container takes place other than by screwing, especially via a bayonet mechanism, by click-fastening or by clamping.
  • click- fastening is understood to mean, in particular, any system that involves surmounting a rim or bead of material by elastic deformation of a portion, especially of the sealing member, then by returning to the elastically unstressed position of said portion after the rim or bead has been surmounted.
  • the container may be at least partly made of a thermoplastic.
  • thermoplastics mention may be made of polypropylene or polyethylene.
  • the container is made from a non- thermoplastic material, especially from glass or from metal or an alloy.
  • the container is preferably equipped with a wringer placed in the vicinity of the opening of the container.
  • a wringer makes it possible to wipe the applicator and optionally the wand to which it may be attached.
  • Such a wringer is described, for example, in patent FR 2 792 618.
  • polyalkene-based supramolecular polymer is understood to mean a polymer comprising, in its structure, at least one polyalkene part and at least one part comprising at least one group capable of forming at least 3 H bonds, preferably 4 H bonds.
  • the polyalkene is preferably chosen from poly (ethylene/butylene) s, polybutadienes and polyisoprenes .
  • the polyalkene-based supramolecular polymers according to the invention may be derived from the condensation of at least one polyalkene polymer functionalized by at least one reactive group, with at least one graft functionalized by at least one reactive group capable of reacting with the reactive group or groups of the functionalized polyalkene polymer, said graft bearing at least one group capable of forming at least 3 H bonds, preferably at least 4 H bonds.
  • the functionalized polyalkene polymer is of formula A:
  • HX-R-X'H XH and X' H being reactive groups, with X and X', which are identical or different, chosen from O, S, NH, or NR a , R a representing a Ci-C ⁇ alkyl group; preferably, X and/or X' denote O; more preferably still, X and X' denote O; R represents a homopolymer or a copolymer derived from one or more monounsaturated or polyunsaturated C2-C10, and preferably C2-C4, alkenes; R preferably represents a poly (ethylene/butylene) , a polybutadiene or a polyisoprene .
  • the functionalized polyalkene polymer is chosen from hydroxyl-terminated poly (ethylene/butylene) s, hydroxyl-terminated polybutadienes and hydroxyl-terminated polyisoprenes.
  • the poly (ethylene/butylene) s are copolymers of 1-butene and ethylene. They can be represented schematically by the sequence of units of structures:
  • the polybutadienes may be poly (1, 4-butadiene) s or poly (1, 2-butadiene) s, which may be respectively represented schematically by the sequences of following units :
  • the functionalization preferably takes place at the end of the chains. Reference is then made to telechelic polymers.
  • the functionalization groups may be attached to the polyalkene polymer via linkers, preferably linear or branched Ci-C 4 alkylene groups.
  • polyalkenes may be hydrogenated in order to avoid risks of crosslinking.
  • They may comprise, in their structure, other units resulting from other monomers.
  • comonomers mention may in particular be made of styrene.
  • Polydienes preferably hydrogenated polydienes having hydroxyl end groups and polyolefins having hydroxyl end groups are preferred polymeric backbones according to the invention.
  • polyolefins which are homopolymers or copolymers, having CC, CO-hydroxyl end groups, such as: • polyisobutylene oligomers having CC, C ⁇ -hydroxyl end groups; and
  • the supramolecular polymers of the present invention have, in their structure, at least one graft bearing at least one group capable of forming at least 3 H bonds, preferably at least 4 H bonds.
  • These groups capable of forming at least 3 H bonds can comprise, for example, at least 3 functional groups, preferably at least 4 functional groups, chosen from:
  • the groups capable of forming at least 3 H bonds form a base structural element comprising at least 3 functional groups, preferably at least 4 functional groups and more preferably 4 functional groups capable of establishing H bonds.
  • the base structural elements capable of establishing 3 or 4 H bonds can be represented schematically in the following way:
  • each structural element must be able to establish H bonds with one or more partner structural elements which are identical (that is to say, self- complementary) or different, so that each pairing of two partner structural elements takes place by formation of at least three H bonds, preferably at least four H bonds and more preferably 4 H bonds.
  • a proton acceptor X will be paired with a proton donor Y.
  • Several possibilities are offered, for example pairing of: XXXX with YYYY; XXXY with YYYX; XXYX with YYXY; XYYX with YXXY; XXYY with YYXX, which may or may not be self- complementary;
  • XYXY with YXYX which may or may not be self- complementary.
  • 2 donor bonds for example NH
  • the groups capable of forming at least 3 H bonds comprise rings having 5 or 6 atoms (aromatic rings or unsaturated heterocycles) , very often constituted of C and/or N atoms and with conjugated double bonds in order to stabilize and control the H interactions .
  • the groups capable of forming at least 3 H bonds are involved in rings having 6 atoms comprising C and/or N atoms and with conjugated double bonds in order to stabilize and control the H interactions .
  • the groups capable of forming 3 or 4 H bonds are chosen from the following families, it being understood that all the tautomeric forms are included: - (i) aminopyrimidones of formula:
  • ureidotriazines and in particular mono-, di- and triureidotriazines, especially the ureidoaminotriazines with the structure:
  • acylamino aminotriazines (mono- or diacylamino and mono- or diamino) and in particular the compounds with the structure:
  • ureidopyridines in particular mono- or diureidopyridines, especially those of formulae:
  • the Ri radicals which are identical or different, represent a single bond, a hydrogen atom, a halogen atom and/or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-C ⁇ ooo carbon-based (in particular alkyl) group which can comprise one or more heteroatoms, such as O, S, N, P, Cl, Br or F; or a combination of these meanings.
  • the Ri radical can in particular be a C4-C12 cycloalkyl group, a linear or branched C1-C30 alkyl group or a C4-C12 aryl group which are optionally substituted by an amino, ester and/or hydroxyl functional group.
  • the Ri radical may also be a C4H9, phenyl, 1,4- nitrophenyl, 1, 2-ethylene, 1, 6-hexylene, 1, 4-butylene, 1, 6- (2, 4, 4-trimethylhexylene) , 1,4- (4-methylpentylene) , 1, 5- (5-methylhexylene) , 1, 6- ( 6-methylheptylene) , 1,5- (2,2, 5-trimethylhexylene) , 1,7- (3, 7-dimethyloctylene) , -isophorone-, 4, 4 ' -methylenebiscyclohexylene, tolylene, 2-methyl-l , 3-phenylene, 4-methyl-1, 3-phenylene or 4,4- biphenylenemethylene group; and preferably an -isophorone-, - (CH 2 ) 2 -, ⁇ (CH 2 ) ⁇ , -CH 2 CH(CH 3 ) -CH 2 -C (CHs) 2 -CH 2 -CH 2 -
  • Ri is a single bond.
  • the R 2 radicals which are identical or different within one and the same formula, represent a single bond, a hydrogen atom, a halogen atom (-Br, -Cl or -F) , an -OH radical, an -N(R) 2 radical (with R being H or a linear or branched Ci-Ci 2 , preferably Ci-C 4 , alkyl radical and better still a methyl or ethyl radical) or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-C ⁇ ooo hydrocarbon-based group which can comprise one or more heteroatoms, such as O, S, N, P or F; or a combination of these meanings.
  • R 2 radicals can in particular be H, CN, NH 2 or else:
  • R 2 represents H, CH 3 , Ci 3 H 27 , C 7 Hi 5 or phenyl.
  • the R 3 radicals which are identical or different within one and the same formula, represent a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-C ⁇ ooo hydrocarbon-based group which can comprise one or more heteroatoms, such as 0, S, N, P or F; or a combination of these meanings.
  • the R3 radical can in particular be a C4-C12 cycloalkyl group, a linear or branched C1-C30 alkyl group or a C4-C12 aryl group; optionally substituted by an amino, ester and/or hydroxyl functional group.
  • R3 represents a methyl radical.
  • at least one, in particular one or two, of the Ri and/or R 2 groups is a single bond constituting the point of attachment of the group capable of forming at least 3 H bonds on the residue of the graft.
  • said point of attachment is borne by Ri and/or R 2 and preferably it is borne by Ri.
  • the groups capable of forming at least 3 H bonds may be chosen in particular from:
  • ureidotriazines in particular ureidoaminotriazines, or diaminotriazines
  • Ri is a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-C ⁇ ooo hydrocarbon-based group which can comprise one or more heteroatoms, such as O, S, N, P or F,
  • - cytidine complementary to thymine
  • - triamino-s-triazine complementary to uracil or to succinimide or to glutarimide or to cyanuric acid or to thymine or to maleimide or to (di) aminopyrimidine or to barbituric acid
  • acylamino amino-s-triazine complementary to uracil or to succinimide or to glutarimide or to cyanuric acid or to thymine or to maleimide or to (di) aminopyrimidine or to barbituric acid.
  • 3 H bonds are chosen from the groups capable of establishing at least three H bonds with themselves
  • acylamino-s-triazines in particular (acyl) diamino-s- triazines
  • groups capable of forming at least 3 H bonds of the groups derived from ureidopyrimidones, in particular from 2-ureidopyrimidone or from 6-methyl-2- ureidopyrimidone .
  • the residue of the graft is constituted of a linker L bearing at least one reactive group capable of reacting with the functionalized polyalkene group or groups .
  • This reactive group may be, for example, a carboxy group or an isocyanate group.
  • the linker L is a phenylene; 1,4- nitrophenyl; 1, 2-ethylene; 1, 6-hexylene; 1, 4-butylene; 1, 6- (2, 4, 4-trimethylhexylene) ; 1,4- (4-methylpentylene) ; 1, 5- (5-methylhexylene) ; 1, 6- ( 6-methylheptylene) ; 1,5- (2, 2, 5-trimethylhexylene) ; 1, 7- (3, 7-dimethyloctylene; -isophorone-; 4, 4 ' -methylenebiscyclohexylene; tolylene; 2-methyl-l , 3-phenylene; 4-methyl-l, 3-phenylene or 4,4- biphenylenemethylene group, and preferably an -isophorone-; - (CH 2 ) 2 -; - (CH 2 ) 6 -; -CH 2 CH (CH 3 ) -CH 2 -C (CH 3 ) 2 - CH 2 -CH 2 -; 4
  • the grafts are of formula (B) :
  • the supramolecular polymer of the invention is of formula C:
  • R, X, X' and L having the meanings indicated previously.
  • X and X' denote an oxygen atom.
  • the polyalkene-based supramolecular polymer or polymers may be present in the composition at a content ranging from 0.1% to 40% by weight, preferably ranging from 0.1% to 30% by weight, more preferably ranging from 0.5% to 20% by weight, and more preferably still ranging from 1% to 15% by weight relative to the total weight of the composition.
  • the polyalkene-based supramolecular polymer or polymers of the invention may also be obtained from a polymer (Al) comprising a polyalkene part, said polymer being functionalized by at least one reactive group (Bl), by condensation with at least one molecule (A3) comprising at least one reactive group (B2), said molecule being such that, after reaction of the (Bl) and (B2) groups, there is formation of a species capable of forming at least 3 H bonds, preferably at least 4 H bonds.
  • these species have the structures (i) to (xxiv) as defined previously, with Ri denoting a single bond.
  • the polymer (Al) may especially result from the action, on a polyalkene polymer of formula A as defined above, of compounds (A2) comprising two reactive groups (B' 2) capable of reacting with the functionalized groups of the polyalkene.
  • These reactive groups may be, for example, carboxy groups or isocyanate groups.
  • the B2 groups are identical to the B' 2 groups .
  • the compounds (A2) have the following structure (C ) :
  • the polymers Al are of formula (Cl) :
  • the molecule (A3) is 6- methylisocytosine of formula:
  • the supramolecular polymer according to the invention can be prepared by the processes normally employed by a person skilled in the art, in order to form a urethane bond between the free OH functional groups of a polyalkene and the isocyanate functional groups borne by the joining group.
  • a general preparation process comprises:
  • the polymer comprising at least two reactive functional groups, especially OH, to a temperature which can be between 60° C and 140 °C.
  • the hydroxyl number of the polymer could act as reference in order to measure the state of progression of the reaction; directly adding the joining group bearing the reactive functional groups, in particular isocyanate functional groups;
  • reaction could also be monitored by quantitative determinations of the hydroxyl functional groups; - it could also be possible to add ethanol in order to make sure that the residual isocyanate functional groups have completely disappeared;
  • the mixture could be filtered if necessary.
  • the reaction can be carried out in the presence of a solvent, in particular methyltetrahydrofuran, tetrahydrofuran, toluene, butyl acetate or else propylene carbonate.
  • a solvent in particular methyltetrahydrofuran, tetrahydrofuran, toluene, butyl acetate or else propylene carbonate.
  • the compound can be washed and dried, indeed even purified, according to the general knowledge of a person skilled in the art.
  • the reaction can comprise the following stages:
  • the diisocyanate can optionally be in excess with respect to the polymer.
  • This first stage can be carried out in the presence of solvent, at a temperature of between 20°C and 100°C. This first stage can be followed by a period of stirring, under a controlled atmosphere, for a period ranging from 1 hour to 24 hours. The mixture can optionally be heated. The state of progression of this first stage can be monitored by quantitative determination of the hydroxyl functional groups; then
  • This second stage can optionally be carried out in the presence of a cosolvent, such as toluene, butyl acetate or else propylene carbonate.
  • a cosolvent such as toluene, butyl acetate or else propylene carbonate.
  • the reaction mixture can be heated at between 80 °C and 140 °C for a time varying between 1 hour and 24 hours.
  • the presence of a catalyst can promote the production of the desired final product. Mention may be made, for example, of the use of dibutyltin dilaurate.
  • the reaction can be monitored by infrared spectroscopy, by monitoring the disappearance of the peak characteristic of the isocyanate between 2200 and 2300 cm “1 .
  • ethanol can be added to the reaction medium in order to neutralize the residual isocyanate functional groups.
  • the reaction mixture can optionally be filtered.
  • the polymer could be directly stripped in a cosmetic solvent.
  • composition comprising an oily continuous phase is understood to mean that the composition has a conductivity, measured at 25°C, of less than 23 ⁇ S/cm (microSiemens/cm) , the conductivity being measured, for example, using an MPC227 conductivity meter from Mettler Toledo and an Inlab730 conductivity measurement cell.
  • the measurement cell is immersed in the composition, so as to remove the air bubbles liable to be formed between the 2 electrodes of the cell.
  • the conductivity is read as soon as the value of the conductivity meter has stabilized. An average is taken over at least 3 successive measurements.
  • oil is understood to mean any fatty substance which is in liquid form at ambient temperature (20-25 0 C) and at atmospheric pressure.
  • the oil may be volatile or non-volatile.
  • volatile oil is understood to mean, within the meaning of the invention, any oil capable of evaporating on contact with keratin materials in less than one hour, at ambient temperature and atmospheric pressure.
  • volatile oils of the invention are volatile cosmetic oils that are liquid at ambient temperature and that have a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging from 0.13 Pa to 40 000 Pa (10 ⁇ 3 to
  • non-volatile oil is understood to mean an oil that remains on the keratin materials at ambient temperature and atmospheric pressure for at least several hours and that has, in particular, a non- zero vapour pressure, at ambient temperature and atmospheric pressure, of less than 0.13 Pa (10 ⁇ 3 mmHg).
  • the continuous oily phase according to the invention may be present at a content that varies from
  • the continuous oily phase that is suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluorinated or unfluorinated oils, or mixtures thereof.
  • the oils may be of animal, plant, mineral or synthetic origin.
  • silicon oil is understood to mean an oil comprising at least one silicon atom, and especially at least one Si-O group.
  • said composition may comprise less than 10% by weight of silicone oil (s) relative to the total weight of the composition, better still less than 5% by weight, or may even be free of silicone oil.
  • silicone oil is understood to mean an oil comprising at least one fluorine atom.
  • hydrocarbon-based oil is understood to mean an oil that mainly contains hydrogen and carbon atoms .
  • the oils may optionally comprise oxygen, nitrogen, sulphur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
  • volatile oils may be chosen from hydrocarbon- based oils having from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffins) , such as isododecane (also known as 2, 2, 4, 4, 6-pentamethylheptane) , isodecane, isohexa- decane, and, for example, the oils sold under the trade names ISOPARS ® or PERMETHYLS ® .
  • hydrocarbon- based oils having from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffins) , such as isododecane (also known as 2, 2, 4, 4, 6-pentamethylheptane) , isodecane, isohexa- decane, and, for example, the oils sold under the trade names ISOPARS ® or PERMETHYLS ® .
  • the volatile hydrocarbon-based oil may also be a linear volatile alkane chosen from volatile linear alkanes comprising from 7 to 17 carbon atoms, and in particular from 9 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms, especially of plant origin.
  • alkanes By way of example of a volatile linear alkane suitable for the invention, mention may be made of the alkanes described in patent application WO 2007/068371 by Cognis. These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil.
  • n- nonadecane Cg
  • n-decane Cio
  • n-undecane Cn
  • n- dodecane C12
  • n-tridecane C13
  • n-tetradecane Ci 4
  • n-pentadecane Ci 5
  • n-hexadecane Ci ⁇
  • mixtures thereof and in particular the mixture of n-undecane (Cn) and n-tridecane (C13) sold under the reference CETIOL UT by Cognis.
  • volatile oils of volatile silicones, such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity of ⁇ 8 centiStokes (cSt) (8 x 10 ⁇ 6 m 2 /s) and having in particular from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
  • volatile silicones such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity of ⁇ 8 centiStokes (cSt) (8 x 10 ⁇ 6 m 2 /s) and having in particular from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
  • volatile silicone oil that can be used in the invention, mention may in particular be made of dimethicones having a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa- siloxane, heptamethylhexyltrisiloxane, heptamethyl- octyltrisiloxane, hexamethyldisiloxane, octamethyl- trisiloxane, decamethyltetrasiloxane, dodecamethyl- pentasiloxane, and mixtures thereof.
  • volatile fluorinated oils such as nonafluoromethoxybutane or perfluoro- methylcyclopentane, and mixtures thereof.
  • Non-volatile oils may in particular be selected from non-volatile hydrocarbon-based, fluorinated and/or silicone oils.
  • non-volatile hydrocarbon-based oil mention may in particular be made of: - hydrocarbon-based oils of animal origin,
  • oils of plant origin such as phytostearyl esters, for instance phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/ phytostearyl glutamate (Ajinomoto, Eldew PS203) , triglycerides constituted of fatty acid esters of glycerol, in particular in which the fatty acids may have chain lengths ranging from C4 to C36, and in particular from Cis to C36, it being possible for these oils to be linear or branched, and saturated or unsaturated; these oils may in particular be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppyseed oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe oil, sweet almond oil, peach kernel oil, groundnut oil, argan oil, avocado oil
  • John's wort oil monoi oil, hazelnut oil, apricot kernel oil, nut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grapeseed oil, pistachio oil, pumpkin oil, winter squash oil, quinoa oil, musk rose oil, sesame oil, soya bean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810 ® , 812 ® and 818 ® by the company Dynamit Nobel,
  • esters for instance oils of formula R1COOR2, in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that Ri + R2 is > 10.
  • the esters may in particular be selected from fatty acid and alcohol esters, such as, for example:
  • cetostearyl octanoate isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2- ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and palmitate, alkyl benzoate, poly(
  • - copolymers of a diol dimer and of a diacid dimer, and esters thereof such as copolymers of dilinoleyl diol dimers/dilinoleic dimers and esters thereof, for instance Plandool-G, - copolymers of polyols and of diacid dimers, and esters thereof, such as Hailuscent ISDA,
  • - fatty alcohols that are liquid at ambient temperature, with a branched and/or unsaturated carbon chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol,
  • - C12-C22 higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof, and
  • oils of high molar mass having in particular a molar mass ranging from approximately 400 to approximately 10 000 g/mol, in particular from approximately 650 to approximately 10 000 g/mol, in particular from approximately 750 to approximately 7500 g/mol, and more particularly ranging from approximately 1000 to approximately 5000 g/mol.
  • oils of high molar mass that can be used in the present invention, mention may in particular be made of the oils selected from: • lipophilic polymers,
  • an oil of high molar mass may be selected from: a) lipophilic polymers, such as:
  • polyisobutylenes for example hydrogenated polyisobutylenes, such as Panalane H-300 E sold or manufactured by the company Amoco
  • PVP polyvinylpyrrolidone
  • PVP copolymers that may be used in the invention, mention may be made of the PVP/vinyl laurate copolymer, the PVP/vinyl stearate copolymer, butylated PVP, the PVP/hexadecene copolymer, the PVP/triacontene copolymer or the PVP/acrylic acid/lauryl methacrylate copolymer, esters, such as:
  • non-volatile silicone oils that can be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMSs) , PDMSs comprising alkyl or alkoxy groups that are pendant and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyl- diphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, and dimethicones or phenyl trimethicone with a viscosity of less than or equal to 100 cSt, and mixtures thereof, and also mixtures of the oils a) and/or b) and/or c) .
  • PDMSs non-volatile polydi
  • the continuous oily phase is chosen from volatile hydrocarbon-based oils, preferably chosen from volatile branched alkanes having from 8 to 16 carbon atoms and volatile linear alkanes comprising from 7 to 17 carbon atoms.
  • composition of the invention contains at least one colorant such as pulverulent colorants, liposoluble dyes and water-soluble dyes.
  • the pulverulent colorants may be chosen from pigments and pearlescent agents.
  • the pigments may be chosen from organic pigments or inorganic pigments.
  • the colorant is chosen from organic pigments, inorganic pigments and pearlescent agents.
