WO2011083240A1

WO2011083240A1 - Cosmetic composition comprising functionalised capsules, cosmetic treatment method and capsules

Info

Publication number: WO2011083240A1
Application number: PCT/FR2010/052762
Authority: WO
Inventors: Sandrine Chodorowski-Kimmes; Valérie Jeanne-Rose
Original assignee: L'oreal
Priority date: 2010-01-05
Filing date: 2010-12-16
Publication date: 2011-07-14
Also published as: FR2954910A1; FR2954910B1

Abstract

The invention relates to: a cosmetic composition comprising capsules functionalised by groups that can form hydrogen bonds, a cosmetic treatment method using said composition, and the capsules.

Description

The present invention relates to a cosmetic composition comprising capsules functionalized with groups capable of forming hydrogen bonds, a cosmetic treatment method using said composition, as well as said capsules. It is known to use supramolecular polymers in cosmetics, in particular in applications such as colored sheathing of the hair or makeup, especially lipstick. These polymers are generally film-forming and lead to transparent deposits, comfortable to wear, shiny and not very sticky on the skin, the hair, the eyelash or the nail. The film-forming material is generally formed after evaporation of the solvent, by physical cross-linking through the hydrogen bonds between the different entities.

Upon application, the cosmetic properties obtained are acceptable; however, it appears that some of these materials are too sensitive to external aggressions, such as edible oils or sebum. Their behavior in time must be improved.

The object of the present invention is to provide a means for further improving the resistance over time and resistance to aggression by the fatty substances of supramolecular polymers or molecules.

The subject of the present invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, a capsule functionalized on the surface by at least one linking group, obtainable by reaction between:

at least one capsule carrying at least one reactive function, and

at least one linking group capable of establishing hydrogen bonds with one or more partner joining groups, each pairing of a linking group involving at least 3 hydrogen bonds, said linking group carrying at least one reactive function capable of to react with the reactive function carried by the capsule, said joining group further comprising at least one unit of formula (I) or (II) as defined below.

Another object of the invention is the capsules as such.

It has been found that, by mixing supramolecular polymers or molecules with functionalized capsules according to the invention, it is possible to obtain a film-forming deposit with improved holding properties after evaporation of the solvent.

In addition, it may also be envisaged to use the functional capsules only according to the invention, in the cosmetic composition; in fact, it is possible to prepare capsules comprising, inside the capsule, various cosmetic active ingredients, for example colored materials (pigments or dyes); in this case, the capsule can be used alone to bring color to the cosmetic compositions; the colored capsule can of course also be used in admixture with a polymer and / or a supramolecular molecule.

The capsules according to the invention can be obtained by reaction between:

on the one hand at least one previously formed capsule bearing at least one reactive function, especially at the surface, said reactive function being able to be nucleophilic or electrophilic, and

on the other hand, at least one linking group capable of establishing hydrogen bonds with one or more joining junction groups, each pairing of a junction group involving at least 3 hydrogen bonds, said junction group carrying at least one reactive function capable of reacting with the reactive function carried by said capsule, said joining group comprising at least one unit of formula (I) or (II) as defined below.

The previously formed capsule is preferably obtained by covalent, organic and / or inorganic polymerization. It can be obtained in particular by radical polymerization and / or by polycondensation. Mention may in particular be made of polyurethane, polyurea and / or polyurethane / polyurea capsules, crosslinked and obtained in particular by interfacial polycondensation; such capsules are described in particular in application EP1837073.

The non-functionalized capsules may in particular be obtained by reacting at least two reagents, one of isocyanate type and the other of alcohol and / or amine type, at least one of these reagents bearing at least 3 identical or different functions. different, chosen for one of the isocyanate functions, and for the other of the hydroxyl and amine functions. This reagent ensures in particular the function of crosslinking agent.

According to a first variant embodiment, the capsule can be obtained by reacting an alcohol-type and / or amine-type reagent comprising at least three identical or different functions, chosen from hydroxyl and amine functional groups, with an isocyanate type reactant comprising a alone, or even preferably two, isocyanate function (s).

According to another variant embodiment, the capsule can be obtained by reacting a tri- or polyisocyanate with an alcohol-type and / or amine-type reagent comprising only one, or even preferably two, identical or different function (s). - optionally, selected from hydroxyl and amine functions. Isocyanate-type reagents

The isocyanate-type reagents that can be used to form the capsules according to the invention may comprise one or more, and especially two or even three isocyanate functional groups. They may for example be chosen from aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic di- or poly-isocyanates such as those described, for example, by W. SIEFKEN in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.

According to one embodiment of the invention, the isocyanate type reactants may be chosen from diisocyanates, and in particular ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2 4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3-and 1,4-diisocyanate and any isomers, 4,4'-methylenebis (cyclohexyl) diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexane-hydrotolylene diisocyanate and any mixture of its isomers, hexahydro-1,3- and 1,4-phenylene diisocyanate, perhydro-1,4'- and 4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,6-tolylene diisocyanate and any mixture of its isomers, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 1,5-naphthylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate; amethylxylylene diisocyanate, m- and p-isocyanatophenylsulfonyl isocyanates, lysine alkyl ester diisocyanate wherein the alkyl is C ₁ -C 10 or 2-butyl-2-ethylpentamethylene diisocyanate, and mixtures thereof.