  • pigment is understood to mean any organic and/or inorganic entity having a solubility in water of less than 0.01% at 20 0 C, preferably of less than 0.0001%, and exhibiting an absorption between 350 and 750 nm, preferably an absorption with a maximum.
  • These pigments may be in the form of a powder or of a pigment paste. They can be coated or uncoated.
  • the pigment can be an inorganic pigment.
  • inorganic pigment is understood to mean any pigment which corresponds to the definition of Ullmann's Encyclopedia in the "Inorganic Pigment” chapter. Mention may be made, among inorganic pigments of use in the present invention, of titanium dioxide, which is or is not surface-treated, zirconium, zinc or cerium oxides, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
  • the following inorganic pigments can be used: Ta 2 O 5 , Ti 3 O 5 , Ti 2 O 3 , TiO, ZrO 2 as a mixture with TiO 2 , ZrO 2 , Nb 2 O 5 , CeO 2 , ZnS.
  • the pigment that is not surface-treated, subsequently referred to as “pigment”, may be an organic pigment.
  • organic pigment is understood to mean any pigment which corresponds to the definition of Ullmann' s Encyclopedia in the "Organic Pigment” chapter.
  • the organic pigment can in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone or phthalocyanine compounds, compounds of metal complex type, or isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.
  • white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100,
  • the pigments in accordance with the invention can also be in the form of composite pigments, as are described in patent EP 1 184 426.
  • These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder, which provides for the attachment of the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
  • the organic pigment can also be a lake.
  • the term "lake” is understood to mean dyes adsorbed onto insoluble particles, the combination thus obtained remaining insoluble during use.
  • the inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
  • Mention may be made, among the dyes, of cochineal carmine. Mention may also be made of the dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).
  • the colorant can also be a pearlescent agent.
  • pearlescent agents of white pearlescent pigments, such as mica covered with titanium dioxide or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium dioxide or with iron oxides, mica covered with titanium dioxide and in particular with ferric blue or with chromium oxide or mica covered with titanium dioxide and with an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride.
  • pearlescent pigments of the following pearlescent agents: Cellini sold by Engelhard (mica-Ti ⁇ 2-lake) , Prestige sold by Eckart (mica-Ti ⁇ 2) , Prestige Bronze sold by Eckart (mica-Fe2 ⁇ 3) or Colorona sold by Merck
  • multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
  • the colorant may also be a liposoluble dye.
  • Liposoluble dyes are, for example, Sudan red, D&C Red 17, D&C Green 6, ⁇ -carotene, soya bean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.
  • These colorants may be present at a content ranging from 0.01 to 30% by weight relative to the total weight of the composition.
  • composition according to the invention may comprise at least one agent for structuring the continuous oily phase (formed by the volatile or nonvolatile oils described above) chosen from waxes, pastes, semi-crystalline polymers, lipophilic gelling agents, and mixtures thereof.
  • agent for structuring the continuous oily phase chosen from waxes, pastes, semi-crystalline polymers, lipophilic gelling agents, and mixtures thereof.
  • the structuring agent may represent from 5 to 80% by weight relative to the total weight of the composition, preferably from 7 to 75% and more preferably still from 10 to 55% by weight.
  • the amount of structuring agent may be adjusted by a person skilled in the art as a function of the structuring properties of said agents.
  • the wax under consideration in the context of the present invention is generally a lipophilic compound which is solid at ambient temperature (25°C), which exhibits a reversible solid/liquid change in state and which has a melting point of greater than or equal to 30 0 C which can range up to 200 0 C and in particular up to 120°C.
  • a melting point of greater than or equal to 30 0 C which can range up to 200 0 C and in particular up to 120°C.
  • the waxes suitable for the invention can exhibit a melting point of greater than or equal to 45°C and in particular of greater than or equal to 55°C.
  • the melting point corresponds to the temperature of the most endothermic peak observed by thermal analysis (DSC) as described in the standard ISO 11357-3; 1999.
  • the melting point of the wax can be measured using a differential scanning calorimeter (DSC) , for example the calorimeter sold under the name "MDSC 2920" by TA Instruments .
  • DSC differential scanning calorimeter
  • a 5 mg sample of wax placed in a crucible is subjected to a first rise in temperature ranging from -20 0 C to 100 0 C at a heating rate of 10°C/minute, is then cooled from 100 0 C to -20°C at a cooling rate of 10°C/minute and, finally, is subjected to a second rise in temperature ranging from -20 0 C to 100 0 C at a heating rate of 5°C/minute.
  • the variation in the difference in power absorbed by the empty crucible and by the crucible comprising the sample of wax is measured as a function of the temperature.
  • the melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
  • the waxes capable of being used in the compositions according to the invention are chosen from waxes of animal, plant, mineral or synthetic origin, and their mixtures, which are solid at ambient temperature.
  • the waxes which can be used in the compositions according to the invention generally exhibit a hardness ranging from 0.01 MPa to 15 MPa, in particular of greater than 0.05 MPa and in particular of greater than 0.1 MPa.
  • the hardness is determined by the measurement of the compressive force measured at 20 0 C using a texture analyser sold under the name TA-XT2 by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm which is displaced at the measuring rate of 0.1 mm/s and which penetrates the wax to a penetration depth of 0.3 mm.
  • the measurement protocol is as follows:
  • the wax is melted at a temperature equal to the melting point of the wax + 10 0 C.
  • the molten wax is cast in a receptacle with a diameter of 25 mm and a depth of 20 mm.
  • the wax is recrystallized at ambient temperature (25°C) for 24 hours, so that the surface of the wax is flat and smooth, and then the wax is stored at 20 0 C for at least one hour before measuring the hardness or the tack.
  • the rotor of the texture analyser is displaced at the rate of 0.1 mm/s and then penetrates the wax to a penetration depth of 0.3 mm. When the rotor has penetrated the wax to the depth of 0.3 mm, the rotor is held stationary for 1 second (corresponding to the relaxation time) and is then withdrawn at the rate of 0.5 mm/s.
  • the value of the hardness is the maximum compressive force measured divided by the surface area of the cylinder of the texture analyser in contact with the wax.
  • waxes suitable for the invention of hydrocarbon-based waxes, such as beeswax, lanolin wax and Chinese insect waxes; rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto wax, berry wax, shellac wax, Japan wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffin waxes and ozokerite; polyethylene waxes, the waxes obtained by the Fischer-Tropsch synthesis and waxy copolymers, and their esters.
  • hydrocarbon-based waxes such as beeswax, lanolin wax and Chinese insect waxes
  • montan wax orange and lemon waxes, microcrystalline waxes, paraffin waxes and ozokerite
  • polyethylene waxes
  • Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils having linear or branched C8-C32 fatty chains. Mention may in particular be made, among these, of hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and di (1,1,1- trimethylolpropane) tetrastearate, sold under the name of Hest 2T-4S® by Heterene.
  • silicone waxes or fluorinated waxes Mention may also be made of silicone waxes or fluorinated waxes.
  • compositions according to the invention can comprise at least one wax referred to as a "tacky wax", that is to say having a tack of greater than or equal to 0.1 N. s and a hardness of less than or equal to 3.5 MPa.
  • a tacky wax that is to say having a tack of greater than or equal to 0.1 N. s and a hardness of less than or equal to 3.5 MPa.
  • the tacky wax used can have in particular a tack ranging from 0.1 N. s to 10 N.s, in particular ranging from 0.1 N.s to 5 N.s, preferably ranging from 0.2 to 5 N.s and better still ranging from 0.3 to 2 N.s.
  • the tack of the wax is determined by the measurement of the change in the force (compressive force) as a function of the time at 20 0 C according to the protocol indicated above for the hardness.
  • the tack corresponds to the integral of the curve of the force as a function of the time for the part of the curve corresponding to the negative values of the force.
  • the value of the tack is expressed in N.s.
  • the tacky wax which can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa.
  • tacky wax of a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture.
  • a wax is sold in particular under the names "Kester Wax K 82 P®” and "Kester Wax K 80 P®” by Koster Keunen.
  • waxes provided in the form of small particles having a size, expressed as volume-average "effective" diameter D[4,3], of the order of 0.5 to 30 micrometres, in particular of 1 to 20 micrometres and more particularly of 5 to 10 micrometres, subsequently denoted by the expression "microwaxes" .
  • the sizes of the particles can be measured by various techniques. Mention may in particular be made of light scattering techniques (dynamic and static) , Coulter counter methods, measurements by rate of sedimentation (related to the size via Stokes' law) and microscopy. These techniques make it possible to measure a particle diameter and, for some of them, a particle size distribution.
  • the sizes and size distributions of the particles of compositions according to the invention are measured by static light scattering using a commercial particle sizer of MasterSizer 2000 type from Malvern.
  • the data are processed on the basis of the Mie scattering theory.
  • This theory exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter.
  • This theory is described in particular in the work by Van de Hulst, H. C, “Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.
  • the composition is characterized by its volume- average "effective" diameter D [4, 3], defined in the following way: where V 1 represents the volume of the particles with an effective diameter Cl 1 . This parameter is described in particular in the technical documentation of the particle sizer.
  • the measurements are performed at 25°C on a dilute particle dispersion, obtained from the composition in the following manner: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) standing of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant.
  • the "effective" diameter is obtained by taking a refractive index of 1.33 for the water and a mean refractive index of 1.42 for the particles.
  • microwaxes which can be used in the compositions according to the invention, of carnauba microwaxes, such as that sold under the name of MicroCare 350 ® by Micro Powders, synthetic wax microwaxes, such as that sold under the name of MicroEase 114S ® by Micro Powders, microwaxes composed of a mixture of carnauba wax and of polyethylene wax, such as those sold under the names of Micro Care 300 ® and 310 ® by Micro Powders, microwaxes composed of a mixture of carnauba wax and of synthetic wax, such as that sold under the name Micro Care 325 ® by Micro Powders, polyethylene microwaxes, such as those sold under the names of Micropoly 200 ® , 220 ® , 220L ® and 250S ® by Micro Powders, and polytetrafluoroethylene microwaxes, such as those sold under the names of Microslip 519 ® and 519 L ® by Micro Powders.
  • synthetic wax microwaxes such as that sold
  • composition according to the invention can comprise a content of waxes ranging from 5 to 70% by weight, with respect to the total weight of the composition; in particular, it can comprise from 7 to 50% by weight thereof, more particularly from 10 to 45% by weight thereof.
  • composition according to the invention may comprise at least one pasty compound.
  • pastes is understood, within the meaning of the present invention, to mean a lipophilic fatty compound having a reversible solid/liquid change in state and comprising, at a temperature of 23°C, a liquid fraction and a solid fraction.
  • the pasty compound preferably has a hardness at 20 0 C ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.
  • the hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyser (for example, the TA-XT2i from Stable Micro Systems Ltd.) equipped with a stainless steel cylinder with a diameter of 2 mm.
  • the hardness measurement is carried out at 20 0 C at the centre of 5 samples.
  • the cylinder is introduced into each sample at a pre-rate of 1 mm/s and then at a measuring rate of 0.1 mm/s, the depth of penetration being 0.3 mm.
  • the value recorded for the hardness is that of the maximum peak.
  • This pasty compound is, additionally, at a temperature of 23°C, in the form of a liquid fraction and of a solid fraction.
  • the starting melting point of the pasty compound is below 23°C.
  • the liquid fraction of the pasty compound measured at 23°C represents from 23 to 97% by weight of the compound.
  • This liquid fraction at 23°C preferably represents between 40 and 85% by weight of the compound.
  • the liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the pasty compound.
  • the enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound to change from the solid state to the liquid state.
  • the pasty compound is "in the solid state” when the whole of its mass is in the solid form.
  • the pasty compound is "in the liquid state” when the whole of its mass is in the liquid form.
  • the enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC) , such as the calorimeter sold under the name MDSC 2920 by TA Instrument, with a rise in temperature of 5 or 10 0 C per minute, according to standard ISO 11357- 3:1999.
  • DSC differential scanning calorimeter
  • the enthalpy of fusion of the pasty compound is the amount of energy necessary to change the compound from the solid state to the liquid state. It is expressed in J/g.
  • the enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state which it exhibits at 23°C, composed of a liquid fraction and of a solid fraction.
  • the liquid fraction of the pasty compound measured at 32°C preferably represents from 40 to 100% by weight of the compound, preferably from 50 to 100%, preferably from 80 to 100%, more preferably from 90 to 100% by weight of the compound.
  • the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
  • the liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32°C to the enthalpy of fusion of the pasty compound.
  • the enthalpy of fusion consumed at 32 0 C is calculated in the same way as the enthalpy of fusion consumed at 23°C.
  • the pasty compound is preferably chosen from synthetic compounds and compounds of plant origin.
  • a pasty compound may be obtained by synthesis from starting products of plant origin.
  • the pasty compound is advantageously chosen from: lanolin and its derivatives, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins; polymeric or non-polymeric silicone compounds, such as high molecular weight polydimethylsiloxanes, polydimethylsiloxanes with side chains of the alkyl or alkoxy type that have from 8 to 24 carbon atoms, especially stearyl dimethicones; polymeric or non-polymeric fluorinated compounds; vinyl polymers, especially:
  • (meth) acrylates preferably having a C8-C30 alkyl group; • oligomers which are homopolymers and copolymers of vinyl esters having C8-C30 alkyl groups;
  • oligomers which are homopolymers and copolymers of vinyl ethers having C8-C30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C2-C100, preferably C2-C50, diols; polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and mixtures thereof, the ether of pentaerythritol and of polyethylene glycol comprising 5 oxyethylenated units (5 EO) (CTFA name: PEG-5 Pentaerythrityl Ether) , the ether of pentaerythritol and of polypropylene glycol comprising 5 oxypropylenated units (5 PO) (CTFA name: PPG-5 Pentaerythrityl Ether) , and mixtures thereof and more especially the PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythr
  • the pasty compound is preferably a polymer and especially a hydrocarbon-based polymer.
  • a preferred silicone and fluorinated pasty compound is polymethyltrifluoropropylmethylalkyl- dimethylsiloxane, manufactured under the name X22-1088 by Shin-Etsu.
  • the composition advantageously comprises a compatibilizer such as short-chain esters, for instance isodecyl neopentanoate .
  • liposoluble polyethers that are especially preferred are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30.
  • copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight of from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 EO) sold under the brand name Elfacos ST9 by Akzo Nobel.
  • a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 EO) sold under the brand name Elfacos ST9 by Akzo Nobel.
  • esters of a glycerol oligomer especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, for instance those sold under the brand name Softisan 649 by the company Sasol,
  • a diacid dimer formed from at least one unsaturated fatty acid • for instance the ester of fatty acid dimer of tall oil containing 36 carbon atoms and of a mixture i) of Guerbet alcohols containing 32 carbon atoms and ii) of behenyl alcohol; the ester of linoleic acid dimer and of a mixture of two Guerbet alcohols, 2-tetradecyl- octadecanol (32 carbon atoms) and 2-hexadecyleicosanol (36 carbon atoms) ,
  • the aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid and docosanoic acid, and mixtures thereof.
  • the aliphatic carboxylic acid is preferably branched.
  • the aliphatic hydroxycarboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid containing from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 20 hydroxyl groups, preferably from 1 to 10 hydroxyl groups and better still from 1 to 6 hydroxyl groups.
  • the aliphatic hydroxycarboxylic acid ester is chosen from: a) partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids; b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids; c) partial or total esters of saturated mono- hydroxylated aliphatic polycarboxylic acids; d) partial or total esters of saturated poly- hydroxylated aliphatic polycarboxylic acids; e) partial or total esters of C2 to C16 aliphatic polyols that have reacted with a monohydroxylated or polyhydroxylated aliphatic monocarboxylic or polycarboxylic acid, and mixtures thereof.
  • the aliphatic esters of an ester are advantageously chosen from: - the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 1 (1/1) or hydrogenated castor oil monoisostearate, the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 2 (1/2) or hydrogenated castor oil diisostearate, the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 3 (1/3) or hydrogenated castor oil triisostearate, and mixtures thereof.
  • the pasty compound may also be of plant origin.
  • isomerized jojoba oil such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Joj oba-50®, orange wax, such as for example the product sold under the reference Orange Peel Wax by the company Koster Keunen, shea butter, partially hydrogenated olive oil such as for example the compound sold under the reference Beurrolive by the company Soliance, cocoa butter, and mango oil, such as for example Lipex 302 from the company Aarhuskarlshamn .
  • polymer is understood to mean compounds containing at least two repeat units, preferably at least three repeat units and more especially at least ten repeat units.
  • si-crystalline polymer is understood to mean polymers comprising a crystallizable portion, a crystallizable pendant chain or a crystallizable block in the backbone, and an amorphous portion in the backbone and having a first- order reversible phase-change temperature, in particular of melting (solid-liquid transition) .
  • the amorphous portion of the polymer is in the form of an amorphous block; in this case, the semi-crystalline polymer is a block copolymer, for example, of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block.
  • block is generally understood to mean at least five identical repeat units.
  • the crystallizable block(s) is (are) thus of chemical nature different than that of the amorphous block (s) .
  • the semi-crystalline polymer has a melting point of greater than or equal to 30 0 C (especially ranging from 30 0 C to 80°C), preferably ranging from 30 0 C to
  • This melting point is a first-order change of state temperature.
  • This melting point may be measured by any known method and in particular using a differential scanning calorimeter (DSC) .
  • DSC differential scanning calorimeter
  • the semi-crystalline polymer (s) to which the invention applies has (have) a number-average molecular weight of greater than or equal to 1000.
  • the semi-crystalline polymer (s) of the composition of the invention has (have) a number- average molecular weight Mn ranging from 2000 to 800 000, preferably from 3000 to 500 000, better still from 4000 to 150 000, especially less than 100 000 and better still from 4000 to 99 000.
  • they have a number-average molecular weight of greater than 5600, for example ranging from 5700 to 99 000.
  • the term “crystallizable chain or block” is understood to mean a chain or block which, if it were alone, would reversibly change from the amorphous state to the crystalline state, depending on whether the system is above or below the melting point.
  • a chain is a group of atoms, which is pendant or lateral relative to the polymer backbone.
  • a block is a group of atoms belonging to the backbone, this group constituting one of the repeat units of the polymer.
  • the "crystallizable pendant chain” may be a chain containing at least six carbon atoms .
  • the semi-crystalline polymer may be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, and homopolymers and copolymers bearing at least one crystallizable side chain per repeat unit, and mixtures thereof .
  • Polymers bearing in the backbone at least one crystallizable block are especially block copolymers constituted of at least two blocks of different chemical nature, one of which is crystallizable.
  • the block polymers defined in patent US-A-5 156 911 may be used; -
  • the copolymers may be copolymers containing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature) . These copolymers may also contain two crystallizable blocks of different chemical nature.
  • the preferred copolymers are those that simultaneously contain at room temperature a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; mention may be made, for example, of polymers containing one of the crystallizable blocks and one of the amorphous blocks below: - Block that is crystallizable by nature: a) of polyester type, for instance poly (alkylene terephthalate) , b) of polyolefin type, for instance polyethylenes or polypropylenes .
  • Amorphous and lipophilic block for instance: amorphous polyolefins or copoly (olefin) s such as poly (isobutylene) , hydrogenated polybutadiene or hydrogenated poly (isoprene) .
  • amorphous polyolefins or copoly (olefin) s such as poly (isobutylene) , hydrogenated polybutadiene or hydrogenated poly (isoprene) .
  • copolymers containing a crystallizable block and an amorphous block that are different, mention may be made of: ⁇ ) poly ( ⁇ -caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in the article "Melting behavior of poly ( ⁇ -caprolactone) -block-polybutadiene copolymers" by S.
  • the semi-crystalline polymers in the composition according to the invention are non- crosslinked.
  • the polymer is chosen from copolymers resulting from the polymerization of at least one monomer containing a crystallizable chain chosen from saturated Ci 4 to C24 alkyl (meth) acrylates, Cu to Ci 5 perfluoroalkyl (meth) acrylates, Ci 4 to C24 N-alkyl (meth) acrylamides with or without a fluorine atom, vinyl esters containing Ci 4 to C2 4 alkyl or perfluoroalkyl chains, vinyl ethers containing Ci 4 to C2 4 alkyl or perfluoroalkyl chains, Ci 4 to C2 4 OC-olefins, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated Ci to Cio monocarboxylic acid ester or amide, which may be represented by the following formula :
  • the polymer is derived from a monomer containing a crystallizable chain chosen from saturated Ci 4 to C 22 alkyl (meth) acrylates .
  • the gelling agents that may be used in the compositions according to the invention may be organic or mineral, polymeric or molecular lipophilic gelling agents .
  • Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a Cio to C22 fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, such as for example the product sold under the name Bentone 38V ® by the company Elementis. Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 ⁇ m. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica.
  • hydrophobic silica is then obtained.
  • the hydrophobic groups may be: - trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane .
  • Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R812 ® by the company Degussa, and Cab-O-Sil TS- 530 ® by the company Cabot;
  • silica thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R972 ® and Aerosil R974 ® by the company Degussa, and Cab-O-Sil TS-610 ® and Cab-O-Sil TS- 720 ® by the company Cabot.