According to another embodiment of the invention, the isocyanate-type reagents can comprise at least three isocyanate functional groups and thus act as a crosslinking agent. They can then in particular be chosen from triisocyanates, for example triphenylmethane 4,4 ', 4 "-triisocyanate, or 4-isocyanatomethyl-1,8-octanemethylene diisocyanate or else from polyisocyanates, and in particular polyphenylpolymethylene polyisocyanates. perchlorinated aryl polyisocyanates, polyisocyanates having carbodiimide groups, polyisocyanates having allophanate groups, polyisocyanates having isocyanurate groups, polyisocyanates having acylated urea groups, polyisocyanates having bis-urea groups, polyisocyanates having isocyanates prepared by a telomerization reaction, the polyisocyanates having ether groups, the reaction products of the abovementioned isocyanates with acetals, the polyisocyanates containing polymeric fatty acid radicals and any mixture of the polyisocyanates mentioned therein. -above.

It is also possible to use, as the isocyanate type reactant, mixtures of said isocyanates, i.e. mixtures of aliphatic isocyanates, mixtures of aromatic isocyanates, mixtures of aliphatic isocyanates and aromatic compounds, and in particular mixtures which optionally comprise modified diphenylmethane diisocyanates. By way of illustration of these mixtures, mention may notably be made of hexamethylene diisocyanate biurethique, mixed with 4,4'-diphenylmethane isocyanate, and optionally with 2,4-diphenylmethane isocyanate and trimerized hexamethylene diisocyanate, in admixture with 4,4'-diphenylmethane diisocyanate, and optionally with 2,4-diphenylmethane diisocyanate.

It is also possible to use, as isocyanate type reactant, oligo- or poly-isocyanates which may be prepared from the di- or polyisocyanates mentioned above or their mixtures by binding them by means of urethane structures. , allophanate, urea, bisurea, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione.

Mention may also be made of di- or polyisocyanates, such as mixtures of diphenylmethane diisocyanate monomers and diphenylmethane diisocyanate oligomers (also called MDI polymers), 2,4-tolylene diisocyanate (2,4-TDI), 2, 4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -isocyantomethyl-1 methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI), which can more particularly be used for of isocyanate type reagent.

Thus, according to a preferred embodiment, the isocyanate-type reagents that can be used to form the capsules according to the invention are chosen from di- or polyisocyanates, and in particular mixtures of monomers diphenylmethane diisocyanates and oligomers diphenylmethane diisocyanates (MDI polymers), tolylene diisocyanate (TDI), and in particular 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, as well as their mixture, 4,4'-diphenylmethane diisocyanate (4,4'-MDI) or isophorone diisocyanate (IPDI).

The amount of isocyanate reagent to be used for carrying out the invention varies in the range customarily used in interfacial polyaddition processes.

Reagents of alcohol and / or amine type

The reagents of the alcohol and / or amine type that can be used to form the capsules according to the invention may comprise one or more, and especially two or even three identical or different functions chosen from hydroxyl and amine functions. They may for example be chosen from alcohol-type reagents, amine-type reagents and aminoalcohol-type reagents, used alone or as a mixture with one another. They preferably have a molecular weight ranging from 200 to 4000 g / mol.

The alcohol-type reagents may comprise one or more, and especially two or even three hydroxyl functions.

More particularly, these reagents may be a polyol. By polyol, we mean sense of the invention any organic molecule having in its chemical structure at least two hydroxyl groups -OH. The polyol may be, for example, a hydrocarbon compound, linear, branched or cyclic, saturated or unsaturated bearing at least two hydroxyl functions. The polyol may in particular be a (hydro) carbon compound preferably comprising from 2 to 300 carbon atoms, and bearing at least two hydroxyl groups, preferably from 2 to 10 hydroxyl groups. Preferably, it is a compound (hydro) carbon having 3 to 32 carbon atoms, and especially 4 to 18 carbon atoms, or even 4 to 12 carbon atoms. In particular, the polyol may be a compound having 2 to 18 carbon atoms and 2 to 6 hydroxyl functions.

According to one embodiment of the invention, the alcohol-type reagents can be chosen from diols and in particular glycol derivatives, such as diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol, propylene glycol and the like. hexylene glycol, isoprene glycol, butylene glycol, and pentylene glycol, or else butane diol, propane-1,2 diol, pentanediols and in particular 1,2-pentanediol, dodecanediol, or mixtures thereof.

According to another embodiment of the invention, the alcohol-type reagents may comprise at least three hydroxyl functions, and thus act as a crosslinking agent. They can then be chosen in particular from trimethylpropane, glycerol, pentaerythritol, 1,2,3-trihydroxyhexane, erythritol, arabitol, adonitol, dulcitol and sorbitol, polymers and copolymers. glycerol, such as, for example, hexaglycerol and diglycerol, glycerol derivatives, for example butyldiglycol, polyglyceryl-3-diisostearate and castor oil, glycol derivatives, for example polyethylene glycols and especially polyethylene glycols (PEG) having from 4 to 150 ethylene glycol units, such as PEG-400, PEG-600, PEG-800 and PEG-1200, polypropylene glycols, copolymers of ethylene glycol and propylene glycol or sugars such as glucose, fructose, xylose, trehalose, sucrose, maltose, lactose, and mixtures thereof. In a preferred manner, the alcohol-type reagents that are useful for acting as crosslinking agents are chosen from trimethylpropane, glycerol, pentaerythritol and sugars.