  • the hydrophobic fumed silica in particular has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
  • the polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6 ® , KSG16 ® and KSG18 ® from Shin-Etsu, Trefil E-505C ® and Trefil E-506C ® from Dow Corning, Gransil SR-CYC ® , SR DMF10 ® , SR-DC556 ® , SR 5CYC gel ® , SR DMF 10 gel ® and SR DC 556 gel ® from Grant Industries and SF 1204 ® and JK 113 ® from General Electric; ethyl cellulose, for instance the product sold under the name Ethocel ® by Dow Chemical; polycondensates of polyamide type resulting from the condensation
  • Block copolymers of "diblock”, “triblock” or “radial” type of the polystyrene/poly- isoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB ® by the company BASF, of the polystyrene/copoly (ethylene-propylene) type, such as the products sold under the name Kraton ® by the company Shell Chemical Co., or of the polystyrene/copoly (ethylene-butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel ® , for instance the mixture of butylene/ethylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
  • lipophilic gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl TL ® or Rheopearl KL ® by the company Chiba Flour.
  • composition according to the invention may comprise at least one film-forming polymer.
  • the film-forming polymer may be present in the composition according to the invention in a solids (or active material) content ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the total weight of the composition.
  • film- forming polymer is understood to mean a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous film that adheres to the keratin fibres, preferably a cohesive film and better still a film whose cohesion and mechanical properties are such that said film can be isolated and manipulated separately, for example when said film is made by casting on a non-stick surface, for instance a Teflon- coated or silicone-coated surface.
  • film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof.
  • free-radical film-forming polymer is understood to mean a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates) .
  • the film-forming polymers of free-radical type may be, in particular, vinyl polymers or copolymers, in particular acrylic polymers.
  • the vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers .
  • Monomers bearing an acid group which may be used are CC, ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid.
  • (Meth) acrylic acid and crotonic acid are preferably used, and more preferably (meth) acrylic acid.
  • esters of acid monomers are advantageously chosen from (meth) acrylic acid esters (also known as (meth) acrylates) , especially (meth) acrylates of an alkyl, in particular of a C1-C30 and preferably C1-C20 alkyl, (meth) acrylates of an aryl, in particular of a C ⁇ -Cio aryl, and (meth) acrylates of a hydroxyalkyl, in particular of a C2-C6 hydroxyalkyl.
  • acrylic acid esters also known as (meth) acrylates
  • alkyl in particular of a C1-C30 and preferably C1-C20 alkyl
  • aryl in particular of a C ⁇ -Cio aryl
  • a hydroxyalkyl in particular of a C2-C6 hydroxyalkyl.
  • alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate .
  • hydroxyalkyl (meth) acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate .
  • aryl (meth) acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
  • the (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .
  • the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • amides of the acid monomers that may be mentioned are (meth) acrylamides, and especially N- alkyl (meth) acrylamides, in particular of a C2-C12 alkyl.
  • N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .
  • the vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers.
  • these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned above.
  • vinyl esters examples include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate .
  • Styrene monomers that may be mentioned are styrene and ⁇ -methylstyrene .
  • film-forming polycondensates that may be mentioned are polyurethanes, polyesters, polyesteramides, polyamides, epoxyester resins and polyureas.
  • the polyurethanes may be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether- polyurethanes, polyureas and polyurea-polyurethanes, and mixtures thereof.
  • the polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.
  • the dicarboxylic acid may be aliphatic, alicyclic or aromatic.
  • examples of such acids that may be mentioned are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2, 2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1, 3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2, 5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2, 5-naphthalene- dicarboxylic acid or 2, 6-naphthalenedicarboxylic acid.
  • These dicarboxylic acid monomers may be used alone or as a combination of at least
  • the diol may be chosen from aliphatic, alicyclic and aromatic diols.
  • the diol used is preferably chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, cyclohexanedimethanol and 4-butanediol .
  • Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane .
  • the polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols.
  • Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para-phenylenediamine .
  • An amino alcohol that may be used is monoethanolamine .
  • the polyester may also comprise at least one monomer bearing at least one group -SO 3 M, with M representing a hydrogen atom, an ammonium ion NH 4 + or a metal ion such as, for example, an Na + , Li + , K + , Mg 2+ , Ca 2+ , Cu 2+ , Fe 2+ or Fe 3+ ion.
  • M representing a hydrogen atom, an ammonium ion NH 4 + or a metal ion such as, for example, an Na + , Li + , K + , Mg 2+ , Ca 2+ , Cu 2+ , Fe 2+ or Fe 3+ ion.
  • a difunctional aromatic monomer comprising such a group -SO 3 M may be used in particular .
  • the aromatic ring of the difunctional aromatic monomer also bearing a group -SO3M as described above may be chosen, for example, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulphonylbiphenyl and methylenebiphenyl rings.
  • difunctional aromatic monomers also bearing a group -SO3M mention may be made of: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2, 7-dicarboxylic acid.
  • copolymers preferably used are those based on isophthalate/sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulphoisophthalic acid.
  • the polymers of natural origin may be chosen from shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulose polymers, and mixtures thereof.
  • the film-forming polymer may be a polymer dissolved in the continuous oily phase (the film- forming polymer is thus said to be a liposoluble polymer) .
  • liposoluble polymers which may be mentioned are copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present) , an ⁇ -olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allyl or methaiIyI ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) .
  • copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allyl or methaiIyI type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate .
  • crosslinking agents may be either of the vinyl type or of the allyl or methaiIyI type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate .
  • copolymers examples include the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2, 2-dimethyloctanoate/vinyl laurate, allyl 2, 2-dimethylpentanoate/vinyl laurate, vinyl dimethyl- propionate/vinyl stearate, allyl dimethyl- propionate/vinyl stearate, vinyl propionat
  • liposoluble film-forming polymers examples include liposoluble copolymers, and in particular those resulting from the copolymer- ization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 10 to 20 carbon atoms.
  • Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, of polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, copolymers of polystearyl (meth) acrylate, of polyvinyl laurate and of polylauryl (meth) acrylate, it being possible for these poly (meth) acrylates to be crosslinked with the aid of ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.
  • the liposoluble copolymers defined above are known and are described in particular in application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.
  • liposoluble film-forming polymers which may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkyl celluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethyl cellulose and propyl cellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still C3 to C20 alkene.
  • polyalkylenes and in particular copolymers of C2-C20 alkenes such as polybutene, alkyl celluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethyl cellulose and propyl cellulose
  • VP vinylpyrrolidone
  • V vinylpyrrolidone
  • VP copolymers which may be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP) , VP/ethyl methacrylate/ methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate .
  • PVP polyvinylpyrrolidone
  • silicone resins which are generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers.
  • the nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ” characterizing a type of unit.
  • polymethylsilsesquioxane resins examples include those sold: by the company Wacker under the reference Resin MK, such as Belsil PMS MK; by the company Shin-Etsu under the reference KR- 220L.
  • Siloxysilicate resins that may be mentioned include trimethylsiloxysilicate (TMS) resins such as those sold under the reference SRlOOO by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of the trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning.
  • TMS trimethylsiloxysilicate
  • silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, for instance the pressure-sensitive adhesive copolymers sold by the company Dow Corning under the reference BIO-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073626.
  • the film-forming polymer may also be present in the composition in the form of particles dispersed in a non-aqueous solvent phase, which is generally known as a latex or pseudolatex.
  • a non-aqueous solvent phase which is generally known as a latex or pseudolatex.
  • the techniques for preparing these dispersions are well known to those skilled in the art .
  • non-aqueous film-forming polymer dispersions examples include acrylic dispersions in isododecane, for instance Mexomer PAP 1 from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055081.
  • composition according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer.
  • a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function .
  • composition according to the invention may also comprise at least one filler.
  • the fillers may be chosen from those that are well known to persons skilled in the art and commonly used in cosmetic compositions.
  • the fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, powders of polyamide, for instance Nylon ® sold under the trade name Orgasol ® by the company Atochem, poly- ⁇ -alanine powders and polyethylene powders, powders of tetrafluoroethylene polymers, for instance Teflon ® , lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel ® by the company Nobel Industrie, acrylic powders, such as those sold under the name Polytrap ® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls ® from Toshiba)
  • a compound that is capable of swelling on heating and especially heat- expandable particles such as non-expanded microspheres of vinylidene chloride/acrylonitrile/methyl methacrylate copolymer or of acrylonitrile homopolymer copolymer, for instance those sold, respectively, under the references Expancel ® 820 DU 40 and Expancel ® 007WU by the company Akzo Nobel.
  • the fillers may represent from 0.1 % to 25% and in particular from 1 % to 20% by weight relative to the total weight of the composition.
  • composition according to the invention may also comprise fibres which enable a lengthening effect.
  • fibre should be understood as meaning an object of length L and diameter D such that L is very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed.
  • the ratio L/D is chosen in the range from 3.5 to 2500, especially from 5 to 500 and in particular from 5 to 150.
  • the fibres that may be used in the composition of the invention may be mineral or organic fibres of synthetic or natural origin. They may be short or long, individual or organized, for example braided, and hollow or solid. They may have any shape, and may especially have a circular or polygonal (square, hexagonal or octagonal) cross section, depending on the intended specific application. In particular, their ends are blunt and/or polished to prevent injury.
  • the fibres have a length ranging from 1 ⁇ m to 10 mm, in particular from 0.1 mm to 5 mm and more particularly from 0.3 mm to 3.5 mm.
  • Their cross section may be within a circle of diameter ranging from 2 nm to 500 ⁇ m, in particular ranging from 100 nm to 100 ⁇ m and more particularly from 1 ⁇ m to 50 ⁇ m.
  • the weight or yarn count of the fibres is often given in denier or decitex, and represents the weight in grams per 9 km of yarn.
  • the fibres according to the invention may have a yarn count chosen in the range from 0.15 to 30 denier and especially from 0.18 to 18 denier.
  • the fibres that may be used in the composition of the invention may be chosen from rigid or non-rigid fibres, and may be of synthetic or natural, mineral or organic origin.
  • the fibres may or may not be surface- treated, may be coated or uncoated, and may be coloured or uncoloured.
  • rigid fibres such as polyamide (Nylon ) fibres or rigid fibres such as polyimideamide fibres, for instance those sold under the names Kermel and Kermel Tech by the company Rhodia or poly (p-phenyleneterephthalamide)
  • the fibres may be present in the composition according to the invention in a content ranging from
  • composition according to the invention may comprise an aqueous phase in the form of a dispersed phase.
  • This phase may be present in an amount between 0.1 and 10% by weight relative to the total weight of the composition.
  • the aqueous phase may be composed essentially of water; it may also comprise a mixture of water and of a solvent miscible with water (miscibility in water greater than 50% by weight at 25°C) such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, and dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes and mixtures thereof.
  • the composition according to the invention is anhydrous.
  • anhydrous is understood to mean that the composition comprises water in a content of less than 5% by weight of water, in particular less than 3%, especially less than 2%, and more particularly less than 1% by weight of water relative to the total weight of the composition.
  • composition of the invention is free of water.
  • composition when it comprises an aqueous phase, it may comprise at least one hydrophilic film-forming polymer .
  • the hydrophilic film-forming polymer may be a water-soluble polymer or may be in dispersion in an aqueous medium.
  • proteins such as proteins of plant origin, for instance wheat or soya bean protein
  • proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins
  • - cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and also quaternized derivatives of cellulose
  • acrylic polymers or copolymers such as polyacrylates or polymethacrylates
  • vinyl polymers such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, the copolymers of vinylpyrrolidone and of vinyl acetate, the copolymers of vinylpyrrolidone and of caprolactam, polyvinyl alcohol
  • the film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase, generally known under the name of latex or pseudolatex.
  • the techniques for preparing these dispersions are well known to a person skilled in the art .
  • aqueous dispersion of a film-forming polymer use may be made of the acrylic dispersions sold under the names Neocryl XK-90 ® , Neocryl A-1070 ® , Neocryl A-1090 ® , Neocryl BT-62 ® , Neocryl A-1079 ® and Neocryl A-523 ® by Avecia-Neoresins, Dow Latex 432 ® by Dow chemical, Daitosol 5000 AD ® or Daitosol 5000 SJ ® by Daito Kasey Kogyo; Syntran 5760 ® by Interpolymer, Allianz Opt ® by Rohm and Haas or else aqueous dispersions of polyurethane sold under the names Neorez R-981 ® and Neorez R-974 by Avecia-Neoresins, Avalure UR-405 , Avalure UR-410 ® , Avalure UR-425 ® , Avalure UR-450 ® , San
  • composition according to the invention may comprise at least one surfactant, especially chosen from amphoteric, anionic, cationic or nonionic surfactants, used alone or as a mixture.
  • the surfactants may be generally present in the composition in a proportion which may range, for example from 0.1 to 10% by weight, and preferably from 0.5 to 5% by weight.
  • an emulsifying surfactant suitably chosen in order to obtain a water- in-oil emulsion is generally used.
  • an emulsifying surfactant having, at 25°C, an HLB balance (hydrophilic-lipophilic balance) , within the meaning of Griffin, of less than or equal to 8 may be used.
  • surfactants can be selected from non- ionic, anionic, cationic or amphoteric surfactants.
  • the surfactants preferably used in the composition according to the invention are selected from: a) non-ionic surfactants with an HLB of less than 8 at 25°C, optionally in combination with one or more non-ionic surfactants with an HLB of greater than 8 at 25°C, such as mentioned below, such as:
  • sucrose stearates such as sucrose cocoate, sorbitan stearate and their mixtures, for example Arlatone 2121 ® , sold by the company ICI, or Span 65V, from the company Uniqema;
  • esters of fatty acids in particular C8-C24 and preferably C16-C22 fatty acids, and of a polyol, in particular of glycerol or of sorbitol, such as glyceryl stearate, for example sold under the name Tegin M by the company Goldschmidt, glyceryl laurate, such as the product sold under the name Imwitor 312 by the company
  • lecithins such as soybean lecithins (for instance Emulmetik 100 J from Cargill, or Biophilic H from Lucas Meyer) ;
  • - oxyethylenated and/or oxypropylenated ethers (which can comprise from 1 to 150 oxyethylenated and/or oxypropylenated groups) of fatty alcohols (in particular of a C8-C24 and preferably C12-C18 alcohol) , such as the oxyethylenated ether of stearyl alcohol comprising 2 oxyethylene units (CTFA name "Steareth- 2”), such as Brij 72, sold by the company Uniqema;
  • - monosaccharide esters and ethers such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols, for instance Montanov 68 from Seppic; - oxyethylenated and/or oxypropylenated glycerol ethers which may comprise from 1 to 150 oxyethylene and/or oxypropylene units;
  • - oxyethylenated and/or oxypropylenated ethers (which can comprise from 1 to 150 oxyethylene and/or oxypropylene units) of fatty alcohols, in particular Cs- C24 and preferably C12-C18 fatty alcohols, such as the oxyethylenated ether of stearyl alcohol comprising 20 oxyethylene units (CTFA name "Steareth-20”) , such as Brij 78 sold by the company Uniqema, the oxyethylenated ether of cetearyl alcohol comprising 30 oxyethylene units (CTFA name "Ceteareth-30”) and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols comprising 7 oxyethylene units (CTFA name "C12-15 Pareth-7”), such as that sold under the name Neodol 25-7 ® by Shell Chemicals;
  • - esters of a fatty acid in particular a C8-C24 and preferably C16-C22 fatty acid, and of polyethylene glycol (or PEG) (which can comprise from 1 to 150 oxyethylene units), such as PEG-50 stearate and PEG-40 monostearate, sold under the name Myrj 52P ® by the company Uniqema;
  • PEG polyethylene glycol
  • - esters of a fatty acid in particular a C8-C24 and preferably C16-C22 fatty acid
  • oxyethylenated and/or oxypropylenated glycerol ethers which can comprise from 1 to 150 oxyethylene and/or oxypropylene units
  • polyoxyethylenated glyceryl monostearate comprising 200 oxyethylene units sold under the name Simulsol 220 TM ® by the company SEPPIC
  • polyoxyethylenated glyceryl stearate comprising 30 oxyethylene units, such as the product Tagat S ® sold by the company Goldschmidt, polyoxyethylenated glyceryl oleate comprising 30 oxyethylene units, such as the product Tagat O sold by the company Goldschmidt, polyoxyethylenated glyceryl cocoate comprising 30 oxyethylene units, such as the product Varionic LI 13 sold by the company Sherex, polyoxyethylen
  • - esters of a fatty acid in particular a C8-C24 and preferably C16-C22 fatty acid, and of oxyethylenated and/or oxypropylenated sorbitol ethers (which can comprise from 1 to 150 oxyethylene and/or oxypropylene units) , such as the polysorbate 20 sold under the name
  • Tween 20 by the company Croda, such as the polysorbate 60 sold under the name Tween 60 ® by the company Uniqema;
  • - dimethicone copolyol such as that sold under the name Q2-5220 by the company Dow Corning
  • - dimethicone copolyol benzoate such as that sold under the name Finsolv SLB 101 ® and 201 ® by the company Fintex
  • the EO/PO polycondensates are more particularly copolymers composed of polyethylene glycol and polypropylene glycol blocks, such as, for example, polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates.
  • These triblock polycondensates have, for example, the following chemical structure:
  • the EO/PO polycondensates preferably have a weight-average molecular weight ranging from 1000 to 15 000 and better still ranging from 2000 to 13 000.
  • said EO/PO polycondensates have a cloud point, at 10 g/1 in distilled water, of greater than or equal to 20 0 C, preferably of greater than or equal to 60 0 C.
  • the cloud point is measured according to the ISO 1065 standard.
  • EO/PO polycondensate which can be used according to the invention, of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the Synperonic names, such as Synperonic PE/L44 ® and Synperonic PE/F127 ® , by the company ICI.
  • anionic surfactants such as: - salts of C16-C30 fatty acids, in particular amino salts such as triethanolamine stearate or 2- amino-2-methylpropane-l, 3-diol stearate; - salts of polyoxyethylenated fatty acids, in particular amino salts or alkali metal salts, and mixtures thereof;
  • phosphoric esters and salts thereof such as "DEA oleth-10 phosphate” (Crodafos N ION from the company Croda) or monopotassium monocetyl phosphate (Amphisol K from Givaudan or Arlatone MAP 160K from the company Uniqema) ;
  • sulphosuccinates such as “disodium PEG-5 citrate lauryl sulphosuccinate” and “disodium ricinoleamido MEA sulphosuccinate”;
  • alkyl ether sulphates such as sodium lauryl ether sulphate
  • acylglutamates such as "disodium hydrogenated tallow glutamate” (Amisoft HS-21 R sold by the company Ajinomoto) and sodium stearoyl glutamate
  • citrates such as glyceryl stearate citrate (Axol C 62 Pellets from Degussa) ;
  • proline derivatives such as sodium palmitoyl proline (Sepicalm VG from Seppic) , or the mixture of sodium palmitoyl sarcosinate, magnesium palmitoyl glutamate, palmitic acid and palmitoyl proline (Sepifeel One from Seppic) ;
  • lactylates such as sodium stearoyl lactylate (Akoline SL from Karlshamns AB) ;
  • - sarcosinates such as sodium palmitoyl sarcosinate (Nikkol sarcosinate PN) or the mixture of stearoyl sarcosine and myristoyl sarcosine 75/25 (Crodasin SM from Croda)
  • - sulphonates such as sodium Ci 4 -I 7 alkyl-sec- sulphonate (Hostapur SAS 60 from Clariant) ;
  • a cationic surfactant such as sodium cocoyl glycinate (Amilite GCS-12 from Ajinomoto).
  • a cationic surfactant mention may in particular be made of:
  • - alkylimidazolidiniums such as isostearylethylimidonium ethosulphate
  • - ammonium salts such as (C12-30 alkyl) tri (C1-4 alkyl) ammonium halides, for instance N, N, N-trimethyl-1- docosanaminium chloride (or behentrimonium chloride) .
  • compositions according to the invention may also contain one or more amphoteric surfactants, for instance N-acylamino acids, such as
  • N-alkylaminoacetates and disodium cocoamphodiacetate and amine oxides, such as stearamine oxide, or else silicone surfactants, for instance dimethicone copolyol phosphates, such as that sold under the name Pecosil PS 100 ® by the company Phoenix Chemical.
  • composition according to the invention may comprise a water-soluble gelling agent.
  • the water-soluble gelling agents that can be used in the compositions according to the invention may be selected from: homo- or copolymers of acrylic or methacrylic acids or salts thereof and esters thereof, in particular the products sold under the names Versicol
  • AMPS polyacrylamidomethylpropanesulphonic acid partially neutralized with aqueous ammonia and highly crosslinked
  • Clariant polyacrylamidomethylpropanesulphonic acid partially neutralized with aqueous ammonia and highly crosslinked
  • AMPS/acrylamide copolymers of Sepigel ® or Simulgel type sold by the company SEPPIC;
  • polyoxyethylenated alkyl methacrylate/AMPS copolymers proteins, such as proteins of plant origin for instance wheat or soybean protein; proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins; cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and also quaternized derivatives of cellulose; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and of maleic anhydride, the copolymer of vinyl acetate and of crotonic acid, the copolymers of vinylpyrrolidone and of vinyl acetate, the copolymers of vinylpyrrolidone and of caprolactam, polyvinyl
  • Some of these water-soluble gelling agents may also act as film-forming polymers.
  • the water-soluble gelling polymer may be present in the composition according to the invention at a solids content ranging from 0.01% to 5% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition.
  • compositions according to the invention may also contain at least one agent customarily used in cosmetics, chosen, for example, from reducing agents, softeners, anti-foaming agents, moisturizers, UV- screening agents, mineral colloids, fragrances, proteins or vitamins.
  • agent customarily used in cosmetics chosen, for example, from reducing agents, softeners, anti-foaming agents, moisturizers, UV- screening agents, mineral colloids, fragrances, proteins or vitamins.
  • the above additives are, in general, present in an amount between, for each of them, 0.01 and 20% by weight relative to the weight of the composition.
  • the viscosity of the compositions is measured according to the following protocol :
  • the viscosity of the composition is measured at 25°C using a Rheomat 180 (Lamy) equipped with an MS-Rl, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen as function of the consistency of the composition, which rotates at a rotational speed of 200 rpm. The measurement is taken after rotating for 10 min. The viscosity measurements are carried out a maximum of 1 week after manufacture.
  • phase A is heated at 100 0 C with stirring in a Rayneri agitator; phase C is introduced into phase A until a good dispersion is obtained; the bentone gel B is prepared and placed in a waterbath (60-70 0 C); - B is introduced into the A+C mixture, homogenized for 5 minutes at high temperature, then extruded through a three-roll mill (3 passes) .
  • a composition is obtained that has a shiny homogeneous texture with good viscosity (95 poise) .
  • This comparative composition is prepared according to the same protocol as that of Example 1.
  • a composition is obtained having a shiny homogeneous texture with good viscosity (24 poise) .
  • composition 1 has a better dry rubbing resistance than the comparative composition, for an equivalent water and sebum resistance.
  • compositions are produced:
  • This suspension is heated to 140 0 C and is stirred at this temperature for 6 hours.
  • the reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm “1 ) has completely disappeared.
  • the mixture is then brought back down to 30 0 C, and 1 litre of heptane is added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 3 with a solids content of 20%.
  • the polymer is characterized by GPC
  • Preparation of the polymer 4 Supramolecular polymer obtained from GI3000 as compound A and from a graft of formula B in which L denotes a 4, 4' -dicyclohexylmethane radical 89 g of GI3000 polymer sold by Nisso, in the presence of 22 mg of catalyst, dibutyltin dilaurate, are heated at 80 0 C, under vacuum for 2 hours. The temperature of the mixture is decreased to 20 0 C, under argon. 11.6 of 4, 4' -dicyclohexylmethane (5124-30-1) are added, followed by the addition of 60 ml of isododecane.
  • the mixture is stirred for 16 hours at 20 0 C, under a controlled atmosphere, then is heated to 120°C, followed by the addition of 40 ml of propylene carbonate. 6.64 g of 6-methylisocytosine are added, resulting in a white homogeneous suspension. This suspension is heated to 140 0 C and stirred at this temperature for 8 hours. The reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm "1 ) has completely disappeared. The mixture is then brought back down to 30 0 C, and 250 ml of isododecane, and also 500 ml of heptane, are added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 4 with a solids content of 22%.
  • polymer 5 Supramolecular polymer obtained from GI2000 as compound A and from a graft of formula B in which L denotes a 4, 4' -dicyclohexylmethane radical
  • compositions 2 to 5 The protocol for preparing compositions 2 to 5 is identical to that for the composition of Example 1.

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Abstract

One subject of the present invention is a method for making up or caring for eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of at least one layer of a cosmetic composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer, and at least one colorant.

Description

METHOD FOR NlAKING UP OR CARING FOR EYELASHES OR EYEBROWS USING A POLYALKENE-BASED SUPRAMOLECULAR
POLYMER
One subject of the present invention is a method for coating eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of a composition comprising at least one polyalkene-based supramolecular polymer. The composition according to the invention may be in the form of a mascara.
The term "mascara" is understood to mean a composition intended to be applied to the eyelashes: it may be an eyelash makeup composition, an eyelash makeup base, a composition to be applied over a mascara, also known as a topcoat, or else a cosmetic composition for treating eyelashes. The mascara is more particularly intended for human eyelashes, but also for false eyelashes . Generally, eyelash makeup compositions are composed of at least one wax or of a mixture of waxes dispersed in an aqueous liquid phase or in an organic solvent phase.
Anhydrous mascaras or mascaras with a low content of water and/or water-soluble solvents, which are known as "waterproof mascaras", formulated in the form of a dispersion of waxes in non-aqueous solvents, and which have good resistance to water and/or to sebum, are known in particular. However, the makeup film obtained after application of these compositions is not sufficiently water-resistant, when bathing or showering for example, to tears or to sweat or else to sebum. The mascara then has a tendency to run - appearance of rings under the eyes - or to disintegrate over time: grains are deposited and unattractive marks appear around the eyes .
In order to improve the hold of mascaras known as waterproof mascaras, it has been proposed to incorporate a liposoluble film-forming polymer or a polymer in the form of a dispersion of particles in an organic solvent phase, at a higher content of film- forming polymer. However, the presence of a high content of film- forming polymer is reflected by a pasty texture of the composition, which forms, after being deposited on the keratin fibres, a granular, non-uniform film that lacks slipperiness on application. The objective of the present invention is therefore to provide a composition for making up or coating keratin fibres, especially eyelashes or eyebrows, which has good water resistance and/or sebum resistance properties, and also good rubbing resistance properties.
Unexpectedly, the inventors have discovered that the use of a polyalkene-based supramolecular polymer, formulated in a continuous oily phase in the presence of a colorant, makes it possible to obtain a composition having a good water resistance and/or sebum resistance, and also a very good resistance to rubbing.
The expression "water resistance" is understood according to the present application to mean the in vitro water resistance evaluated according to the following protocol:
The composition is applied to 3 samples of straight Caucasian hair having 30 knots (60 eyelashes 1 cm in length) with a fringe length of 2 cm, by making 3 x 10 passes at 2 minute intervals with uptake of product between each series of 10 passes. Each sample is then dried at ambient temperature for a drying time of one hour.
The 3 made-up samples are immersed in a container containing water at 200C for a given time (1 hour, 24 hours or 1 week) . The 3 samples are then wiped back and forth 5 times on a square cloth of the Wypall L40 type from Kimberly Clark.
The presence of marks deposited by the sample is then evaluated. A score between 0 and 9 is attributed to the resulting marks; 0 being the score obtained when no mark is deposited by the sample, and 9 the score obtained when a large number of marks are deposited. The expression "sebum resistance" is understood according to the present application to mean the in vitro sebum resistance evaluated according to the same measurement protocol as for the water resistance described above, except that the 3 made-up samples are immersed in a container containing squalene (the squalene is present at 18% in the composition of sebum), instead of water.
The expression "rubbing resistance" is understood according to the present application to mean the in vitro rubbing resistance evaluated according to the following protocol:
The composition is applied to 3 samples of straight Caucasian hair having 30 knots (60 eyelashes 1 cm in length) with a fringe length of 2 cm, by making 3 x 10 passes at 2 minute intervals with uptake of product between each series of 10 passes. Each sample is then dried at ambient temperature for a drying time of one hour.
The made-up sample is then positioned perpendicularly above a sheet of paper and rubbed using a hard brush of the Keracils® type (30 passes) .
The quantity of grains thus formed, recovered on the sheet of paper, is evaluated.
A score between 0 and 6 is attributed to this quantity of grains; 0 being the score for which no grain is recovered on the sheet of paper and 6 the score for which a very large quantity of grains is recovered.
One subject of the present invention is therefore a method for making up or caring for eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of at least one layer of a cosmetic composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer, and at least one colorant.
Using this process, a deposit is obtained on the eyelashes or the eyebrows that has a good resistance to water and sebum, and also a very good resistance to rubbing.
Another subject of the present invention is an assembly for making up or caring for eyelashes or eyebrows comprising:
- at least one composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer and at least one colorant,
- and at least one applicator of the composition, said applicator comprising means that make it possible to smooth and/or separate the eyelashes or eyebrows, especially in the form of teeth, bristles or other reliefs .
The compositions according to the invention are thus used for making up and/or caring for keratin fibres, in particular eyelashes, for example as mascaras.
The process for making up or coating eyelashes or eyebrows according to the invention consists, in particular, in applying an effective amount of a composition as described above, to the eyelashes or the eyebrows.
APPLICATOR
The applicator included in the makeup or care assembly according to the present invention comprises means that make it possible to smooth and/or separate the eyelashes or eyebrows, especially in the form of teeth, bristles or other reliefs.
The application means, or applicator, may be used to apply the composition to the eyelashes or the eyebrows.
The applicator may also be used for finishing the making-up process in one region of the eyelashes or of the eyebrows made up or loaded with product using another applicator. The composition according to the invention may be withdrawn from a container by immersing the application member into this container.
The application part may comprise, optionally, a member for closing a container that contains the composition according to the invention.
The process of applying the composition according to the invention to the eyelashes or the eyebrows may also comprise the following steps: - forming a deposit of the cosmetic composition on the eyelashes or the eyebrows; and
- leaving the deposit on the eyelashes or the eyebrows, the deposit possibly drying.
The application member is arranged in order to apply a product to the eyelashes or the eyebrows, and may comprise, for example, a brush or a comb.
The brush may comprise a twisted core and bristles held between the turns of the core, or may be produced in yet another way. The comb is, for example, produced from a single part by moulding of a plastic.
The application member may be magnetic.
In certain exemplary embodiments, the application member is mounted at the end of a wand, which wand may be flexible, which may contribute to improving the comfort during application.
The applicator may or may not comprise a reservoir that contains the composition.
When the applicator does not comprise a reservoir that contains the composition, the composition is, for example, contained in a container and the application member is, for example, loaded with composition by being introduced at least partially into this container. The container may or may not comprise a wiping member.
The reservoir may be fastened in a removable or unremovable manner to the applicator. When the reservoir is permanently fastened to the applicator, in order to supply the latter with product, the wall of the reservoir is used, for example, for gripping the applicator .
The assembly according to the invention may also comprise at least two different application members which may be selectively mounted on the applicator.
The assembly will be better understood on reading the detailed description which follows of non-limiting exemplary embodiments of this assembly, and on examining the appended drawing, in which: - Figure 1 schematically represents, with a partial longitudinal cross section, a packaging and application device according to one exemplary embodiment of the invention.
Figure 1, to which reference is now made, illustrates a packaging and application device 1 according to one embodiment of the invention. According to this embodiment, the packaging and application assembly comprises an applicator 2 and a container 3 that contains a reserve of a makeup product P, in this particular case a composition according to the invention, for example mascara.
The container 3 is conventional in the example illustrated and comprises a body 5 equipped with an externally threaded neck 6. A wiping member 7 is fastened inside the neck 6.
The applicator 2 comprises an application member 10 constituted, in the example in question, of a mascara brush. The application member 10 is mounted at the end of a wand 11, the other end of which is attached to a case 13 comprising an end part arranged so as to screw onto the neck 6 and thus seal the container 3 in a leaktight manner.
In this figure, the brush has been represented very schematically in order to clearly illustrate the fact that the invention is not limited to one particular application member.
The brush 10 comprises, for example, bristles, the ends of which are arranged in helical layers.
The wand may be produced with a constant or variable cross section.
Preferably, the wand 11 is flexible, a person skilled in the art being able to choose the dimensions of the wand as a function, for example, of the nature of the application member, of the product and of the treatment to be carried out.
When the application member is configured in the form of a comb, the latter may be in accordance with what is described, in particular, in the publications US 2003-0089379-A1, US 6 655 390, US 6 814 084, US 6 675 814, US 6 581 610, US 6 546 937, US 6 539 950, US 6 412 496 or US 6 343 607, this list not being limiting.
The invention is not limited to one particular application member and the latter may especially be equipped with a means that makes it possible to heat the product and/or the eyelashes and/or the eyebrows during the application.
Various modifications may be made to the exemplary embodiments which have just been described without departing from the scope of the present invention.
The application members may be of any type, especially with capillary slits or the like.
The application members may be made in various ways, especially by moulding, injection-moulding, staple fastening or twisting.
The application members may be intended for single use, where appropriate.
The application members may be fastened by any means to the application part, especially by bonding, welding, punching, click-fastening, screwing, with magnets, by friction, by attachment of Velcro® type, by gripping between jaws or the arms of pincers.
The application member may be driven in rotation, where appropriate, for example as described in patents US 4 937 326, US 4 922 934 and US 6 565 276.
The application of the product may be carried out, especially when the invention is implemented in order to apply a product to the eyelashes or the eyebrows, after having heated the product, for example by placing it in a microwave oven.
The composition according to the invention may be packaged in a container delimiting at least one compartment which comprises said composition, said container being sealed by a sealing member.
The container may be associated with the applicator .
The applicator may be attached to the container, as described, for example, in patent FR 2 761 959. Advantageously, the applicator is attached to a wand which, itself, is attached to the sealing member.
The sealing member may be coupled to the container by screwing. Alternatively, the coupling between the sealing member and the container takes place other than by screwing, especially via a bayonet mechanism, by click-fastening or by clamping. The term "click- fastening" is understood to mean, in particular, any system that involves surmounting a rim or bead of material by elastic deformation of a portion, especially of the sealing member, then by returning to the elastically unstressed position of said portion after the rim or bead has been surmounted.
The container may be at least partly made of a thermoplastic. As examples of thermoplastics, mention may be made of polypropylene or polyethylene.
Alternatively, the container is made from a non- thermoplastic material, especially from glass or from metal or an alloy. The container is preferably equipped with a wringer placed in the vicinity of the opening of the container. Such a wringer makes it possible to wipe the applicator and optionally the wand to which it may be attached. Such a wringer is described, for example, in patent FR 2 792 618.
Polyalkene-based supramolecular polymers
Within the meaning of the present invention, the expression "polyalkene-based supramolecular polymer" is understood to mean a polymer comprising, in its structure, at least one polyalkene part and at least one part comprising at least one group capable of forming at least 3 H bonds, preferably 4 H bonds. The polyalkene is preferably chosen from poly (ethylene/butylene) s, polybutadienes and polyisoprenes .
The polyalkene-based supramolecular polymers according to the invention may be derived from the condensation of at least one polyalkene polymer functionalized by at least one reactive group, with at least one graft functionalized by at least one reactive group capable of reacting with the reactive group or groups of the functionalized polyalkene polymer, said graft bearing at least one group capable of forming at least 3 H bonds, preferably at least 4 H bonds.
Preferably, the functionalized polyalkene polymer is of formula A:
HX-R-X'H XH and X' H being reactive groups, with X and X', which are identical or different, chosen from O, S, NH, or NRa, Ra representing a Ci-Cε alkyl group; preferably, X and/or X' denote O; more preferably still, X and X' denote O; R represents a homopolymer or a copolymer derived from one or more monounsaturated or polyunsaturated C2-C10, and preferably C2-C4, alkenes; R preferably represents a poly (ethylene/butylene) , a polybutadiene or a polyisoprene . Thus, preferably, the functionalized polyalkene polymer is chosen from hydroxyl-terminated poly (ethylene/butylene) s, hydroxyl-terminated polybutadienes and hydroxyl-terminated polyisoprenes.
The poly (ethylene/butylene) s are copolymers of 1-butene and ethylene. They can be represented schematically by the sequence of units of structures:
[-CH2-CH2-] and [-CH2CH(CH2-CH3)]. The polybutadienes may be poly (1, 4-butadiene) s or poly (1, 2-butadiene) s, which may be respectively represented schematically by the sequences of following units :
[-CH2-CH=CH-CH2-] poly (1, 4-butadiene) s [-CH2-CH(CH=CH2) -] poly (1,2-butadiene) s. Preferably, for the polybutadienes, they are poly (1, 2-butadiene) s .
The functionalization preferably takes place at the end of the chains. Reference is then made to telechelic polymers. The functionalization groups may be attached to the polyalkene polymer via linkers, preferably linear or branched Ci-C4 alkylene groups.
These polyalkenes may be hydrogenated in order to avoid risks of crosslinking.
They may comprise, in their structure, other units resulting from other monomers. As comonomers, mention may in particular be made of styrene.
Polydienes, preferably hydrogenated polydienes having hydroxyl end groups and polyolefins having hydroxyl end groups are preferred polymeric backbones according to the invention.
These hydroxyl-terminated polydienes are defined, for example, in patent FR 2 782 723 by Elf Atochem. They are chosen from the group comprising homopolymers and copolymers of polybutadiene, of polyisoprene and of poly (1, 3-pentadiene) . They are oligomers having a number-average molecular weight of less than 7000, and preferably of 1000 to 5000, having a functionality of hydroxyl end groups of 1.8 to 3, and preferably in the vicinity of 2. Mention will in particular be made of the hydroxylated polybutadienes sold by Elf Atochem under the trade marks POLY BD R-45HT and POLY BD R-20 LM, which will preferably be used in hydrogenated form. Mention may also be made of the di-OH hydrogenated poly (1,2-butadiene) s, such as GI3000 of Mn = 2600-3200 and GI2000 of Mn = 1800-2200 sold by Nisso.
Use may also be made of polyolefins, which are homopolymers or copolymers, having CC, CO-hydroxyl end groups, such as: • polyisobutylene oligomers having CC, Cϋ-hydroxyl end groups; and
• the copolymers sold by Mitsubishi under the trade mark POLYTAIL with, in particular, those corresponding to the formula:
HO CH 2 U CHzCH-hOH
C2H5
The supramolecular polymers of the present invention have, in their structure, at least one graft bearing at least one group capable of forming at least 3 H bonds, preferably at least 4 H bonds.
These groups capable of forming at least 3 H bonds can comprise, for example, at least 3 functional groups, preferably at least 4 functional groups, chosen from:
\ \ \ \ \
C=O C=S P=O C=NH S=O
/ / / / /
—C≡CH -SH -OH XC=N- —C≡N -NH2
/
-NH —C—O- —C- —C-
These functional groups can be categorized into two categories: - functional groups which donate H bonds, such as the groups :
C=CH -SH -OH C=NH -NH -NH2
- and functional groups which accept H bonds, such as the groups : \ \ \ \
C=O C=S C=N- S=O
/ / /
— C≡N r o- —C- —c-
The groups capable of forming at least 3 H bonds form a base structural element comprising at least 3 functional groups, preferably at least 4 functional groups and more preferably 4 functional groups capable of establishing H bonds. The base structural elements capable of establishing 3 or 4 H bonds can be represented schematically in the following way:
Figure imgf000013_0001
(X4 or Y4Y
where X1 (i = natural number) is a functional group which accepts H bonds and Y1 is a functional group which donates H bonds.
Thus, each structural element must be able to establish H bonds with one or more partner structural elements which are identical (that is to say, self- complementary) or different, so that each pairing of two partner structural elements takes place by formation of at least three H bonds, preferably at least four H bonds and more preferably 4 H bonds.
A proton acceptor X will be paired with a proton donor Y. Several possibilities are offered, for example pairing of: XXXX with YYYY; XXXY with YYYX; XXYX with YYXY; XYYX with YXXY; XXYY with YYXX, which may or may not be self- complementary;
XYXY with YXYX, which may or may not be self- complementary.
Preferably, the groups can establish 4 H bonds with an identical (or self-complementary) partner group, among which 2 donor bonds (for example NH) and 2 acceptor bonds (for example CO and -C=N-) .
Preferably, the groups capable of forming at least 3 H bonds comprise rings having 5 or 6 atoms (aromatic rings or unsaturated heterocycles) , very often constituted of C and/or N atoms and with conjugated double bonds in order to stabilize and control the H interactions .
More preferably, the groups capable of forming at least 3 H bonds are involved in rings having 6 atoms comprising C and/or N atoms and with conjugated double bonds in order to stabilize and control the H interactions .
According to one particular embodiment of the invention, the groups capable of forming 3 or 4 H bonds are chosen from the following families, it being understood that all the tautomeric forms are included: - (i) aminopyrimidones of formula:
Figure imgf000014_0001
- (ii) ureidopyrimidones of formula:
Figure imgf000015_0001
- (iii) acylaminopyridines and in particular:
- monoacylaminopyridines with the structure:
Figure imgf000015_0002
di (acylamino) pyridines and more particularly 2,6- di (acylamino) pyridines with the structure:
Figure imgf000015_0003
- (iv) aminopyrimidines and in particular:
- the aminopyrimidine compounds :
Figure imgf000015_0004
- the diaminopyrimidine compounds with the structures:
Figure imgf000015_0005
- the triaminopyrimidine compounds; - (v) ureidotriazines and in particular mono-, di- and triureidotriazines, especially the ureidoaminotriazines with the structure:
Figure imgf000016_0001
(vi) (acylamino) triazines and in particular mono-, di- and triacylaminotriazines, which optionally comprise amino (mono-, di- or triamino) , especially: - di (acylamino) triazines with the structure:
Figure imgf000016_0002
(acylamino) aminotriazines, (mono- or diacylamino and mono- or diamino) and in particular the compounds with the structure:
Figure imgf000016_0003
- acylaminotriazines with the structure
Figure imgf000016_0004
- triacylaminotriazines;
- (vii) aminotriazines and in particular:
- monoaminotriazines; - 2 , 6-diamino- s -triaz ines with the structure :
NHR1 N , N Vv / N H R1
R2
- triamino-s-triazine compounds with the structure:
NHR1^ N .NHR1
N^N
NHR1
- (viii) acylaminotriazoles with the structure:
Figure imgf000017_0001
- (ix) compounds of the family of urazolylbenzoic acid with the structure:
Figure imgf000017_0002
(x) phthalhydrazides with the structure:
Figure imgf000018_0001
- (xi) uracils with the structure
Figure imgf000018_0002
- (xii) thymines with the structure
Figure imgf000018_0003
- (xiii) succinimides with the structure
Figure imgf000018_0004
- (xiv) glutarimides with the structure
Figure imgf000018_0005
(xv) compounds of the family of cyanuric acid with the structure:
Figure imgf000019_0001
(xvi) maleimides:
Figure imgf000019_0002
- (xvii) compounds of the family of barbituric acid, with the structure:
Figure imgf000019_0003
- (xviii) compounds with the structures
Figure imgf000019_0004
and
- (xix) compounds of the family of trimellitic acid, of formula:
Figure imgf000020_0001
(xx) ureidopyridines, in particular mono- or diureidopyridines, especially those of formulae:
Figure imgf000020_0002
- (xxi) carbamoylpyridines, of formulae:
Figure imgf000020_0003
- (xxii) adenines of formula:
Figure imgf000021_0001
- (xxiii) guanines of formula
Figure imgf000021_0002
- (xxiv) cytidines of formula:
Figure imgf000021_0003
In all these formulae, the meanings of the radicals are as follows:
- (a) the Ri radicals, which are identical or different, represent a single bond, a hydrogen atom, a halogen atom and/or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-Cδooo carbon-based (in particular alkyl) group which can comprise one or more heteroatoms, such as O, S, N, P, Cl, Br or F; or a combination of these meanings.