The polyol may also be a polyether alcohol of average molecular weight ranging from 150 to 600, such as polyethylene glycol 300 and polyglycerin 500.

It is also possible to use any mixture of the polyols mentioned above.

The polyol may also be selected from non-etherified polyols and unesterified polyols.

According to a preferred embodiment, the alcohol-type reactants are chosen from diols such as, for example, diethylene glycol, polyols such as, for example, polyethylene glycols, and in particular those having from 4 to 150 ethylene glycol units, or even mixtures of polyethylene glycols and diethylene glycol.

Amino-type reagents may comprise one or more, and two or even three amine functions.

According to one embodiment of the invention, the amine-type reagents can be chosen from diamines, for example diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, and the like. , 3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine or hydrate d hydrazine.

According to another embodiment of the invention, the amine-type reagents can comprise at least three amine functions and thus act as a crosslinking agent. They can then in particular be chosen from triamines, such as for example guanidine, diethylene triamine or 1,8-diamino-4-aminomethyloctane.

The amine reagents can also be used in the form of cetimines, ketazines or corresponding amine salts.

According to a preferred embodiment, the amine reactants comprise at least one amino group selected from the primary amine and secondary amino groups of the NHR type, wherein R represents an alkyl group having from 1 to 8 carbon atoms. The amino alcohol type reactants may comprise at least two different functions chosen from amine and hydroxyl functions.

According to one embodiment of the invention, the aminoalcohol type reactants may be difunctional, that is to say comprise two functions, namely an amine function and a hydroxyl function.

According to another embodiment of the invention, the aminoalcohol type reactants can comprise at least three functions, and thus act as a crosslinking agent. They may for example comprise a single hydroxyl function (respectively amine) and at least two amine functions (respectively hydroxyl), or two hydroxyl functions (respectively amine) and at least one amine function (respectively hydroxyl).

As the aminoalcohol type reagent that can be used in the present invention, mention may notably be made of ethanolamine and triethanolamine.

As specified above, the capsules according to the invention can, according to a first alternative, be obtained by reacting at least one diisocyanate with at least one reagent of alcohol and / or amine type carrying at least three functions, identical or different, chosen from the hydroxyl and amine functions, and acting as a crosslinking agent, optionally in the presence of at least one diol and / or at least one diamine and / or at least one difunctional amino-alcohol.

Preferably, the isocyanate type reactant is a diisocyanate chosen from mixtures of diphenylmethane diisocyanate monomers and of diphenylmethane diisocyanate oligomers (MDI polymers), tolylene diisocyanate (TDI) and especially 2,4-tolylene diisocyanate and 2-diisocyanate. , 6-tolylene diisocyanate, and their mixture, 4,4'-diphenylmethane diisocyanate (4,4'-MDI) or isophorone diisocyanate (IPDI).

As reagent acting as crosslinking agent, it is possible, for example, to use the triols, polyols, triamines and polyamines described above. Preferably, the reagent acting as crosslinking agent is chosen from triols, for example trimethylolpropane, glycerol and pentaerythritol, and polyols, such as, for example, sugars such as glucose, fructose, xylose, trehalose, sucrose, maltose and lactose. Preferably, the diamines comprise at least one amino group selected from the primary amino groups and secondary amines of -NHR type, wherein R represents an alkyl group having from 1 to 8 carbon atoms.

Preferably, the capsules are obtained by interfacial polymerization. Interfacial polycondensation is a polymerization reaction that occurs at the interface of two immiscible liquids, at least one of which contains a suitable polyfunctional reagent. Preferably, at least one monomer and / or reagent is soluble in the first phase, and at least one monomer and / or reagent is soluble in the second phase, immiscible with said first phase

In the case where this reaction is carried out without removing secondary products, it is also called interfacial polymerization.

This reaction may in particular be carried out in an emulsion, in particular biphasic or multiphasic emulsion, at the interface between the immiscible phases. The reaction can be carried out in an oil-in-water or water-in-oil emulsion, or in a multiple emulsion of the E / H / E or H / E / H type. According to a preferred embodiment, the emulsion is of the oil-in-water type.

The capsules are crosslinked. This crosslinking can be obtained by reaction of the polymer chains with a reagent of functionality at least equal to 3, called crosslinking agent.

There are two types of capsules:

those of the reservoir type in which the polymeric matrix forming the capsule is a solid envelope, also called bark, of variable thickness, delimiting a core in which can be imprisoned an asset called 'encapsulated', or which can be empty;

those of matrix type, also called microspheres, in which the polymeric matrix is a continuous network, into which an "encapsulated" active agent may be dispersed. The capsules according to the invention, before functionalization, preferably have a size of between 0.5 and 1200 microns, in particular between 0.6 and 30 microns.

In a particular embodiment, the capsules may comprise an active ingredient encapsulated.

Said encapsulated active agent may in particular be a dyestuff, in particular a pigment, that is to say a solid, white or colored particle, naturally insoluble in the hydrophilic and lipophilic liquid phases usually used in cosmetics, or rendered insoluble by formulation in the form of lacquer for example. Said pigment is preferably at least partly organic or even totally organic. It can also be mineral.