The Ri radical can in particular be a C4-C12 cycloalkyl group, a linear or branched C1-C30 alkyl group or a C4-C12 aryl group which are optionally substituted by an amino, ester and/or hydroxyl functional group.
The Ri radical may also be a C4H9, phenyl, 1,4- nitrophenyl, 1, 2-ethylene, 1, 6-hexylene, 1, 4-butylene, 1, 6- (2, 4, 4-trimethylhexylene) , 1,4- (4-methylpentylene) , 1, 5- (5-methylhexylene) , 1, 6- ( 6-methylheptylene) , 1,5- (2,2, 5-trimethylhexylene) , 1,7- (3, 7-dimethyloctylene) , -isophorone-, 4, 4 ' -methylenebiscyclohexylene, tolylene, 2-methyl-l , 3-phenylene, 4-methyl-1, 3-phenylene or 4,4- biphenylenemethylene group; and preferably an -isophorone-, - (CH2) 2-, ~ (CH2) β~ , -CH2CH(CH3) -CH2-C (CHs)2-CH2-CH2-, 4 , 4 ' -methylenebiscyclohexylene or 2-methyl-l , 3-phenylene group.
More preferably still, Ri is a single bond.
(b) the R2 radicals, which are identical or different within one and the same formula, represent a single bond, a hydrogen atom, a halogen atom (-Br, -Cl or -F) , an -OH radical, an -N(R)2 radical (with R being H or a linear or branched Ci-Ci2, preferably Ci-C4, alkyl radical and better still a methyl or ethyl radical) or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-Cδooo hydrocarbon-based group which can comprise one or more heteroatoms, such as O, S, N, P or F; or a combination of these meanings.
The R2 radicals can in particular be H, CN, NH2 or else:
- a C1-C30 alkyl group;
- a C4-Ci2 cycloalkyl group;
- a C4-Ci2 aryl group;
- a (C4-Ci2) aryl (C1-C30) alkyl group; - a Ci-C4 alkoxy group; an arylalkoxy group, in particular an aryl (Ci-C4) alkoxy group;
- a C4-Ci2 heterocycle;
- a thioalkoxy group; - a sulphoxy group; or their mixtures, these groups optionally being substituted by an amino, ester and/or hydroxyl functional group.
Preferably, R2 represents H, CH3, Ci3H27, C7Hi5 or phenyl.
(c) the R3 radicals, which are identical or different within one and the same formula, represent a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-Cδooo hydrocarbon-based group which can comprise one or more heteroatoms, such as 0, S, N, P or F; or a combination of these meanings.
The R3 radical can in particular be a C4-C12 cycloalkyl group, a linear or branched C1-C30 alkyl group or a C4-C12 aryl group; optionally substituted by an amino, ester and/or hydroxyl functional group.
Preferably, R3 represents a methyl radical. In all these formulae, it is clearly understood that at least one, in particular one or two, of the Ri and/or R2 groups is a single bond constituting the point of attachment of the group capable of forming at least 3 H bonds on the residue of the graft. Preferably, said point of attachment is borne by Ri and/or R2 and preferably it is borne by Ri.
The groups capable of forming at least 3 H bonds may be chosen in particular from:
(a) groups capable of forming at least 3 complementary and identical, that is to say self-complementary, H bonds, in particular: aminopyrimidones or ureidopyrimidones,
- compounds of the family of trimellitic acid or of urazolylbenzoic acid, - acylaminopyridines, ureidopyridines or carbamoylpyridines,
- acylaminotriazines, ureidotriazines, in particular ureidoaminotriazines, or diaminotriazines,
- acylaminotriazoles, - phthalhydrazides,
- compounds of formulae:
Figure imgf000023_0001
and in which Ri is a hydrogen atom or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic monovalent Ci-Cδooo hydrocarbon-based group which can comprise one or more heteroatoms, such as O, S, N, P or F,
(b) groups capable of forming at least 3 complementary but different H bonds, in particular: adenine complementary to guanine,
- cytidine complementary to thymine, - triamino-s-triazine complementary to uracil or to succinimide or to glutarimide or to cyanuric acid or to thymine or to maleimide or to (di) aminopyrimidine or to barbituric acid,
(acylamino) amino-s-triazine complementary to uracil or to succinimide or to glutarimide or to cyanuric acid or to thymine or to maleimide or to (di) aminopyrimidine or to barbituric acid.
Preferably, the groups capable of forming at least
3 H bonds are chosen from the groups capable of establishing at least three H bonds with themselves
(self-complementary groups) , in particular at least four H bonds with themselves. Mention may in particular be made, among these groups, of:
- ureidopyrimidones ; - ureidopyridines or carbamoylpyridines; acylamino-s-triazines, in particular (acyl) diamino-s- triazines;
- ureidotriazines;
- phthalhydrazides; - compounds of formulae:
Figure imgf000024_0001
in which the Ri, R2 and R3 radicals have the meanings given above, in particular the preferred meanings given .
Better still, mention may be made, as preferred examples of groups capable of forming at least 3 H bonds, of the groups derived from ureidopyrimidones, in particular from 2-ureidopyrimidone or from 6-methyl-2- ureidopyrimidone .
The residue of the graft is constituted of a linker L bearing at least one reactive group capable of reacting with the functionalized polyalkene group or groups .
This reactive group may be, for example, a carboxy group or an isocyanate group.
Preferably, it is an -N=C=O or -N=C=S group, and more preferably still an -N=C=O (isocyanate) group.
Preferably, the linker L is a phenylene; 1,4- nitrophenyl; 1, 2-ethylene; 1, 6-hexylene; 1, 4-butylene; 1, 6- (2, 4, 4-trimethylhexylene) ; 1,4- (4-methylpentylene) ; 1, 5- (5-methylhexylene) ; 1, 6- ( 6-methylheptylene) ; 1,5- (2, 2, 5-trimethylhexylene) ; 1, 7- (3, 7-dimethyloctylene; -isophorone-; 4, 4 ' -methylenebiscyclohexylene; tolylene; 2-methyl-l , 3-phenylene; 4-methyl-l, 3-phenylene or 4,4- biphenylenemethylene group, and preferably an -isophorone-; - (CH2) 2-; - (CH2) 6-; -CH2CH (CH3) -CH2-C (CH3) 2- CH2-CH2-; 4 , 4 ' -methylenebiscyclohexylene or 2-methyl- 1, 3-phenylene group.
In one particularly preferred version of the invention, the grafts are of formula (B) :
Figure imgf000025_0001
L having the same meaning as above.
More preferably still, the supramolecular polymer of the invention is of formula C:
Figure imgf000026_0001
R, X, X' and L having the meanings indicated previously. Preferably, in the formula C, X and X' denote an oxygen atom.
The polyalkene-based supramolecular polymer or polymers may be present in the composition at a content ranging from 0.1% to 40% by weight, preferably ranging from 0.1% to 30% by weight, more preferably ranging from 0.5% to 20% by weight, and more preferably still ranging from 1% to 15% by weight relative to the total weight of the composition.
Method of obtaining polymers
The polyalkene-based supramolecular polymer or polymers of the invention may also be obtained from a polymer (Al) comprising a polyalkene part, said polymer being functionalized by at least one reactive group (Bl), by condensation with at least one molecule (A3) comprising at least one reactive group (B2), said molecule being such that, after reaction of the (Bl) and (B2) groups, there is formation of a species capable of forming at least 3 H bonds, preferably at least 4 H bonds.
Preferably, these species have the structures (i) to (xxiv) as defined previously, with Ri denoting a single bond.
The polymer (Al) may especially result from the action, on a polyalkene polymer of formula A as defined above, of compounds (A2) comprising two reactive groups (B' 2) capable of reacting with the functionalized groups of the polyalkene.
These reactive groups may be, for example, carboxy groups or isocyanate groups. Preferably, they are -N=C=O or -N=C=S groups, and more preferably still -N=C=O (isocyanate) groups.
Preferably, the B2 groups are identical to the B' 2 groups .
Preferably, the compounds (A2) have the following structure (C ) :
B' 2-1/ -B' 2 (C) the linker L' having the same meanings as L defined previously.
In one particularly preferred version of the invention, the polymers Al are of formula (Cl) :
CON L NCO X —R X' CON L NCO
(C1) in which L, X, X' and R have the same meanings as before .
Preferably, the molecule (A3) is 6- methylisocytosine of formula:
Figure imgf000027_0001
In practice, the supramolecular polymer according to the invention can be prepared by the processes normally employed by a person skilled in the art, in order to form a urethane bond between the free OH functional groups of a polyalkene and the isocyanate functional groups borne by the joining group.
By way of illustration, a general preparation process comprises:
- making sure that the polymer to be functionalized does not comprise residual water;
- heating the polymer comprising at least two reactive functional groups, especially OH, to a temperature which can be between 60° C and 140 °C. The hydroxyl number of the polymer could act as reference in order to measure the state of progression of the reaction; directly adding the joining group bearing the reactive functional groups, in particular isocyanate functional groups;
- stirring the mixture, under a controlled atmosphere, at a temperature of the order of 90-130 °C, for 1 to 24 hours; monitoring, by infrared spectroscopy, the disappearance of the band characteristic of the isocyanates (between 2500 and 2800 cm"1) , so as to halt the reaction at the complete disappearance of the peak, and then allowing the final product to return to ambient temperature;
- the reaction could also be monitored by quantitative determinations of the hydroxyl functional groups; - it could also be possible to add ethanol in order to make sure that the residual isocyanate functional groups have completely disappeared;
- the mixture could be filtered if necessary.
The reaction can be carried out in the presence of a solvent, in particular methyltetrahydrofuran, tetrahydrofuran, toluene, butyl acetate or else propylene carbonate.
It is also possible to add a catalyst conventional for the formation of the urethane bond. Mention may be made, as example, of dibutyltin dilaurate.
At the end, the compound can be washed and dried, indeed even purified, according to the general knowledge of a person skilled in the art.
According to the 2nd method of preparation, the reaction can comprise the following stages:
(i) functionalization of the predried polyhydroxylated polyalkene polymer P, by a diisocyanate according to the reaction scheme:
OH-P-OH (1 eq.) + NCO-X-NCO (1 eq.) → OCN-X-NH-(O)CO-P- OC(O)-NH-X-NCO
The diisocyanate can optionally be in excess with respect to the polymer. This first stage can be carried out in the presence of solvent, at a temperature of between 20°C and 100°C. This first stage can be followed by a period of stirring, under a controlled atmosphere, for a period ranging from 1 hour to 24 hours. The mixture can optionally be heated. The state of progression of this first stage can be monitored by quantitative determination of the hydroxyl functional groups; then
(ii) reaction of the prepolymer obtained in stage (i) with 6-methylisocytosine :
OCN-X-NH-(O)CO-P-OC(O)-NH-X-NCO
Figure imgf000029_0001
This second stage can optionally be carried out in the presence of a cosolvent, such as toluene, butyl acetate or else propylene carbonate. The reaction mixture can be heated at between 80 °C and 140 °C for a time varying between 1 hour and 24 hours.
The presence of a catalyst can promote the production of the desired final product. Mention may be made, for example, of the use of dibutyltin dilaurate.
The reaction can be monitored by infrared spectroscopy, by monitoring the disappearance of the peak characteristic of the isocyanate between 2200 and 2300 cm"1.
At the end of the reaction, ethanol can be added to the reaction medium in order to neutralize the residual isocyanate functional groups. The reaction mixture can optionally be filtered. For application purposes, the polymer could be directly stripped in a cosmetic solvent.
CONTINUOUS OILY PHASE
The expression "composition comprising an oily continuous phase" is understood to mean that the composition has a conductivity, measured at 25°C, of less than 23 μS/cm (microSiemens/cm) , the conductivity being measured, for example, using an MPC227 conductivity meter from Mettler Toledo and an Inlab730 conductivity measurement cell. The measurement cell is immersed in the composition, so as to remove the air bubbles liable to be formed between the 2 electrodes of the cell. The conductivity is read as soon as the value of the conductivity meter has stabilized. An average is taken over at least 3 successive measurements. The term "oil" is understood to mean any fatty substance which is in liquid form at ambient temperature (20-250C) and at atmospheric pressure. The oil may be volatile or non-volatile.
The expression "volatile oil" is understood to mean, within the meaning of the invention, any oil capable of evaporating on contact with keratin materials in less than one hour, at ambient temperature and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils that are liquid at ambient temperature and that have a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging from 0.13 Pa to 40 000 Pa (10~3 to
300 mmHg) , in particular ranging from 1.3 Pa to
13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
The expression "non-volatile oil" is understood to mean an oil that remains on the keratin materials at ambient temperature and atmospheric pressure for at least several hours and that has, in particular, a non- zero vapour pressure, at ambient temperature and atmospheric pressure, of less than 0.13 Pa (10~3 mmHg).
The continuous oily phase according to the invention may be present at a content that varies from
40 to 95%, in particular from 45 to 90%, in particular from 50 to 80%, and more particularly from 55 to 75% by weight relative to the total weight of the composition.
The continuous oily phase that is suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluorinated or unfluorinated oils, or mixtures thereof. The oils may be of animal, plant, mineral or synthetic origin.
Within the meaning of the present invention, the expression "silicone oil" is understood to mean an oil comprising at least one silicon atom, and especially at least one Si-O group.
According to one preferred embodiment that improves the adhesion of the composition to the keratin fibres and the drying time of this composition, said composition may comprise less than 10% by weight of silicone oil (s) relative to the total weight of the composition, better still less than 5% by weight, or may even be free of silicone oil. The expression "fluorinated oil" is understood to mean an oil comprising at least one fluorine atom.
The expression "hydrocarbon-based oil" is understood to mean an oil that mainly contains hydrogen and carbon atoms . The oils may optionally comprise oxygen, nitrogen, sulphur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
Volatile oils The volatile oils may be chosen from hydrocarbon- based oils having from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffins) , such as isododecane (also known as 2, 2, 4, 4, 6-pentamethylheptane) , isodecane, isohexa- decane, and, for example, the oils sold under the trade names ISOPARS® or PERMETHYLS®.
The volatile hydrocarbon-based oil may also be a linear volatile alkane chosen from volatile linear alkanes comprising from 7 to 17 carbon atoms, and in particular from 9 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms, especially of plant origin.
By way of example of a volatile linear alkane suitable for the invention, mention may be made of the alkanes described in patent application WO 2007/068371 by Cognis. These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut oil or palm oil. By way of example of a volatile linear alkane suitable for the invention, mention may be made of n- nonadecane (Cg) , n-decane (Cio) , n-undecane (Cn) , n- dodecane (C12) , n-tridecane (C13) , n-tetradecane (Ci4) , n-pentadecane (Ci5) , n-hexadecane (Ciε) , and mixtures thereof, and in particular the mixture of n-undecane (Cn) and n-tridecane (C13) sold under the reference CETIOL UT by Cognis.
Use may also be made, as volatile oils, of volatile silicones, such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity of < 8 centiStokes (cSt) (8 x 10~6 m2/s) and having in particular from 2 to 10 silicon atoms, and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, mention may in particular be made of dimethicones having a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa- siloxane, heptamethylhexyltrisiloxane, heptamethyl- octyltrisiloxane, hexamethyldisiloxane, octamethyl- trisiloxane, decamethyltetrasiloxane, dodecamethyl- pentasiloxane, and mixtures thereof. Use may also be made of volatile fluorinated oils, such as nonafluoromethoxybutane or perfluoro- methylcyclopentane, and mixtures thereof.
Non-volatile oils The non-volatile oils may in particular be selected from non-volatile hydrocarbon-based, fluorinated and/or silicone oils.
As non-volatile hydrocarbon-based oil, mention may in particular be made of: - hydrocarbon-based oils of animal origin,
- hydrocarbon-based oils of plant origin, such as phytostearyl esters, for instance phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/ phytostearyl glutamate (Ajinomoto, Eldew PS203) , triglycerides constituted of fatty acid esters of glycerol, in particular in which the fatty acids may have chain lengths ranging from C4 to C36, and in particular from Cis to C36, it being possible for these oils to be linear or branched, and saturated or unsaturated; these oils may in particular be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppyseed oil, pumpkin oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe oil, sweet almond oil, peach kernel oil, groundnut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, carrot oil, safflower oil, hemp oil, rapeseed oil, cottonseed oil, coconut oil, marrow seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, maize oil, meadowfoam oil, St. John's wort oil, monoi oil, hazelnut oil, apricot kernel oil, nut oil, olive oil, evening primrose oil, palm oil, blackcurrant seed oil, kiwi seed oil, grapeseed oil, pistachio oil, pumpkin oil, winter squash oil, quinoa oil, musk rose oil, sesame oil, soya bean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,
- synthetic ethers containing from 10 to 40 carbon atoms;
- synthetic esters, for instance oils of formula R1COOR2, in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that Ri + R2 is > 10. The esters may in particular be selected from fatty acid and alcohol esters, such as, for example:
• cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2- ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol 2- diethylhexanoate, and mixtures thereof, C12- Ci5 alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate or octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, hydroxylated esters such as isostearyl lactate and diisostearyl malate;
- polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxy- stearate/tetraisostearate,
- esters of diol dimers and diacid dimers, such as Lusplan DD-DA5® and Lusplan DD-DA7®, sold by the company Nippon Fine Chemical and described in application US 2004-175338,
- copolymers of a diol dimer and of a diacid dimer, and esters thereof, such as copolymers of dilinoleyl diol dimers/dilinoleic dimers and esters thereof, for instance Plandool-G, - copolymers of polyols and of diacid dimers, and esters thereof, such as Hailuscent ISDA,
- fatty alcohols that are liquid at ambient temperature, with a branched and/or unsaturated carbon chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol,
- C12-C22 higher fatty acids, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof, and
- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC® by Cognis, - oils of high molar mass, having in particular a molar mass ranging from approximately 400 to approximately 10 000 g/mol, in particular from approximately 650 to approximately 10 000 g/mol, in particular from approximately 750 to approximately 7500 g/mol, and more particularly ranging from approximately 1000 to approximately 5000 g/mol. As oils of high molar mass that can be used in the present invention, mention may in particular be made of the oils selected from: • lipophilic polymers,
• linear fatty acid esters having a total carbon number ranging from 35 to 70,
• hydroxylated esters,
• aromatic esters, • esters of C24-C28 branched fatty acids or fatty alcohols,
• silicone oils,
• oils of plant origin,
• and mixtures thereof. For example, an oil of high molar mass may be selected from: a) lipophilic polymers, such as:
• polybutylenes, such as Indopol H-100 (of molar mass MM=965 g/mol) , Indopol H-300 (MM=1340 g/mol), Indopol H-1500 (MM=2160 g/mol) sold or manufactured by the company Amoco,
• polyisobutylenes, for example hydrogenated polyisobutylenes, such as Panalane H-300 E sold or manufactured by the company Amoco
(MM=1340 g/mol), Viseal 20000 sold or manufactured by the company Synteal
(MM=6000 g/mol), Rewopal PIB 1000 sold or manufactured by the company Witco
(MM=IOOO g/mol) ,
• polydecenes and hydrogenated polydecenes, such as: Puresyn 10 (MM=723 g/mol), Puresyn 150 (MM=9200 g/mol) sold or manufactured by the company Mobil Chemicals,
• vinylpyrrolidone copolymers, such as: the vinylpyrrolidone/1-hexadecene copolymer Antaron V-216 sold or manufactured by the company ISP (MM=7300 g/mol), and polyvinylpyrrolidone (PVP) copolymers, such as copolymers of a C2-C30, for instance C3- C22, alkene, and combinations thereof, may be used. As examples of PVP copolymers that may be used in the invention, mention may be made of the PVP/vinyl laurate copolymer, the PVP/vinyl stearate copolymer, butylated PVP, the PVP/hexadecene copolymer, the PVP/triacontene copolymer or the PVP/acrylic acid/lauryl methacrylate copolymer, esters, such as:
• esters of linear fatty acids having a total carbon number ranging from 35 to 70, such as pentaerythrityl tetrapelargonate (MM=697 g/mol) ,
• hydroxylated esters, such as polyglyceryl-2 triisostearate (MM=965 g/mol) ,
• aromatic esters, such as tridecyl trimellitate (MM=757 g/mol), • esters of C24-C28 branched fatty acids or fatty alcohols, such as those described in patent US 6,491,927, and pentaerythritol esters, and especially triisoarachidyl citrate (MM=1033.76 g/mol) , pentaerythrityl tetraisononanoate (MM=697 g/mol) , glyceryl triisostearate (MM=891 g/mol), glyceryl 2- tridecyl tetradecanoate (MM=I 143 g/mol) , pentaerythrityl tetraisostearate (MM=1202 g/mol), polyglyceryl-2 tetraisostearate (MM=1232 g/mol) or else pentaerythrityl 2-tetradecyl tetradecanoate (MM=1538 g/mol) ,
• diol dimer esters and polyesters, such as the diol dimer esters of a fatty acid and the diol dimer esters of a diacid, for instance Lusplan DD-DA5® and Lusplan DD-DA7® sold by the company Nippon Fine Chemical and described in application US 2004- 175338, silicone oils, such as phenyl silicones, for instance Belsil PDM 1000 from the company Wacker (MM=9000 g/mol) . Other non-volatile silicone oils that can be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMSs) , PDMSs comprising alkyl or alkoxy groups that are pendant and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyl- diphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, and dimethicones or phenyl trimethicone with a viscosity of less than or equal to 100 cSt, and mixtures thereof, and also mixtures of the oils a) and/or b) and/or c) .
Preferably, the continuous oily phase is chosen from volatile hydrocarbon-based oils, preferably chosen from volatile branched alkanes having from 8 to 16 carbon atoms and volatile linear alkanes comprising from 7 to 17 carbon atoms.
COLORANT The composition of the invention contains at least one colorant such as pulverulent colorants, liposoluble dyes and water-soluble dyes.
The pulverulent colorants may be chosen from pigments and pearlescent agents. The pigments may be chosen from organic pigments or inorganic pigments.
Preferably, the colorant is chosen from organic pigments, inorganic pigments and pearlescent agents.
Within the meaning of the present invention, the term "pigment" is understood to mean any organic and/or inorganic entity having a solubility in water of less than 0.01% at 200C, preferably of less than 0.0001%, and exhibiting an absorption between 350 and 750 nm, preferably an absorption with a maximum. These pigments may be in the form of a powder or of a pigment paste. They can be coated or uncoated.
The pigment can be an inorganic pigment. The term "inorganic pigment" is understood to mean any pigment which corresponds to the definition of Ullmann's Encyclopedia in the "Inorganic Pigment" chapter. Mention may be made, among inorganic pigments of use in the present invention, of titanium dioxide, which is or is not surface-treated, zirconium, zinc or cerium oxides, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. For example, the following inorganic pigments can be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 as a mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS. The pigment that is not surface-treated, subsequently referred to as "pigment", may be an organic pigment. The term "organic pigment" is understood to mean any pigment which corresponds to the definition of Ullmann' s Encyclopedia in the "Organic Pigment" chapter. The organic pigment can in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone or phthalocyanine compounds, compounds of metal complex type, or isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.
In particular, white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, or the pigments obtained by oxidative polymerization of indole or phenol derivatives, as are described in patent FR 2 679 771.
The pigments in accordance with the invention can also be in the form of composite pigments, as are described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder, which provides for the attachment of the organic pigments to the core, and at least one organic pigment which at least partially covers the core. The organic pigment can also be a lake. The term "lake" is understood to mean dyes adsorbed onto insoluble particles, the combination thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
Mention may be made, among the dyes, of cochineal carmine. Mention may also be made of the dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).
Mention may be made, as examples of lakes, of the product known under the following name: D & C Red 7 (CI 15 850:1) .
The colorant can also be a pearlescent agent. Mention may be made, as examples of pearlescent agents, of white pearlescent pigments, such as mica covered with titanium dioxide or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium dioxide or with iron oxides, mica covered with titanium dioxide and in particular with ferric blue or with chromium oxide or mica covered with titanium dioxide and with an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Mention may be made, as pearlescent pigments, of the following pearlescent agents: Cellini sold by Engelhard (mica-Tiθ2-lake) , Prestige sold by Eckart (mica-Tiθ2) , Prestige Bronze sold by Eckart (mica-Fe2θ3) or Colorona sold by Merck
Figure imgf000040_0001
In addition to pearlescent agents on a mica support, it is possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
The colorant may also be a liposoluble dye.
Liposoluble dyes are, for example, Sudan red, D&C Red 17, D&C Green 6, β-carotene, soya bean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.
These colorants may be present at a content ranging from 0.01 to 30% by weight relative to the total weight of the composition.
STRUCTURING AGENT
The composition according to the invention may comprise at least one agent for structuring the continuous oily phase (formed by the volatile or nonvolatile oils described above) chosen from waxes, pastes, semi-crystalline polymers, lipophilic gelling agents, and mixtures thereof.
The structuring agent may represent from 5 to 80% by weight relative to the total weight of the composition, preferably from 7 to 75% and more preferably still from 10 to 55% by weight.
The amount of structuring agent may be adjusted by a person skilled in the art as a function of the structuring properties of said agents.
Wax (es)
The wax under consideration in the context of the present invention is generally a lipophilic compound which is solid at ambient temperature (25°C), which exhibits a reversible solid/liquid change in state and which has a melting point of greater than or equal to 300C which can range up to 2000C and in particular up to 120°C. On bringing the wax to the liquid state (melting) , it is possible to render it miscible with oils and to form a microscopically homogeneous mixture but, on bringing the temperature of the mixture back to ambient temperature, recrystallization of the wax in the oils of the mixture is obtained.
In particular, the waxes suitable for the invention can exhibit a melting point of greater than or equal to 45°C and in particular of greater than or equal to 55°C.
Within the meaning of the invention, the melting point corresponds to the temperature of the most endothermic peak observed by thermal analysis (DSC) as described in the standard ISO 11357-3; 1999. The melting point of the wax can be measured using a differential scanning calorimeter (DSC) , for example the calorimeter sold under the name "MDSC 2920" by TA Instruments . The measurement protocol is as follows:
A 5 mg sample of wax placed in a crucible is subjected to a first rise in temperature ranging from -200C to 1000C at a heating rate of 10°C/minute, is then cooled from 1000C to -20°C at a cooling rate of 10°C/minute and, finally, is subjected to a second rise in temperature ranging from -200C to 1000C at a heating rate of 5°C/minute. During the second rise in temperature, the variation in the difference in power absorbed by the empty crucible and by the crucible comprising the sample of wax is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.
The waxes capable of being used in the compositions according to the invention are chosen from waxes of animal, plant, mineral or synthetic origin, and their mixtures, which are solid at ambient temperature.
The waxes which can be used in the compositions according to the invention generally exhibit a hardness ranging from 0.01 MPa to 15 MPa, in particular of greater than 0.05 MPa and in particular of greater than 0.1 MPa.
The hardness is determined by the measurement of the compressive force measured at 200C using a texture analyser sold under the name TA-XT2 by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm which is displaced at the measuring rate of 0.1 mm/s and which penetrates the wax to a penetration depth of 0.3 mm. The measurement protocol is as follows:
The wax is melted at a temperature equal to the melting point of the wax + 100C. The molten wax is cast in a receptacle with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25°C) for 24 hours, so that the surface of the wax is flat and smooth, and then the wax is stored at 200C for at least one hour before measuring the hardness or the tack. The rotor of the texture analyser is displaced at the rate of 0.1 mm/s and then penetrates the wax to a penetration depth of 0.3 mm. When the rotor has penetrated the wax to the depth of 0.3 mm, the rotor is held stationary for 1 second (corresponding to the relaxation time) and is then withdrawn at the rate of 0.5 mm/s.
The value of the hardness is the maximum compressive force measured divided by the surface area of the cylinder of the texture analyser in contact with the wax.
Mention may in particular be made, by way of illustration of the waxes suitable for the invention, of hydrocarbon-based waxes, such as beeswax, lanolin wax and Chinese insect waxes; rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto wax, berry wax, shellac wax, Japan wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffin waxes and ozokerite; polyethylene waxes, the waxes obtained by the Fischer-Tropsch synthesis and waxy copolymers, and their esters.
Mention may also be made of waxes obtained by catalytic hydrogenation of animal or plant oils having linear or branched C8-C32 fatty chains. Mention may in particular be made, among these, of hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and di (1,1,1- trimethylolpropane) tetrastearate, sold under the name of Hest 2T-4S® by Heterene.
Mention may also be made of silicone waxes or fluorinated waxes.
Use may also be made of the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol which are sold under the names of Phytowax
Castor 16L64® and 22L73® by Sophim. Such waxes are described in application FR-A-2 792 190.
According to a specific embodiment, the compositions according to the invention can comprise at least one wax referred to as a "tacky wax", that is to say having a tack of greater than or equal to 0.1 N. s and a hardness of less than or equal to 3.5 MPa.
The tacky wax used can have in particular a tack ranging from 0.1 N. s to 10 N.s, in particular ranging from 0.1 N.s to 5 N.s, preferably ranging from 0.2 to 5 N.s and better still ranging from 0.3 to 2 N.s.
The tack of the wax is determined by the measurement of the change in the force (compressive force) as a function of the time at 200C according to the protocol indicated above for the hardness.
During the relaxation time of 1 s, the force (compressive force) strongly decreases until it becomes zero and then, during the withdrawal of the rotor, the force (stretching force) becomes negative to subsequently again increase towards the value 0. The tack corresponds to the integral of the curve of the force as a function of the time for the part of the curve corresponding to the negative values of the force. The value of the tack is expressed in N.s. The tacky wax which can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa. Use may be made, as tacky wax, of a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture. Such a wax is sold in particular under the names "Kester Wax K 82 P®" and "Kester Wax K 80 P®" by Koster Keunen.
In the present invention, use may also be made of waxes provided in the form of small particles having a size, expressed as volume-average "effective" diameter D[4,3], of the order of 0.5 to 30 micrometres, in particular of 1 to 20 micrometres and more particularly of 5 to 10 micrometres, subsequently denoted by the expression "microwaxes" .
The sizes of the particles can be measured by various techniques. Mention may in particular be made of light scattering techniques (dynamic and static) , Coulter counter methods, measurements by rate of sedimentation (related to the size via Stokes' law) and microscopy. These techniques make it possible to measure a particle diameter and, for some of them, a particle size distribution.
Preferably, the sizes and size distributions of the particles of compositions according to the invention are measured by static light scattering using a commercial particle sizer of MasterSizer 2000 type from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" particle diameter. This theory is described in particular in the work by Van de Hulst, H. C, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. The composition is characterized by its volume- average "effective" diameter D [4, 3], defined in the following way:
Figure imgf000046_0001
where V1 represents the volume of the particles with an effective diameter Cl1. This parameter is described in particular in the technical documentation of the particle sizer.
The measurements are performed at 25°C on a dilute particle dispersion, obtained from the composition in the following manner: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) standing of the solution for 18 hours, 4) recovery of the whitish homogeneous supernatant. The "effective" diameter is obtained by taking a refractive index of 1.33 for the water and a mean refractive index of 1.42 for the particles.
Mention may in particular be made, as microwaxes which can be used in the compositions according to the invention, of carnauba microwaxes, such as that sold under the name of MicroCare 350® by Micro Powders, synthetic wax microwaxes, such as that sold under the name of MicroEase 114S® by Micro Powders, microwaxes composed of a mixture of carnauba wax and of polyethylene wax, such as those sold under the names of Micro Care 300® and 310® by Micro Powders, microwaxes composed of a mixture of carnauba wax and of synthetic wax, such as that sold under the name Micro Care 325® by Micro Powders, polyethylene microwaxes, such as those sold under the names of Micropoly 200®, 220®, 220L® and 250S® by Micro Powders, and polytetrafluoroethylene microwaxes, such as those sold under the names of Microslip 519® and 519 L® by Micro Powders.
The composition according to the invention can comprise a content of waxes ranging from 5 to 70% by weight, with respect to the total weight of the composition; in particular, it can comprise from 7 to 50% by weight thereof, more particularly from 10 to 45% by weight thereof.
Pastes The composition according to the invention may comprise at least one pasty compound.
The term "pastes" is understood, within the meaning of the present invention, to mean a lipophilic fatty compound having a reversible solid/liquid change in state and comprising, at a temperature of 23°C, a liquid fraction and a solid fraction.
The pasty compound preferably has a hardness at 200C ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa. The hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyser (for example, the TA-XT2i from Stable Micro Systems Ltd.) equipped with a stainless steel cylinder with a diameter of 2 mm. The hardness measurement is carried out at 200C at the centre of 5 samples. The cylinder is introduced into each sample at a pre-rate of 1 mm/s and then at a measuring rate of 0.1 mm/s, the depth of penetration being 0.3 mm. The value recorded for the hardness is that of the maximum peak.
This pasty compound is, additionally, at a temperature of 23°C, in the form of a liquid fraction and of a solid fraction. In other words the starting melting point of the pasty compound is below 23°C. The liquid fraction of the pasty compound measured at 23°C represents from 23 to 97% by weight of the compound. This liquid fraction at 23°C preferably represents between 40 and 85% by weight of the compound.
The liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the pasty compound.
The enthalpy of fusion of the pasty compound is the enthalpy consumed by the compound to change from the solid state to the liquid state. The pasty compound is "in the solid state" when the whole of its mass is in the solid form. The pasty compound is "in the liquid state" when the whole of its mass is in the liquid form.
The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC) , such as the calorimeter sold under the name MDSC 2920 by TA Instrument, with a rise in temperature of 5 or 100C per minute, according to standard ISO 11357- 3:1999. The enthalpy of fusion of the pasty compound is the amount of energy necessary to change the compound from the solid state to the liquid state. It is expressed in J/g.
The enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state which it exhibits at 23°C, composed of a liquid fraction and of a solid fraction. The liquid fraction of the pasty compound measured at 32°C preferably represents from 40 to 100% by weight of the compound, preferably from 50 to 100%, preferably from 80 to 100%, more preferably from 90 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32°C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32°C.
The liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32°C to the enthalpy of fusion of the pasty compound. The enthalpy of fusion consumed at 320C is calculated in the same way as the enthalpy of fusion consumed at 23°C.
The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound may be obtained by synthesis from starting products of plant origin.
The pasty compound is advantageously chosen from: lanolin and its derivatives, such as lanolin alcohol, oxyethylenated lanolins, acetylated lanolin, lanolin esters such as isopropyl lanolate, and oxypropylenated lanolins; polymeric or non-polymeric silicone compounds, such as high molecular weight polydimethylsiloxanes, polydimethylsiloxanes with side chains of the alkyl or alkoxy type that have from 8 to 24 carbon atoms, especially stearyl dimethicones; polymeric or non-polymeric fluorinated compounds; vinyl polymers, especially:
• olefin homopolymers;
• olefin copolymers;
• hydrogenated diene homopolymers and copolymers;
• linear or branched oligomers which are homopolymers or copolymers of alkyl
(meth) acrylates preferably having a C8-C30 alkyl group; • oligomers which are homopolymers and copolymers of vinyl esters having C8-C30 alkyl groups;
• oligomers which are homopolymers and copolymers of vinyl ethers having C8-C30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C2-C100, preferably C2-C50, diols; polyol ethers chosen from ethers of pentaerythritol and of polyalkylene glycol, ethers of fatty alcohol and of sugar, and mixtures thereof, the ether of pentaerythritol and of polyethylene glycol comprising 5 oxyethylenated units (5 EO) (CTFA name: PEG-5 Pentaerythrityl Ether) , the ether of pentaerythritol and of polypropylene glycol comprising 5 oxypropylenated units (5 PO) (CTFA name: PPG-5 Pentaerythrityl Ether) , and mixtures thereof and more especially the PEG-5 Pentaerythrityl Ether, PPG-5 Pentaerythrityl Ether and soya bean oil mixture sold under the name "Lanolide" by Vevy, in which mixture the constituents are in a weight ratio of 46/46/8: 46% of PEG-5 Pentaerythrityl Ether, 46% of PPG-5 Pentaerythrityl Ether and 8% of soya bean oil; - esters and polyesters; and mixtures thereof.
The pasty compound is preferably a polymer and especially a hydrocarbon-based polymer.
A preferred silicone and fluorinated pasty compound is polymethyltrifluoropropylmethylalkyl- dimethylsiloxane, manufactured under the name X22-1088 by Shin-Etsu.
When the pasty compound is a silicone and/or fluorinated polymer, the composition advantageously comprises a compatibilizer such as short-chain esters, for instance isodecyl neopentanoate .
Among the liposoluble polyethers that are especially preferred are copolymers of ethylene oxide and/or of propylene oxide with C6-C30 long-chain alkylene oxides, more preferably such that the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will be made especially of copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight of from 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 EO) sold under the brand name Elfacos ST9 by Akzo Nobel.
Among the esters that are especially preferred are : esters of a glycerol oligomer, especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, for instance those sold under the brand name Softisan 649 by the company Sasol,
- phytosterol esters, pentaerythritol esters, - esters formed from:
• at least one alcohol, at least one of the alcohols being a Guerbet alcohol, and
• a diacid dimer formed from at least one unsaturated fatty acid, • for instance the ester of fatty acid dimer of tall oil containing 36 carbon atoms and of a mixture i) of Guerbet alcohols containing 32 carbon atoms and ii) of behenyl alcohol; the ester of linoleic acid dimer and of a mixture of two Guerbet alcohols, 2-tetradecyl- octadecanol (32 carbon atoms) and 2-hexadecyleicosanol (36 carbon atoms) ,
- non-crosslinked polyesters resulting from polycondensation between a linear or branched C4-C5O dicarboxylic acid or polycarboxylic acid and a C2-C50 diol or polyol,
- polyesters resulting from the esterification, with a polycarboxylic acid, of an aliphatic hydroxy- carboxylic acid ester, for instance Risocast DA-L and Risocast DA-H sold by the Japanese company Kokyu Alcohol Kogyo, which are esters resulting from the esterification reaction of hydrogenated castor oil with dilinoleic acid or isostearic acid, aliphatic esters of an ester resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic carboxylic acid; (Salacos
HCIS (V)-L sold by the company Nishing Oil).
The aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid and docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched.
The aliphatic hydroxycarboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid containing from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 20 hydroxyl groups, preferably from 1 to 10 hydroxyl groups and better still from 1 to 6 hydroxyl groups. The aliphatic hydroxycarboxylic acid ester is chosen from: a) partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids; b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids; c) partial or total esters of saturated mono- hydroxylated aliphatic polycarboxylic acids; d) partial or total esters of saturated poly- hydroxylated aliphatic polycarboxylic acids; e) partial or total esters of C2 to C16 aliphatic polyols that have reacted with a monohydroxylated or polyhydroxylated aliphatic monocarboxylic or polycarboxylic acid, and mixtures thereof.
The aliphatic esters of an ester are advantageously chosen from: - the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 1 (1/1) or hydrogenated castor oil monoisostearate, the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 2 (1/2) or hydrogenated castor oil diisostearate, the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 3 (1/3) or hydrogenated castor oil triisostearate, and mixtures thereof.
The pasty compound may also be of plant origin. In this case, mention may be made especially of isomerized jojoba oil such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Joj oba-50®, orange wax, such as for example the product sold under the reference Orange Peel Wax by the company Koster Keunen, shea butter, partially hydrogenated olive oil such as for example the compound sold under the reference Beurrolive by the company Soliance, cocoa butter, and mango oil, such as for example Lipex 302 from the company Aarhuskarlshamn .
Semi-crystalline polymers
The term "polymer" is understood to mean compounds containing at least two repeat units, preferably at least three repeat units and more especially at least ten repeat units. The term "semi-crystalline polymer" is understood to mean polymers comprising a crystallizable portion, a crystallizable pendant chain or a crystallizable block in the backbone, and an amorphous portion in the backbone and having a first- order reversible phase-change temperature, in particular of melting (solid-liquid transition) . When the crystallizable portion is in the form of a crystallizable block of the polymer backbone, the amorphous portion of the polymer is in the form of an amorphous block; in this case, the semi-crystalline polymer is a block copolymer, for example, of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. The term "block" is generally understood to mean at least five identical repeat units. The crystallizable block(s) is (are) thus of chemical nature different than that of the amorphous block (s) .
The semi-crystalline polymer has a melting point of greater than or equal to 300C (especially ranging from 300C to 80°C), preferably ranging from 300C to
60°C. This melting point is a first-order change of state temperature.
This melting point may be measured by any known method and in particular using a differential scanning calorimeter (DSC) .
Advantageously, the semi-crystalline polymer (s) to which the invention applies has (have) a number-average molecular weight of greater than or equal to 1000. Advantageously, the semi-crystalline polymer (s) of the composition of the invention has (have) a number- average molecular weight Mn ranging from 2000 to 800 000, preferably from 3000 to 500 000, better still from 4000 to 150 000, especially less than 100 000 and better still from 4000 to 99 000. Preferably, they have a number-average molecular weight of greater than 5600, for example ranging from 5700 to 99 000.
For the purposes of the invention, the term "crystallizable chain or block" is understood to mean a chain or block which, if it were alone, would reversibly change from the amorphous state to the crystalline state, depending on whether the system is above or below the melting point. For the purposes of the invention, a chain is a group of atoms, which is pendant or lateral relative to the polymer backbone. A block is a group of atoms belonging to the backbone, this group constituting one of the repeat units of the polymer. Advantageously, the "crystallizable pendant chain" may be a chain containing at least six carbon atoms . The semi-crystalline polymer may be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, and homopolymers and copolymers bearing at least one crystallizable side chain per repeat unit, and mixtures thereof .
Such polymers are described, for example, in document EP 1 396 259.
A. Semi-crystalline polymers containing crystalliz- able side chains
Mention may be made in particular of those defined in documents US-A-5 156 911 and WO-A-01/19333. They are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers bearing a crystallizable hydrophobic side chain.
These homopolymers or copolymers are of any nature, provided that they meet the conditions mentioned previously.
B . Polymers bearing in the backbone at least one crystallizable block These polymers are especially block copolymers constituted of at least two blocks of different chemical nature, one of which is crystallizable.