The capsules preferably comprise 0.5 to 80% by weight, especially 1 to 70% by weight, especially 20 to 65% by weight, or even 30 to 60% by weight of pigment relative to the total weight of the capsule.

Mention may in particular be made of carbon black, pigments of D & C, FD & C type and their lacquers, and especially those known under the names D & C Blue No. 4, D & C Brown No. 1, D & C Green No. 5, D & C Green No. 6 , D & C Orange # 4, D & C Orange # 5, D & C Orange # 10, D & C Orange # 1 1, D & C Red # 6, D & C Red # 7, D & C Red # 17, D & C Red # 21, D & C Red # 22, D & C Red # 27, D & C Red # 31, D & C Red # 33, D & C Red # 34, D & C Red # 36, D & C Purple No. 2, D & C Yellow No. 6, FDC Blue 1, D & C Yellow No. 7, D & C Yellow No. 8, D & C Yellow No. 10, and D & C Yellow No. 11; as well as their lacquers, in particular lacquers based on barium, strontium, calcium, aluminum, or diketopyrrolopyrroles.

Mention may also be made, as dyestuff, of inorganic pigments, optionally surface-treated and / or coated, and especially of titanium dioxide, zirconium or cerium oxides, zinc oxides, iron oxides (black, yellow or red). or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metallic powders such as aluminum powder, copper powder, gold powder and powder of money.

It is also possible to mention optical effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas. said substrate being coated or not with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide.

Mention may also be made among dyestuffs, nacres, that is to say iridescent pigments especially produced by some shellfish in their shell, or synthesized. The nacres can be chosen from mica coated with titanium or bismuth oxychloride, micatitane coated with iron oxides, mica titanium coated with ferric blue or chromium oxide, micatitane coated with an organic pigment, as well as pearlescent pigments based on bismuth oxychloride.

It is also possible to use interferential pigments, in particular liquid crystal or multilayer pigments; or pigments having a microsphere-like structure of silica containing iron oxide.

The dyestuffs may also be (soluble) dyes, among which may be mentioned those listed in Annex IV, such as D & C red27, D & C red21, D & C orange No. 5, D & C yellow 1 1, D & C green 6, D & C violet 2, Red 4, Red 6, D & C Red22, Red 28, D & C Red30, Red 33, Orange 4, Yellow 5, Yellow 6, D & C yellow No. 8, D & C Green 5, FDC Green 3, FDC Blue 1; Beta Vulgaris; Bismuth Oxychloride; Bromocresol Green; Bromothymol Blue; Paprika oleoresin / Capsorubin; Caramel; Cl 10006; Cl 10020; Cl 10316, CI 1 1920; Cl 12010; Cl 12150; Cl 12700; Cl 13015; Cl 14270; Cl 14700; Cl 14720; Cl 14815; Cl 15620; Cl 15980; Cl 15985; Cl, 16035; Cl 16185; Cl 16230; Cl 16255; Cl 16290; Cl 17200; Cl 18050; Cl 18130; Cl 18690; Cl 18736; Cl 18820; Cl 18965; Cl 19140; Cl 20170; Cl 20470; Cl 21230; Cl 24790; Cl 26100; Cl 27290; Cl 27755; Cl 28440; Cl 40800; Cl 40820; Cl 40825; Cl 40850; Cl 42045; Cl 42051; Cl 42053; Cl 42080; Cl 42090; Cl 42100; Cl 42170; Cl 42510; Cl 42520; Cl 42735; Cl 44045; Cl 44090; Cl 45100; Cl 45190; Cl 45220; Cl 45350; Cl 45370; Cl 45370; Cl 45380; Cl 45380; Cl 45380; Cl 45396; Cl 45405; Cl 45410; Cl 45425; Cl 45430; Cl 47000; Cl 47005; Cl 50325; Cl 50420; Cl 59040; Cl 60725; Cl 60730; Cl 61565; Cl 61570; Cl 61585; Cl 62045; Cl 73015; Cl 73900; Cl 75100; Cl 75120; Cl 75125; Cl 75130; Cl 75135; Cl 75300; Cl 75810; Cl 77713; Cl 77820; Cl 77891; Cl 77947; Cl 40215; Cl 74180; Cl 75470; ACID RED 195; Cl 19140; Cl 45370; Cl 47005; Cl 75810; Cl 75810; riboflavin; and their mixtures.

The encapsulated asset may also be a gas, such as air, carbon dioxide or nitrogen; and / or a constituent chosen from cosmetic oils and waxes, in particular mineral, animal, vegetable or synthetic waxes, and cosmetic active ingredients such as vitamins, UV filters, perfumes, moisturizers and skincare active ingredients.

In general, one can consider any type of encapsulable asset. The encapsulated asset can be trapped in the bark or in the heart of the capsule, when the latter is of reservoir type.

The capsules may be prepared by interfacial polymerization, in particular as described in EP1837073. They may also be of polyurethane, polyester, polyamide, polycarbonate, polysiloxane, polysaccharide, cellulose, polyether, polyamine, polypeptide, protein, polyvinyl alcohol and polyvinyl acetate type.

They can also be prepared by radical polymerization and be of the C 1 -C 16 alkylpoly (meth) acrylate type, in particular PMMA; or in polystyrene or their copolymers.

The capsules may be copolymers of the above types, or mixtures of these polymers.

The capsules may also be totally or partially inorganic, for example silica, ΤΊΟ2, ZrO2, alumina, SnO2, iron oxide, or mixtures thereof; they may also be of clay type, sepiolite, montmorillonite, or mixtures thereof.

The capsules may also combine organic polymers with inorganic materials.

The preformed capsule thus prepared, by covalent polymerization, organic or inorganic, must carry on the surface at least one reactive function, which may be nucleophilic or electrophilic, and in particular selected from OH, C = O (carbonyl) and NH ₂ , and which must be able to react with a complementary function carried by the joining group.

In the end, the functionalized capsules according to the invention therefore comprise at least one part coming from the preformed capsule, and at least one part coming from the joining group, said part comprising at least one unit of formula (I) or (II). In particular, said parts are connected by a covalent bond, in particular formed during the reaction between the reactive functions carried by the preformed capsule and the reactive functions carried by the joining group. The joining group that can be used to prepare the functionalized capsule according to the invention carries at least one reactive function and comprises at least one unit of formula (I) or (II) as defined below.

The reactive functional group may be in particular of the isocyanate or imidazole type, capable of reacting with the reactive functions of the capsule, in order to form a covalent bond, in particular of the urea or urethane type, between said capsule and said joining group.

Said linking group is capable of establishing H bonds with one or more joint joining groups of identical or different chemical nature, each pairing of a joining group involving at least 3 H (hydrogen) bonds, preferably at least 4 H bonds, preferably 4 H bonds. For the purpose of the invention, the term "linking group" means any functional group comprising H bond donor or acceptor groups and capable of establishing at least three bonds. H, preferably at least 4 H bonds, preferably 4 H bonds, with a mating partner group, identical or not. For the purposes of the invention, the term "partner joining group" means any joining group capable of establishing H bonds with one or more joining groups of the same or another polymer according to the invention. The joining groups can be of identical or different chemical nature. If they are identical, they can then establish H links between them and are then called self-complementary join groups. If they are different, they are chosen so that they are complementary to the H interactions. Said linking group, bearing isocyanate groups, can therefore be schematized (G) - (NCO) _p , p being a non-zero integer, preferably equal to 1 or 2.

The joining group also comprises at least one monovalent unit of formula (I) and / or at least one divalent unit of formula (II), as defined below:

(l) (he)

in which :

- R1 and R3, identical or different, represent a divalent carbon radical Choiseul if from (i) a linear alkyl group or branched C1-C32, (ii) a cycloalkyl group having ₄ -Ci6 and (iii) aryl in C ₄ -C 16; optionally comprising 1 to 8 heteroatoms selected from O, N, S, F, Si and P; and / or optionally substituted with an ester, amide or a C1-C12 alkyl radical; or a mixture of these groups;

R 2 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, C 1 -C 32 hydrocarbon (alkyl) radical, which may comprise one or more heteroatoms chosen from O, N, S; , F, Si and P. In particular, the radical R1 may especially be:

a linear or branched C2-C12 divalent alkylene group, in particular a 1,2-ethylene, 1,6-hexylene, 1,4-butylene or 1,6 (2,4,4-trimethylhexylene) group, 1,4- (4-methylpentylene), 1,5- (5-methylhexylene), 1,6- (6-methylheptylene), 1,5- (2,2,5-trimethylhexylene), 1,7- , 7-diméthyloctylène).

a divalent C 4 -C 12 cycloalkylene or arylene group, especially chosen from the following radicals: isophorone, tolylene, 2-methyl-1,3-phenylene, 4-methyl-1,3-phenylene; 4,4'-méthylènebiscyclohexylène;4,4-bisphenylenemethylene; or structure:

By -isophorone- is meant the divalent radical of structure:

Preferably, R 1 represents -isophorone-, - (CH ₂ ) 6- or 4,4'-methylenebiscyclohexylene. In particular, the radical R2 can in particular be H, or else:

a C ₁ -C ₃ , in particular C ₁ -C 16 or even C ₁ -C ₁₀ alkyl group;

a C ₄ -C ₁₂ cycloalkyl group;

a C ₄ -C ₁₂ aryl group;

an aryl (C ₄ -C 12) alkyl group having _{1 to 18} carbon atoms

- alkoxy, Ci-C _4;

an arylalkoxy group, in particular an aryl (CrC ₄ ) alkoxy group;

a C ₄ -Ci ₂ heterocycle

or a combination of these radicals, which may optionally be substituted by an amino, ester and / or hydroxy function.

Preferably, R 2 represents H, CH ₃ , ethyl, C 13 H 27, C ₇ H 15, phenyl, isopropyl, isobutyl, n-butyl, tert-butyl, n-propyl or -CH (C ₂ H ₅ ) (C ₄ H ₉ ).

Preferably, R3 represents a divalent radical -R'3-OC (O) -NH-R'4- in which R'3 and R'4, identical or different, represent a divalent carbon radical chosen from a linear alkyl group or branched C ₁ -C 3 ₂ or a cycloalkyl group having ₄ -Ci6 aryl or C ₄ -Ci6; or their mixture.