The block polymers defined in patent US-A-5 156 911 may be used; - The block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:
- cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo (2, 2, 1) -2-heptene) , 5-methy1- norbornene, 5-ethylnorbornene, 5, 6-dimethylnorbornene, 5, 5, 6-trimethylnorbornene, 5-ethylidenenorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnor- bornene, 1,4,5, 8-dimethano-l, 2,3,4, 4a, 5, 8a-octahydro- naphthalene, dicyclopentadiene, or mixtures thereof, - with ethylene, propylene, 1-butene, 3-methyl-l- butene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene or 1-eicosene, or mixtures thereof, and in particular copoly (ethylene/norbornene) blocks and (ethylene/propylene/ethylidene-norbornene) block terpolymers. Those resulting from the block copolymerization of at least two C2-C16, better still C2- C12 and even better still C4-C12 α-olefins such as those mentioned above and in particular block bipolymers of ethylene and of 1-octene may also be used.
- The copolymers may be copolymers containing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature) . These copolymers may also contain two crystallizable blocks of different chemical nature. The preferred copolymers are those that simultaneously contain at room temperature a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; mention may be made, for example, of polymers containing one of the crystallizable blocks and one of the amorphous blocks below: - Block that is crystallizable by nature: a) of polyester type, for instance poly (alkylene terephthalate) , b) of polyolefin type, for instance polyethylenes or polypropylenes .
- Amorphous and lipophilic block, for instance: amorphous polyolefins or copoly (olefin) s such as poly (isobutylene) , hydrogenated polybutadiene or hydrogenated poly (isoprene) .
As examples of such copolymers containing a crystallizable block and an amorphous block that are different, mention may be made of: α) poly ( ε-caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in the article "Melting behavior of poly ( ε-caprolactone) -block-polybutadiene copolymers" by S. Nojima, Macromolecules, 32, 3727-3734 (1999), β) the hydrogenated block or multiblock poly (butylene terephthalate) -b-poly (isoprene) block copolymers cited in the article "Study of morphological and mechanical properties of PP/PBT" by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995), γ) the poly (ethylene) -b-copoly (ethylene/propylene) block copolymers cited in the articles "Morphology of semi-crystalline block copolymers of ethylene- (ethylene- alt-propylene) " by P. Rangarajan et al . , Macromolecules, 26, 4640-4645 (1993) and "Polymer aggregates with crystalline cores: the system poly (ethylene) - poly (ethylene-propylene) " by P. Richter et al . , Macromolecules, 30, 1053-1068 (1997), δ) the poly (ethylene) -b-poly (ethylethylene) block copolymers cited in the general article "Crystallization in block copolymers" by I. W. Hamley, Advances in Polymer Science, Vol. 148, 113-137 (1999). Preferably, the semi-crystalline polymers in the composition according to the invention are non- crosslinked.
According to one particular embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one monomer containing a crystallizable chain chosen from saturated Ci4 to C24 alkyl (meth) acrylates, Cu to Ci5 perfluoroalkyl (meth) acrylates, Ci4 to C24 N-alkyl (meth) acrylamides with or without a fluorine atom, vinyl esters containing Ci4 to C24 alkyl or perfluoroalkyl chains, vinyl ethers containing Ci4 to C24 alkyl or perfluoroalkyl chains, Ci4 to C24 OC-olefins, para-alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated Ci to Cio monocarboxylic acid ester or amide, which may be represented by the following formula :
H2C^C C X R
R1 O in which Ri is H or CH3, R represents an optionally fluorinated C1-C10 alkyl group and X represents O, NH or NR2, in which R2 represents an optionally fluorinated Ci-Cio alkyl group.
According to a more particular embodiment of the invention, the polymer is derived from a monomer containing a crystallizable chain chosen from saturated Ci4 to C22 alkyl (meth) acrylates .
As a particular example of a structuring semi- crystalline polymer that may be used in the composition according to the invention, mention may be made of the
® Intelimer products from the company Landec described in
® the brochure "Intelimer Polymers", Landec IP22 (Rev.
4-97) . These polymers are in solid form at room temperature (25°C). They bear crystallizable side chains and have the above formula X.
Lipophilic gelling agents
The gelling agents that may be used in the compositions according to the invention may be organic or mineral, polymeric or molecular lipophilic gelling agents .
Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a Cio to C22 fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, such as for example the product sold under the name Bentone 38V® by the company Elementis. Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 μm. Specifically, it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: - trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane . Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R812® by the company Degussa, and Cab-O-Sil TS- 530® by the company Cabot;
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyl- dichlorosilane . Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6th edition, 1995) . They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS- 720® by the company Cabot.
The hydrophobic fumed silica in particular has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm. The polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for instance those sold under the names KSG6®, KSG16® and KSG18® from Shin-Etsu, Trefil E-505C® and Trefil E-506C® from Dow Corning, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® from Grant Industries and SF 1204® and JK 113® from General Electric; ethyl cellulose, for instance the product sold under the name Ethocel® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between (α) at least one acid chosen from dicarboxylic acids containing at least 32 carbon atoms, such as fatty acid dimers, and (β) an alkylenediamine and in particular ethylenediamine, in which the polyamide polymer comprises at least one carboxylic acid end group esterified or amidated with at least one saturated and linear monoalcohol or one saturated and linear monoamine containing from 12 to 30 carbon atoms, and in particular ethylenediamine/stearyl dilinoleate copolymers such as the product sold under the name Uniclear 100 VG® by the company Arizona Chemical; silicone polyamides of the polyorganosiloxane type, for instance those described in documents US-A-5 874 069, US-A-5 919 441, US-A-6 051 216 and US-A-5 981 680, such as for example those sold under the reference Dow Corning 2-8179 Gellant by the company Dow Corning; galactomannans comprising from one to six and in particular from two to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated alkyl chain, for instance guar gum alkylated with Ci to Ce, and in particular Ci to C3, alkyl chains, and mixtures thereof. Block copolymers of "diblock", "triblock" or "radial" type, of the polystyrene/poly- isoprene or polystyrene/polybutadiene type, such as the products sold under the name Luvitol HSB® by the company BASF, of the polystyrene/copoly (ethylene-propylene) type, such as the products sold under the name Kraton® by the company Shell Chemical Co., or of the polystyrene/copoly (ethylene-butylene) type, and mixtures of triblock and radial (star) copolymers in isododecane, such as those sold by the company Penreco under the name Versagel®, for instance the mixture of butylene/ethylene/styrene triblock copolymer and of ethylene/propylene/styrene star copolymer in isododecane (Versagel M 5960).
Among the lipophilic gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name Rheopearl TL® or Rheopearl KL® by the company Chiba Flour.
FILM-FORMING POLYMER
According to one particular embodiment, the composition according to the invention may comprise at least one film-forming polymer.
The film-forming polymer may be present in the composition according to the invention in a solids (or active material) content ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the total weight of the composition.
In the present invention, the expression "film- forming polymer" is understood to mean a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous film that adheres to the keratin fibres, preferably a cohesive film and better still a film whose cohesion and mechanical properties are such that said film can be isolated and manipulated separately, for example when said film is made by casting on a non-stick surface, for instance a Teflon- coated or silicone-coated surface.
Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, and polymers of natural origin, and mixtures thereof.
The expression "free-radical film-forming polymer" is understood to mean a polymer obtained by polymerization of unsaturated and especially ethylenically unsaturated monomers, each monomer being capable of homopolymerizing (unlike polycondensates) .
The film-forming polymers of free-radical type may be, in particular, vinyl polymers or copolymers, in particular acrylic polymers.
The vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers .
Monomers bearing an acid group which may be used are CC, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth) acrylic acid and crotonic acid are preferably used, and more preferably (meth) acrylic acid. The esters of acid monomers are advantageously chosen from (meth) acrylic acid esters (also known as (meth) acrylates) , especially (meth) acrylates of an alkyl, in particular of a C1-C30 and preferably C1-C20 alkyl, (meth) acrylates of an aryl, in particular of a Cδ-Cio aryl, and (meth) acrylates of a hydroxyalkyl, in particular of a C2-C6 hydroxyalkyl.
Among the alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate .
Among the hydroxyalkyl (meth) acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate .
Among the aryl (meth) acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
The (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .
According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Examples of amides of the acid monomers that may be mentioned are (meth) acrylamides, and especially N- alkyl (meth) acrylamides, in particular of a C2-C12 alkyl.
Among the N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .
The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned above.
Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate . Styrene monomers that may be mentioned are styrene and α-methylstyrene .
Among the film-forming polycondensates that may be mentioned are polyurethanes, polyesters, polyesteramides, polyamides, epoxyester resins and polyureas.
The polyurethanes may be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether- polyurethanes, polyureas and polyurea-polyurethanes, and mixtures thereof.
The polyesters may be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.
The dicarboxylic acid may be aliphatic, alicyclic or aromatic. Examples of such acids that may be mentioned are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2, 2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1, 3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2, 5-norbornanedicarboxylic acid, diglycolic acid, thiodipropionic acid, 2, 5-naphthalene- dicarboxylic acid or 2, 6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or as a combination of at least two dicarboxylic acid monomers. Among these monomers, the ones preferentially chosen are phthalic acid, isophthalic acid and terephthalic acid.
The diol may be chosen from aliphatic, alicyclic and aromatic diols. The diol used is preferably chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, cyclohexanedimethanol and 4-butanediol . Other polyols that may be used are glycerol, pentaerythritol, sorbitol and trimethylolpropane . The polyesteramides may be obtained in a manner analogous to that of the polyesters, by polycondensation of diacids with diamines or amino alcohols. Diamines that may be used are ethylenediamine, hexamethylenediamine and meta- or para-phenylenediamine . An amino alcohol that may be used is monoethanolamine .
The polyester may also comprise at least one monomer bearing at least one group -SO3M, with M representing a hydrogen atom, an ammonium ion NH4 + or a metal ion such as, for example, an Na+, Li+, K+, Mg2+, Ca2+, Cu2+, Fe2+ or Fe3+ ion. A difunctional aromatic monomer comprising such a group -SO3M may be used in particular . The aromatic ring of the difunctional aromatic monomer also bearing a group -SO3M as described above may be chosen, for example, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulphonylbiphenyl and methylenebiphenyl rings. As examples of difunctional aromatic monomers also bearing a group -SO3M, mention may be made of: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2, 7-dicarboxylic acid.
The copolymers preferably used are those based on isophthalate/sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulphoisophthalic acid.
The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulose polymers, and mixtures thereof.
The film-forming polymer may be a polymer dissolved in the continuous oily phase (the film- forming polymer is thus said to be a liposoluble polymer) .
Examples of liposoluble polymers which may be mentioned are copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present) , an α-olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group comprises from 2 to 18 carbon atoms) or an allyl or methaiIyI ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) .
These copolymers may be crosslinked with the aid of crosslinking agents, which may be either of the vinyl type or of the allyl or methaiIyI type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate .
Examples of these copolymers that may be mentioned are the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2, 2-dimethyloctanoate/vinyl laurate, allyl 2, 2-dimethylpentanoate/vinyl laurate, vinyl dimethyl- propionate/vinyl stearate, allyl dimethyl- propionate/vinyl stearate, vinyl propionate/ vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinylbenzene, vinyl acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate/allyl stearate, crosslinked with 0.2% divinylbenzene. Examples of liposoluble film-forming polymers which may also be mentioned are liposoluble copolymers, and in particular those resulting from the copolymer- ization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 10 to 20 carbon atoms.
Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, of polyvinyl stearate crosslinked with the aid of divinylbenzene, of diallyl ether or of diallyl phthalate, copolymers of polystearyl (meth) acrylate, of polyvinyl laurate and of polylauryl (meth) acrylate, it being possible for these poly (meth) acrylates to be crosslinked with the aid of ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.
The liposoluble copolymers defined above are known and are described in particular in application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.
As liposoluble film-forming polymers which may be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkyl celluloses with a linear or branched, saturated or unsaturated Ci-Cs alkyl radical, for instance ethyl cellulose and propyl cellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still C3 to C20 alkene. As examples of VP copolymers which may be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP) , VP/ethyl methacrylate/ methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate .
Mention may also be made of silicone resins, which are generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers. The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ" characterizing a type of unit.
Examples of commercially available polymethylsilsesquioxane resins that may be mentioned include those sold: by the company Wacker under the reference Resin MK, such as Belsil PMS MK; by the company Shin-Etsu under the reference KR- 220L.
Siloxysilicate resins that may be mentioned include trimethylsiloxysilicate (TMS) resins such as those sold under the reference SRlOOO by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of the trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning.
Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, for instance the pressure- sensitive adhesive copolymers sold by the company Dow Corning under the reference BIO-PSA and described in document US 5 162 410, or the silicone copolymers derived from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane, as described in document WO 2004/073626.
The film-forming polymer may also be present in the composition in the form of particles dispersed in a non-aqueous solvent phase, which is generally known as a latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art .
Examples of non-aqueous film-forming polymer dispersions that may be mentioned include acrylic dispersions in isododecane, for instance Mexomer PAP1 from the company Chimex, and dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described especially in document WO 04/055081.
The composition according to the invention may comprise a plasticizer that promotes the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from any compound known to those skilled in the art as being capable of fulfilling the desired function .
FILLERS
The composition according to the invention may also comprise at least one filler.
The fillers may be chosen from those that are well known to persons skilled in the art and commonly used in cosmetic compositions. The fillers may be mineral or organic, and lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, powders of polyamide, for instance Nylon® sold under the trade name Orgasol® by the company Atochem, poly-β-alanine powders and polyethylene powders, powders of tetrafluoroethylene polymers, for instance Teflon®, lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance the products sold under the name Expancel® by the company Nobel Industrie, acrylic powders, such as those sold under the name Polytrap® by the company Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (for example Tospearls® from Toshiba) , precipitated calcium carbonate, magnesium carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos) , glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate and magnesium myristate.
It is also possible to use a compound that is capable of swelling on heating, and especially heat- expandable particles such as non-expanded microspheres of vinylidene chloride/acrylonitrile/methyl methacrylate copolymer or of acrylonitrile homopolymer copolymer, for instance those sold, respectively, under the references Expancel® 820 DU 40 and Expancel® 007WU by the company Akzo Nobel. The fillers may represent from 0.1 % to 25% and in particular from 1 % to 20% by weight relative to the total weight of the composition.
FIBRES
The composition according to the invention may also comprise fibres which enable a lengthening effect.
The term "fibre" should be understood as meaning an object of length L and diameter D such that L is very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or shape factor) is chosen in the range from 3.5 to 2500, especially from 5 to 500 and in particular from 5 to 150.
The fibres that may be used in the composition of the invention may be mineral or organic fibres of synthetic or natural origin. They may be short or long, individual or organized, for example braided, and hollow or solid. They may have any shape, and may especially have a circular or polygonal (square, hexagonal or octagonal) cross section, depending on the intended specific application. In particular, their ends are blunt and/or polished to prevent injury. In particular, the fibres have a length ranging from 1 μm to 10 mm, in particular from 0.1 mm to 5 mm and more particularly from 0.3 mm to 3.5 mm. Their cross section may be within a circle of diameter ranging from 2 nm to 500 μm, in particular ranging from 100 nm to 100 μm and more particularly from 1 μm to 50 μm. The weight or yarn count of the fibres is often given in denier or decitex, and represents the weight in grams per 9 km of yarn. In particular, the fibres according to the invention may have a yarn count chosen in the range from 0.15 to 30 denier and especially from 0.18 to 18 denier.
The fibres that may be used in the composition of the invention may be chosen from rigid or non-rigid fibres, and may be of synthetic or natural, mineral or organic origin.
Moreover, the fibres may or may not be surface- treated, may be coated or uncoated, and may be coloured or uncoloured.
As fibres that may be used in the composition according to the invention, mention may be made of non-
® rigid fibres such as polyamide (Nylon ) fibres or rigid fibres such as polyimideamide fibres, for instance those sold under the names Kermel and Kermel Tech by the company Rhodia or poly (p-phenyleneterephthalamide)
(or aramid) fibres sold especially under the name
Kevlar by the company DuPont de Nemours.
The fibres may be present in the composition according to the invention in a content ranging from
0.01% to 10% by weight, in particular from 0.1% to 5% by weight and more particularly from 0.3% to 3% by weight relative to the total weight of the composition.
AQUEOUS PHASE
The composition according to the invention may comprise an aqueous phase in the form of a dispersed phase. This phase may be present in an amount between 0.1 and 10% by weight relative to the total weight of the composition.
The aqueous phase may be composed essentially of water; it may also comprise a mixture of water and of a solvent miscible with water (miscibility in water greater than 50% by weight at 25°C) such as lower monoalcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, and dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes and mixtures thereof. Preferably, the composition according to the invention is anhydrous.
The term "anhydrous" is understood to mean that the composition comprises water in a content of less than 5% by weight of water, in particular less than 3%, especially less than 2%, and more particularly less than 1% by weight of water relative to the total weight of the composition.
More preferably, the composition of the invention is free of water.
When the composition comprises an aqueous phase, it may comprise at least one hydrophilic film-forming polymer .
Hydrophilic film-forming polymer
The hydrophilic film-forming polymer may be a water-soluble polymer or may be in dispersion in an aqueous medium.
As examples of water-soluble film-forming polymers, mention may be made of: proteins, such as proteins of plant origin, for instance wheat or soya bean protein; proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins; - cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and also quaternized derivatives of cellulose; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, the copolymer of vinyl acetate and of crotonic acid, the copolymers of vinylpyrrolidone and of vinyl acetate, the copolymers of vinylpyrrolidone and of caprolactam, polyvinyl alcohol; anionic, cationic, amphoteric or non ionic chitin or chitosan polymers; gum arabics, guar gum, xanthan derivatives and karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and derivatives thereof; shellac resin, sandarac gum, dammar resins, elemi gums and copal resins; deoxyribonucleic acid; mucopolysaccharides such as chondroitin sulphates; and mixtures thereof.
The film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase, generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to a person skilled in the art .
As an aqueous dispersion of a film-forming polymer, use may be made of the acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by Avecia-Neoresins, Dow Latex 432® by Dow chemical, Daitosol 5000 AD® or Daitosol 5000 SJ® by Daito Kasey Kogyo; Syntran 5760® by Interpolymer, Allianz Opt® by Rohm and Haas or else aqueous dispersions of polyurethane sold under the names Neorez R-981® and Neorez R-974 by Avecia-Neoresins, Avalure UR-405 , Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Avalure UR-445® and Sancure 2060® by Noveon, Impranil 85® by Bayer, Aquamere H-1511® by Hydromer; the sulphopolyesters sold under the brand name Eastman AQ® by Eastman Chemical Products, vinyl dispersions such as Mexomere PAM , aqueous dispersions of polyvinyl acetate such as "Vinybran®" by Nisshin Chemical or those sold by Union Carbide, aqueous dispersions of the vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryldimethylpropylmethacrylamido- ammonium chloride terpolymer such as Styleze W by ISP, aqueous dispersions of hybrid polyurethane/polyacrylic polymers such as those sold under the references "Hybridur " by Air Products or "Duromer " by National Starch, core/shell type dispersions: for example those sold by Atofina under the reference Kynar (core: fluoro; shell: acrylic) or else those described in document US 5 188 899 (core: silica; shell: silicone) and mixtures thereof.
Surfactant The composition according to the invention may comprise at least one surfactant, especially chosen from amphoteric, anionic, cationic or nonionic surfactants, used alone or as a mixture. The surfactants may be generally present in the composition in a proportion which may range, for example from 0.1 to 10% by weight, and preferably from 0.5 to 5% by weight.
According to the invention, an emulsifying surfactant suitably chosen in order to obtain a water- in-oil emulsion is generally used. In particular, an emulsifying surfactant having, at 25°C, an HLB balance (hydrophilic-lipophilic balance) , within the meaning of Griffin, of less than or equal to 8 may be used.
The HLB value according to Griffin is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.