In particular, R '3 and R' 4 may represent methylene, 1,2-ethylene, 1,6-hexylene, 1,4-butylene, 1,6-di (2,4,4-trimethylhexylene), 1,4 (4-methylpentylene), 1,5-5- (5-methylhexylene); 1, 6- (6-methylheptylene); 1,5- (2,2,5-trimethylhexylene), 1,7- (3,7-dimethyloctylene); 4,4'-méthylènebiscyclohexylène; 2-methyl-1,3-phenylene; 4-methyl-1,3-phenylene; 4,4'-bisphénylèneméthylène; 1,2-tolylene, 1,4-tolylene, 2,4-tolylene, 2,6-tolylene; 1,5-naphthylene; tetramethylxylylene; isophorone.

In particular, R'3 may represent a C1-C4 alkylene, in particular 1, 2-ethylene.

Preferably, R'4 may represent the divalent radical derived from isophorone. In particular, R3 can be of structure:

In a particularly preferred manner, in formula (I), one can have

- Ri = -isophorone-, R2 = methyl, which leads to the unit of formula:

- (CH ₂ ) 6-, R2 = methyl, which leads to the formula unit

- (CH ₂ ) 6-, R 2 = isopropyl, which leads to the formula unit

R1 = 4,4'-methylenebiscyclohexylene and R2 = methyl, which leads to the unit of formula:

Particularly preferably, in the formula (II), R 1 represents the radical - isophorone-, R 2 = methyl and R 3 = - (CH ₂ ) ₂ OCO-NH-isophorone-, which leads to the divalent unit of formula:

Junction groups carrying a single isocyanate function may be of formula:

wherein R1 and R2 are as defined above; and especially :

R 1 represents -isophorone-, - (CH ₂ ) ₆ -, -CH ₂ CH (CH 3) -CH ₂ -C (CH 3) 2 -CH ₂ -CH ₂ , 4,4'-methylenebiscyclohexylene, 2-methyl-1,3 phenylene; and or

R 2 represents H, CH ₃ , ethyl, C 13 H 27, C 7 H 15, phenyl, isopropyl, isobutyl, n-butyl, tert-butyl, n-propyl or -CH (C ₂ H ₅ ) (C ₄ H ₉ ).

Preferably, the joining groups can be chosen from the following groups:

The joining groups carrying two isocyanate functional groups can be of formula:

wherein R1, R2 and R3 are as defined above, and in particular:

R1 represents -isophorone-, - (CH ₂ ) ₂ -, - (CH ₂ ) ₆ -, -CH ₂ CH (CH 3) -CH ₂ -C (CH ₃ ) 2 -CH ₂ -CH ₂ , 4,4'- methylenebiscyclohexylene, 2-methyl-1,3-phenylene; and or

- R2 represents H, CH _3, ethyl, C13H27, C 7 H 15, phenyl, isopropyl, isobutyl, n-butyl, tert-butyl, n-propyl, or -CH (C 2 H ₅₎ (C ₄ H _9); and or

- R3 represents a divalent radical -R'3-OC (O) -NH-R'4- in which R'3 and R'4, identical or different, represent a divalent carbon radical chosen from a linear or branched alkyl group; C1-C30 cycloalkyl or C ₄ -Ci2 aryl or C ₄ -C _2; or their mixtures; and in particular R'3 represents a C1-C4 alkylene, especially 1, 2-ethylene and R'4 represents the divalent radical derived from isophorone. A particularly preferred joining group is that of formula

Among the junction groups carrying an imidazole group, there may be mentioned the following compound:

According to a particular embodiment of the invention, the linking groups can be attached to the capsule via the functionalization of the linking group by an isocyanate or imidazole.

According to another embodiment, it is possible to make the reverse reaction by prefunctionalizing the capsule with a diisocyanate.

In a ^1st mode of preparation, the capsule functionalized according to the invention can result from the chemical reaction between a preformed capsule carrying a reactive functional group and a linking group bearing a complementary reactive function. The capsule may be prepared by the methods usually employed by those skilled in the art to form a urethane linkage, between the free OH functions of the capsule and the isocyanate functions carried by the linking group. As an illustration, a general method of preparation consists of:

heating the capsule carrying at least one reactive functional group, in particular OH, at a temperature that may be between 25 and 140 ° C., in particular between 60 ° C. and 130 ° C .;

add the junction group carrying the reactive functions, in particular isocyanate;

optionally stirring the mixture, under a controlled atmosphere, at a temperature of the order of 100-130 ° C .; for 1 to 24 hours;

- follow by infrared spectroscopy, the disappearance of the isocyanate characteristic band (between 2500 and 2800 cm-1) so as to stop the reaction to the total disappearance of the peak, then allow the final product to return to ambient temperature.

The reaction may be carried out in the presence of a solvent, especially trahydrofuran, tetrahydrofuran, toluene or butyl acetate. It is also possible to add a conventional catalyst for urethane bond formation. By way of example, mention may be made of dibutyl tin dilaurate. According to the ^2nd embodiment, the reaction may comprise the steps of: (i) functionalizing the capsule by a diisocyanate, and

(iia) or reaction with 6-methylisocytosine:

(iib) or reaction with 5-hydroxyethyl-6-methyl isocytosine:

An illustration of such a reaction is given in FOLMER et al., Adv. Mater, 12, 874-78 (2000).

It has been found that the use of the capsules according to the invention can lead, after application of the composition to keratin materials, to the formation of a supramolecular polymer in the form of a physically crosslinked network, in particular through hydrogen bonds, generally in the form of a film, and having a very good mechanical strength.

For the purposes of the invention, the term "supramolecular polymer" means a polymer chain or network formed of the capsule assembly according to the invention with at least one other capsule according to the invention, identical or different, each semblage comprising at least one pair of paired join groups.

Thus, the supramolecular polymer will have physical cross-linking points provided by the H bonds between these pairs of joining groups. The physical crosslinking will ensure the maintenance and persistence of the cosmetic effect in a manner similar to the chemical crosslinking, while allowing reversibility, that is to say the possibility of completely eliminating the deposit.

The capsules according to the invention can advantageously be used in a cosmetic composition which moreover comprises a cosmetically acceptable medium, that is to say compatible with keratin materials such as the skin of the face or body, the eyelashes, the eyebrows. , lips and nails.

The amount of capsules present in the compositions of course depends on the type of composition and the desired properties and can vary within a very wide range, generally between 5 and 80% by weight, preferably between 10 and 75%. by weight, in particular between 20 and 70% by weight, or even between 25 and 65% by weight, and better still between 30 and 60% by weight, relative to the weight of the final cosmetic composition.

The composition may then comprise, according to the intended application, the usual constituents for this type of composition.

The composition according to the invention may advantageously comprise a liquid fatty phase, which may constitute a solvent medium for the polymers according to the invention, and which may comprise at least one compound chosen from oils and / or solvents of mineral, animal, vegetable or synthetic, carbonated, hydro- carbonaceous, fluorinated and / or silicone, volatile or nonvolatile, singly or in mixture in that they form a homogeneous and stable mixture and are compatible with the intended use.

For the purposes of the invention, the term "volatile" is intended to mean any compound capable of evaporating on contact with keratin materials, or the lips, in less than one hour at ambient temperature (25 ° C.) and atmospheric pressure ( 1 atm). In particular, this volatile compound has a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular ranging from 0.13 Pa to 40 000 Pa (10 ^-3 to 300 mmHg), in particular ranging from 1.3 Pa. at 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg), whereas by 'non-volatile' a compound remaining on the keratin materials or the lips at ambient temperature and atmospheric pressure, at least one hour and in particular having a vapor pressure of less than 10 ^-3 mmHg (0.13 Pa).

Preferably, the physiologically acceptable medium of the composition according to the invention may comprise, in a liquid fatty phase, at least one oil and / or a solvent which may be chosen from, alone or as a mixture: 1 / esters of monocarboxylic acids with monoalcohols and polyalcohols; advantageously, said ester is a C12-C15 alkyl benzoate or has the following formula: R'rCOO-R'2 where:

R '1 represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably 7 to 19 carbon atoms, optionally comprising one or more ethylenic double bonds, optionally substituted and whose hydrocarbon chain may be interrupted by one or more a plurality of heteroatoms selected from N and O and / or one or more carbonyl functions, and

R'2 represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably of 3 to 30 carbon atoms and better still of 3 to 20 carbon atoms, optionally comprising one or more ethylenic double bonds, optionally substituted and wherein the hydrocarbon chain can be interrupted by one or more heteroatoms selected from N and O and / or one or more carbonyl functions.

By "optionally substituted" is meant that R'i and / or R'2 may carry one or more substituents selected, for example, from groups comprising one or more heteroatoms selected from O and / or N, such as amino, amino , alkoxy, hydroxyl.

Examples of the R'i groups are those derived from the preferably higher fatty acids selected from the group consisting of acetic, propionic, butyric, caproic, caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic acids. , isostearic, arachidic, behenic, oleic, linolenic, linoleic, oleostearic, arachidonic, erucic, and mixtures thereof. Preferably, R'i is an unsubstituted branched alkyl group of 4 to 14 carbon atoms. carbon, preferably from 8 to 10 carbon atoms and R ₂ is an unsubstituted branched alkyl group of 5 to 15 carbon atoms, preferably 9 to 11 carbon atoms.

Mention may in particular be mentioned, preferably, the esters of Cs-C ₄ 8, optionally incorporating in their hydrocarbon chain one or more heteroatoms from N and O and / or one or more carbonyl functions; and more particularly purcellin oil (cetostearyl octanoate), isononyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyl-2 stearate -dodecyl, octyl-2-dodecyl erucate, isostearyl isostearate, C12-C15 alcohol benzoate, hexyl laurate, diisopropyl adipate; and the heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, for example of fatty alcohols such as propylene glycol dioctanoate, as well as isopropyl N-lauroyl sarcosinate (in particular Eldew-205SL from Ajinomoto); hydroxylated esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; branched C8-C16 esters, especially isohexyl neopentanoate.

21 hydrocarbonaceous vegetable oils with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids may have varied chain LON gueurs from C ₄ to C 2 _4, these chains possibly being linear or branched, saturated or unsaturated; these oils include wheat germ, maize, sunflower, shea, castor oil, sweet almond, macadamia, apricot, soya, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape seed or blackcurrant, unripe, millet, barley, quinoa, olive, rye, safflower, bancoulier, passionflower, muscat rose, jojoba, palm, calophyllum; or the triglycerides of caprylic / capric acids such as those sold by the company Stearinerie Dubois or those sold under the names "Miglyol 810®", "812®" and "818®" by the company Dynamit Nobel.