These surfactants can be selected from non- ionic, anionic, cationic or amphoteric surfactants. Reference may be made to the document "Encyclopedia of Chemical Technology, Kirk-Othmer", volume 22, p. 333- 432, 3rd edition, 1979, Wiley, for the definition of the properties and emulsifying functions of surfactants, in particular p. 347-377 of this reference, for anionic, amphoteric and non-ionic surfactants . The surfactants preferably used in the composition according to the invention are selected from: a) non-ionic surfactants with an HLB of less than 8 at 25°C, optionally in combination with one or more non-ionic surfactants with an HLB of greater than 8 at 25°C, such as mentioned below, such as:
- esters and ethers of monosaccharides, such as sucrose stearates, sucrose cocoate, sorbitan stearate and their mixtures, for example Arlatone 2121®, sold by the company ICI, or Span 65V, from the company Uniqema;
- esters of fatty acids, in particular C8-C24 and preferably C16-C22 fatty acids, and of a polyol, in particular of glycerol or of sorbitol, such as glyceryl stearate, for example sold under the name Tegin M by the company Goldschmidt, glyceryl laurate, such as the product sold under the name Imwitor 312 by the company
HuIs, polyglyceryl-2 stearate, sorbitan tristearate and glyceryl ricinoleate;
- lecithins, such as soybean lecithins (for instance Emulmetik 100 J from Cargill, or Biophilic H from Lucas Meyer) ;
- oxyethylenated and/or oxypropylenated ethers (which can comprise from 1 to 150 oxyethylenated and/or oxypropylenated groups) of fatty alcohols (in particular of a C8-C24 and preferably C12-C18 alcohol) , such as the oxyethylenated ether of stearyl alcohol comprising 2 oxyethylene units (CTFA name "Steareth- 2"), such as Brij 72, sold by the company Uniqema;
- the cyclomethicone/dimethicone copolyol mixture sold under the name Q2-3225C by the company Dow Corning; b) non-ionic surfactants with an HLB of greater than or equal to 8 at 25°C, used alone or as a mixture; mention may in particular be made of:
- monosaccharide esters and ethers, such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols, for instance Montanov 68 from Seppic; - oxyethylenated and/or oxypropylenated glycerol ethers which may comprise from 1 to 150 oxyethylene and/or oxypropylene units;
- oxyethylenated and/or oxypropylenated ethers (which can comprise from 1 to 150 oxyethylene and/or oxypropylene units) of fatty alcohols, in particular Cs- C24 and preferably C12-C18 fatty alcohols, such as the oxyethylenated ether of stearyl alcohol comprising 20 oxyethylene units (CTFA name "Steareth-20") , such as Brij 78 sold by the company Uniqema, the oxyethylenated ether of cetearyl alcohol comprising 30 oxyethylene units (CTFA name "Ceteareth-30") and the oxyethylenated ether of the mixture of C12-C15 fatty alcohols comprising 7 oxyethylene units (CTFA name "C12-15 Pareth-7"), such as that sold under the name Neodol 25-7® by Shell Chemicals;
- esters of a fatty acid, in particular a C8-C24 and preferably C16-C22 fatty acid, and of polyethylene glycol (or PEG) (which can comprise from 1 to 150 oxyethylene units), such as PEG-50 stearate and PEG-40 monostearate, sold under the name Myrj 52P® by the company Uniqema;
- esters of a fatty acid, in particular a C8-C24 and preferably C16-C22 fatty acid, and of oxyethylenated and/or oxypropylenated glycerol ethers (which can comprise from 1 to 150 oxyethylene and/or oxypropylene units) , such as the polyoxyethylenated glyceryl monostearate comprising 200 oxyethylene units sold under the name Simulsol 220 TM® by the company SEPPIC; polyoxyethylenated glyceryl stearate comprising 30 oxyethylene units, such as the product Tagat S® sold by the company Goldschmidt, polyoxyethylenated glyceryl oleate comprising 30 oxyethylene units, such as the product Tagat O sold by the company Goldschmidt, polyoxyethylenated glyceryl cocoate comprising 30 oxyethylene units, such as the product Varionic LI 13 sold by the company Sherex, polyoxyethylenated glyceryl isostearate comprising 30 oxyethylene units, such as the product Tagat L® sold by the company Goldschmidt, and polyoxyethylenated glyceryl laurate comprising 30 oxyethylene units, such as the product Tagat I® from the company Goldschmidt;
- esters of a fatty acid, in particular a C8-C24 and preferably C16-C22 fatty acid, and of oxyethylenated and/or oxypropylenated sorbitol ethers (which can comprise from 1 to 150 oxyethylene and/or oxypropylene units) , such as the polysorbate 20 sold under the name
Tween 20 by the company Croda, such as the polysorbate 60 sold under the name Tween 60® by the company Uniqema;
- dimethicone copolyol, such as that sold under the name Q2-5220 by the company Dow Corning; - dimethicone copolyol benzoate, such as that sold under the name Finsolv SLB 101® and 201® by the company Fintex;
- copolymers of propylene oxide and of ethylene oxide, also known as EO/PO polycondensates, - and mixtures thereof.
The EO/PO polycondensates are more particularly copolymers composed of polyethylene glycol and polypropylene glycol blocks, such as, for example, polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates. These triblock polycondensates have, for example, the following chemical structure:
H- (O-CH2-CH2)a- (0-CH(CH3) -CH2)b- (0-CH2-CH2) a-OH,
in which formula a ranges from 2 to 120 and b ranges from 1 to 100.
The EO/PO polycondensates preferably have a weight-average molecular weight ranging from 1000 to 15 000 and better still ranging from 2000 to 13 000. Advantageously, said EO/PO polycondensates have a cloud point, at 10 g/1 in distilled water, of greater than or equal to 200C, preferably of greater than or equal to 600C. The cloud point is measured according to the ISO 1065 standard. Mention may be made, as EO/PO polycondensate which can be used according to the invention, of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the Synperonic names, such as Synperonic PE/L44® and Synperonic PE/F127®, by the company ICI. c) anionic surfactants such as: - salts of C16-C30 fatty acids, in particular amino salts such as triethanolamine stearate or 2- amino-2-methylpropane-l, 3-diol stearate; - salts of polyoxyethylenated fatty acids, in particular amino salts or alkali metal salts, and mixtures thereof;
- phosphoric esters and salts thereof, such as "DEA oleth-10 phosphate" (Crodafos N ION from the company Croda) or monopotassium monocetyl phosphate (Amphisol K from Givaudan or Arlatone MAP 160K from the company Uniqema) ;
- sulphosuccinates, such as "disodium PEG-5 citrate lauryl sulphosuccinate" and "disodium ricinoleamido MEA sulphosuccinate";
- alkyl ether sulphates, such as sodium lauryl ether sulphate;
- isethionates; - acylglutamates, such as "disodium hydrogenated tallow glutamate" (Amisoft HS-21 R sold by the company Ajinomoto) and sodium stearoyl glutamate
(Amisoft HS-Il PF sold by the company Ajinomoto), and mixtures thereof; - soybean derivatives, such as potassium soyate;
- citrates, such as glyceryl stearate citrate (Axol C 62 Pellets from Degussa) ;
- proline derivatives, such as sodium palmitoyl proline (Sepicalm VG from Seppic) , or the mixture of sodium palmitoyl sarcosinate, magnesium palmitoyl glutamate, palmitic acid and palmitoyl proline (Sepifeel One from Seppic) ;
- lactylates, such as sodium stearoyl lactylate (Akoline SL from Karlshamns AB) ;
- sarcosinates, such as sodium palmitoyl sarcosinate (Nikkol sarcosinate PN) or the mixture of stearoyl sarcosine and myristoyl sarcosine 75/25 (Crodasin SM from Croda) ; - sulphonates, such as sodium Ci4-I7 alkyl-sec- sulphonate (Hostapur SAS 60 from Clariant) ;
- glycinates, such as sodium cocoyl glycinate (Amilite GCS-12 from Ajinomoto). By way of examples of a cationic surfactant, mention may in particular be made of:
- alkylimidazolidiniums, such as isostearylethylimidonium ethosulphate, - ammonium salts, such as (C12-30 alkyl) tri (C1-4 alkyl) ammonium halides, for instance N, N, N-trimethyl-1- docosanaminium chloride (or behentrimonium chloride) .
The compositions according to the invention may also contain one or more amphoteric surfactants, for instance N-acylamino acids, such as
N-alkylaminoacetates and disodium cocoamphodiacetate, and amine oxides, such as stearamine oxide, or else silicone surfactants, for instance dimethicone copolyol phosphates, such as that sold under the name Pecosil PS 100® by the company Phoenix Chemical.
Hydrophilic gelling agent
The composition according to the invention may comprise a water-soluble gelling agent. The water-soluble gelling agents that can be used in the compositions according to the invention may be selected from: homo- or copolymers of acrylic or methacrylic acids or salts thereof and esters thereof, in particular the products sold under the names Versicol
(R) (R)
F or Versicol K by the company Allied Colloid, Utrahold 8® by the company Ciba-Geigy, polyacrylic acids of Synthalen K type; acrylic acid/acrylamide copolymers sold in the form of their sodium salt, under the name Reten by the company Hercules, the poly (sodium methacrylate) sold under the name Darvan No. 7 by the company Vanderbilt, the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F ® by the company Henkel; polyacrylic acid/alkyl acrylate copolymers of the Pemulen type ;
AMPS (polyacrylamidomethylpropanesulphonic acid partially neutralized with aqueous ammonia and highly crosslinked) sold by the company Clariant, AMPS/acrylamide copolymers of Sepigel® or Simulgel type sold by the company SEPPIC;
(crosslinked or uncrosslinked) polyoxyethylenated alkyl methacrylate/AMPS copolymers; proteins, such as proteins of plant origin for instance wheat or soybean protein; proteins of animal origin such as keratins, for example keratin hydrolysates and sulphonic keratins; cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and also quaternized derivatives of cellulose; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and of maleic anhydride, the copolymer of vinyl acetate and of crotonic acid, the copolymers of vinylpyrrolidone and of vinyl acetate, the copolymers of vinylpyrrolidone and of caprolactam, polyvinyl alcohol; optionally modified polymers of natural origin, such as : gum arabics, guar gum, xanthan derivatives and karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and derivatives thereof; shellac resin, sandarac gum, dammar resins, elemi gums and copal resins; deoxyribonucleic acids; mucopolysaccharides such as chondroitin sulphates; and mixtures thereof.
Some of these water-soluble gelling agents may also act as film-forming polymers.
The water-soluble gelling polymer may be present in the composition according to the invention at a solids content ranging from 0.01% to 5% by weight, preferably from 0.5% to 2% by weight relative to the total weight of the composition.
The compositions according to the invention may also contain at least one agent customarily used in cosmetics, chosen, for example, from reducing agents, softeners, anti-foaming agents, moisturizers, UV- screening agents, mineral colloids, fragrances, proteins or vitamins.
The above additives are, in general, present in an amount between, for each of them, 0.01 and 20% by weight relative to the weight of the composition.
Of course, a person skilled in the art will be sure to choose this or these optional additives so that the advantageous properties intrinsically linked to the formation of the coating according to the invention are not, or are not substantially impaired.
EXAMPLES
In the following examples, the viscosity of the compositions is measured according to the following protocol :
The viscosity of the composition is measured at 25°C using a Rheomat 180 (Lamy) equipped with an MS-Rl, MS-R2, MS-R3, MS-R4 or MS-R5 spindle chosen as function of the consistency of the composition, which rotates at a rotational speed of 200 rpm. The measurement is taken after rotating for 10 min. The viscosity measurements are carried out a maximum of 1 week after manufacture.
EXAMPLE 1 (according to the invention)
The following composition is produced:
Figure imgf000081_0001
Figure imgf000082_0002
Preparation of the polymer Ia:
100 g of GI3000 polymer sold by Nisso are dried at 800C, under vacuum overnight. This polymer is put into solution in 400 ml of anhydrous toluene. 25 μl of catalyst, dibutyltin dilaurate, are added to the reaction mixture. The medium is heated at 800C, and mixed until a homogeneous solution is obtained. 15 g of isocyanate-functionalized molecule with the following structure:
in solution in 300 ml of anhydrous toluene, are added under a controlled atmosphere at 400C. The reaction mixture is heated at 1000C and stirred at this temperature for 4 hours. The reaction is monitored by infrared spectroscopy, with monitoring of the complete disappearance of the peak characteristic of the isocyanates at 2260 cm"1. At the end of the reaction, 100 ml of ethanol are added in order to remove any trace of residual isocyanate, the mixture is filtered after having added isododecane in order to render the solution less viscous. The polymer solution is then directly stripped with isododecane.
The final polymer is obtained with a solids content of 16% in isododecane and is characterized by GPC (Mn = 6400 and polydispersity index of 1.85) and 1H NMR (spectrum in accordance with what is expected) .
Preparation of the composition:
phase A is heated at 1000C with stirring in a Rayneri agitator; phase C is introduced into phase A until a good dispersion is obtained; the bentone gel B is prepared and placed in a waterbath (60-700C); - B is introduced into the A+C mixture, homogenized for 5 minutes at high temperature, then extruded through a three-roll mill (3 passes) .
A composition is obtained that has a shiny homogeneous texture with good viscosity (95 poise) .
COMPARATIVE EXAMPLE
The following comparative composition is produced:
Figure imgf000083_0001
This comparative composition is prepared according to the same protocol as that of Example 1.
A composition is obtained having a shiny homogeneous texture with good viscosity (24 poise) .
The hold of the composition of Example 1 and of the comparative composition on the eyelashes is then tested by the protocols described below:
Figure imgf000084_0001
It is therefore observed that the composition 1 has a better dry rubbing resistance than the comparative composition, for an equivalent water and sebum resistance.
EXAMPLES 2 to 5 (according to the invention)
The following compositions are produced:
Figure imgf000084_0002
Figure imgf000085_0001
* = supramolecular polymer 2 to 5 as described below, in dispersion in isododecane
Preparation of polymer 2 : Supramolecular polymer obtained from GI2000 as compound A and from a graft of formula B in which L denotes an isophorone radical
106.1 g of GI2000 polymer sold by Nisso, in the presence of 22 mg of catalyst, dibutyltin dilaurate, are heated at 800C, under vacuum, for 2 hours. The temperature of the mixture is reduced to 200C, under argon, followed by addition of 10 ml of isododecane. 19.3 g of isophorone (4098-71-9) are added. The mixture is stirred for 16 hours at 200C, under a controlled atmosphere, then is heated to 1200C, followed by addition of 25 ml of propylene carbonate. 12 g of 6-methylisocytosine (3977-29-5) are added, resulting in a white homogeneous suspension. This suspension is heated to 1400C and is stirred at this temperature for 6 hours. The reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm"1) has completely disappeared. The mixture is then brought back down to 300C, and 400 ml of heptane, 200 ml of THF and 50 ml of ethanol are added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 2 with a solids content of 20%. The polymer is characterized by GPC (Mn = 7000 with an Ip of 2.05). Preparation of polymer 3: Supramolecular polymer obtained by GI3000 as compound A and from a graft of formula B in which L denotes an isophorone radical
99 g of GI3000 polymer sold by Nisso, in the presence of 22 mg of catalyst, dibutyltin dilaurate, are heated at 800C, under vacuum, for 2 hours. The temperature of the mixture is reduced to 200C, under argon. 11 g of IPDI (isophorone diisocyanate) (4098-71- 9) are added, and also 30 ml of isododecane. The mixture is stirred for 16 hours at 200C, under a controlled atmosphere, then is heated to 1200C, followed by the addition of 25 ml of propylene carbonate. 8.1 g of 6-methylisocytosine are added, resulting in a white homogeneous suspension. This suspension is heated to 1400C and is stirred at this temperature for 6 hours. The reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm"1) has completely disappeared. The mixture is then brought back down to 300C, and 1 litre of heptane is added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 3 with a solids content of 20%. The polymer is characterized by GPC
(Mn = 4200 with an Ip of 2.34).
Preparation of the polymer 4 : Supramolecular polymer obtained from GI3000 as compound A and from a graft of formula B in which L denotes a 4, 4' -dicyclohexylmethane radical 89 g of GI3000 polymer sold by Nisso, in the presence of 22 mg of catalyst, dibutyltin dilaurate, are heated at 800C, under vacuum for 2 hours. The temperature of the mixture is decreased to 200C, under argon. 11.6 of 4, 4' -dicyclohexylmethane (5124-30-1) are added, followed by the addition of 60 ml of isododecane. The mixture is stirred for 16 hours at 200C, under a controlled atmosphere, then is heated to 120°C, followed by the addition of 40 ml of propylene carbonate. 6.64 g of 6-methylisocytosine are added, resulting in a white homogeneous suspension. This suspension is heated to 1400C and stirred at this temperature for 8 hours. The reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm"1) has completely disappeared. The mixture is then brought back down to 300C, and 250 ml of isododecane, and also 500 ml of heptane, are added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 4 with a solids content of 22%. The polymer is characterized by GPC (Mn = 10700 with an Ip of 2.26).
Preparation of polymer 5: Supramolecular polymer obtained from GI2000 as compound A and from a graft of formula B in which L denotes a 4, 4' -dicyclohexylmethane radical
143.1 g of GI2000 polymer sold by Nisso, in the presence of 33 mg of catalyst, dibutyltin dilaurate, are heated at 800C, under vacuum, for 2 hours. The temperature of the mixture is reduced to 200C, under argon, followed by addition of 85 ml of isododecane. 30.8 g of 4, 4' -dicyclohexylmethane (5124-30-1) are added. The mixture is stirred for 16 hours at 200C, under a controlled atmosphere, then is heated to 1200C, followed by addition of 70 ml of propylene carbonate. 22.6 g of 6-methylisocytosine are added, resulting in a white homogeneous suspension. This suspension is heated to 1400C and is stirred at this temperature for 8 hours. The reaction is monitored by infrared spectroscopy, until the peak characteristic of the isocyanates (2250 cm"1) has completely disappeared. The mixture is then brought back down to 200C, and 700 ml of isododecane and also 500 ml of heptane are added to the mixture, before filtering through celite. Stripping with isododecane makes it possible to obtain the polymer 5 with a solids content of 20%. The polymer is characterized by GPC (Mn = 8400 with an Ip of 2.00). Preparation of the composition:
The protocol for preparing compositions 2 to 5 is identical to that for the composition of Example 1.

Claims

1. Method for making up or caring for eyelashes or eyebrows comprising the application to the eyelashes or the eyebrows of at least one layer of a cosmetic composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer, and at least one colorant.
2. Method according to Claim 1, characterized in that the polyalkene-based supramolecular polymer is derived from the condensation of at least one polyalkene polymer functionalized by at least one reactive group, with at least one graft functionalized by at least one reactive group capable of reacting with the reactive group or groups of the functionalized polyalkene polymer, said graft bearing at least one group capable of forming at least 3 H bonds.
3. Method according to Claim 2, characterized in that the functionalized polyalkene is of formula A:
HX-R-X'H
XH and X' H being reactive groups, with X and X', which are identical or different, chosen from O, S, NH, or NRa, Ra representing a Ci-Cε alkyl group,
R represents a homopolymer or a copolymer derived from one or more monounsaturated or polyunsaturated C2-C10 alkenes .
4. Method according to either one of Claims 2 and 3, characterized in that the functionalized polyalkene is chosen from hydroxyl-terminated poly (ethylene/ butylene)s, hydroxyl-terminated polybutadienes and hydroxyl-terminated polyisoprenes .
5. Method according to any one of Claims 2 to 4, characterized in that the graft has at least one ureidopyrimidone group.
6. Method according to one of Claims 2 to 5, characterized in that the reactive group or groups of the graft are isocyanate groups.
7. Method according to any one of Claims 2 to 6, in which the graft is of formula (B) :
Figure imgf000090_0001
L denoting a phenylene; 1, 4-nitrophenyl; 1, 2-ethylene; 1, 6-hexylene; 1, 4-butylene; 1, 6- (2, 4, 4-trimethyl- hexylene) ; 1, 4- (4-methylpentylene) ; 1,5- (5- methylhexylene) ; 1, 6- (6-methylheptylene) ; 1, 5- (2,2,5- trimethylhexylene) ; 1,7- (3, 7-dimethyloctylene) ; -isophorone-; 4, 4' -methylenebiscyclohexylene; tolylene; 2-methyl-1, 3-phenylene; 4-methyl-l, 3-phenylene or 4,4- biphenylenemethylene group.
8. Method according to one of the preceding claims, characterized in that the supramolecular polymer of the invention is of formula C:
Figure imgf000090_0002
with X and X' , which are identical or different, chosen from 0, S, NH, or NRa, Ra representing a Ci-Cε alkyl group;
R representing a homopolymer or a copolymer derived from one or more monounsaturated or polyunsaturated C2-
Cio alkenes; and L denoting a phenylene; 1, 4-nitrophenyl; 1,2- ethylene; 1, 6-hexylene; 1, 4-butylene; 1, 6- (2,4,4- trimethylhexylene) ; 1, 4- (4-methylpentylene) ; 1,5- (5- methylhexylene) ; 1, 6- (6-methylheptylene) ; 1, 5- (2,2,5- trimethylhexylene) ; 1,7- (3, 7-dimethyloctylene) ;
-isophorone- ; 4, 4' -methylenebiscyclohexylene; tolylene; 2-methyl-l, 3-phenylene; 4-methyl-l, 3-phenylene or 4,4- biphenylenemethylene group.
9. Method according to one of the preceding claims, characterized in that the continuous oily phase is present in the composition at a content ranging from 40 to 95%, preferably from 45 to 90%, preferably from 50 to 80%, and more particularly from 55 to 75% by weight relative to the total weight of the composition.
10. Method according to one of the preceding claims, characterized in that the continuous oily phase is chosen from volatile hydrocarbon-based oils.
11. Method according to one of the preceding claims, characterized in that the continuous oily phase is chosen from volatile branched alkanes having from 8 to 16 carbon atoms, and volatile linear alkanes comprising from 7 to 17 carbon atoms.
12. Method according to any one of the preceding claims, in which the colorant is chosen from organic pigments, inorganic pigments and pearlescent agents.
13. Method according to any one of the preceding claims, characterized in that the composition comprises at least one agent for structuring the continuous oily phase chosen from waxes, pastes, semi-crystalline polymers, lipophilic gelling agents, and mixtures thereof .
14. Method according to Claim 13, characterized in that the structuring agent is present in the composition at a content ranging from 5 to 80% by weight relative to the total weight of the composition, preferably from 7 to 75% and more preferably still from 10 to 55% by weight.
15. Method according to any one of the preceding claims, characterized in that the composition comprises less than 10% by weight of silicone oil (s) relative to the total weight of the composition, better still less than 5% by weight, or is even free of silicone oil.
16. Assembly (1) for making up or caring for eyelashes or eyebrows comprising:
- at least one composition comprising a continuous oily phase, at least one polyalkene-based supramolecular polymer and at least one colorant,
- and at least one applicator (2) of the composition, said applicator comprising means that make it possible to smooth and/or separate the eyelashes or eyebrows, especially in the form of teeth, bristles or other reliefs .
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US8932573B2 (en) 2013-03-22 2015-01-13 L'oreal Mascara compositions comprising a semicrystalline polymer, a silicone elastomer, and a hydrophilic gelling agent
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