3 / alcohols, and especially C6-C32 monoalcohols, in particular C12-C26, such as oleic alcohol, linoleic alcohol, linolenic alcohol, isostearyl alcohol, 2-hexyldecanol, 2 -butyloctanol, 2-undecylpentadecanol and octyldodecanol;

4 / linear or branched hydrocarbon oils, volatile or not, of synthetic or mineral origin, which may be chosen from hydrocarbon-based oils having from 5 to 100 carbon atoms, and in particular petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam, squalane, perhydrosqualine and their mixtures.

It is more particularly possible to mention linear, branched and / or cyclic C5-C48 alkanes, and preferably branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also called isoparaffins); particular decane, heptane, dodecane, cyclohexane; as well as isododecane, isodecane, isohexadecane.

5 / silicone oils, volatile or non-volatile;

Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, in particular those having a viscosity of less than 8 centistokes, and especially having from 2 to 10 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups. having from 1 to 22 carbon atoms; and in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, rheptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethylsiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, methylhexyldimethylsiloxane and mixtures thereof.

The non-volatile silicone oils that may be used according to the invention may be polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, and phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

Preferably, the physiologically acceptable medium of the composition according to the invention comprises, in a liquid fatty phase, at least one oil and / or a solvent chosen from, alone or as a mixture, isododecane, Parleam, the isononanoate of isononyl, octyldodecanol, phenyl trimethicone, C12-C15 alkyl benzoates, butyl and ethyl acetates, and / or D5 (decamethylcyclopentasiloxane).

The liquid fatty phase may further comprise additional oils and / or solvents, which may be chosen from, alone or as a mixture:

fluorinated oils such as perfluoropolyethers, perfluoroalkanes such as perfluorodecalin, perfluorodamantanes, monoesters, diesters and triesters of perfluoroalkylphosphates and fluorinated ester oils;

- oils of animal origin;

- ethers, C 6 to C ₄ o, especially C10-C40; propylene glycol ethers which are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether;

- C8-C32 fatty acids, such as oleic acid, linoleic acid, linolenic acid and mixtures thereof.

- Bifunctional oils, comprising two functions selected from ester and / or amide and comprising from 6 to 30 carbon atoms, in particular 8 to 28 carbon atoms, more preferably 10 to 24 carbons, and 4 heteroatoms selected from O and N; of preferably the amide and ester functions being in the chain;

ketones which are liquid at ambient temperature (25 ° C.), such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone;

aldehydes which are liquid at room temperature, such as benzaldehyde or acetaldehyde;

The liquid fatty phase may represent 1 to 90% by weight of the composition, in particular from 5 to 75% by weight, in particular from 10 to 60% by weight, or even 25 to 55% by weight, of the total weight of the composition. .

The composition according to the invention may advantageously comprise a thickening agent which may in particular be chosen from:

- the particular hydrophobic silicas, such as those described in EP-A-898960, for example, under the references "Aerosil R812 ^®" by Degussa, "CAB-O-SIL TS-530 ^®", "CAB O-SIL TS-610 ^® "," CAB-O-SIL TS-720 ^® "by the company Cabot," AEROSIL R972 ^® "," AEROSIL R974 ^® "by Degussa;

clays, such as montmorillonite, modified clays, such as benzones, stearalkonium hectorite, stearalkonium bentonite,

polysaccharide alkyl ethers (in particular in which the alkyl group contains from 1 to 24 carbon atoms, preferably from 1 to 10, better still from 1 to 6, and more particularly from 1 to 3, such as those described in EP-A); A-898958.

The amount of thickening agent in the composition according to the invention may range from 0.05 to 40% by weight, relative to the total weight of the composition, preferably from 0.5 to 20% and better still from 1 to 15%. in weight.

The composition according to the invention may also comprise at least one wax of vegetable, animal, mineral, synthetic or even silicone origin.

In particular, hydrocarbon waxes such as beeswax can be mentioned alone or as a mixture; Carnauba wax, Candellila wax, Ouricoury wax, Japan wax, cork fiber wax or sugar cane wax; paraffin waxes of lignite; microcrystalline waxes; lanolin wax; the wax of Montan; ozokerites; polyethylene waxes; waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils, fatty esters and concrete glycerides at 25 ° C. It is also possible to use silicone waxes, among which mention may be made of alkyls, alkoxys and / or polymethylsiloxane esters.

The amount of wax in the composition according to the invention may range from 0.1 to 70% by weight, relative to the total weight of the composition, preferably from 1 to 40% by weight, and better still from 5 to 30% by weight. weight.

The composition according to the invention may also comprise one or more dyestuffs chosen from pulverulent compounds such as pigments, fillers, pearlescent agents and flakes, and / or liposoluble or hydrophilic dyes. soluble.

The dyestuffs, in particular pulverulent, may be present in the composition in a content of from 0.01 to 50% by weight, relative to the weight of the composition, preferably from 0.1 to 40% by weight, or even from 1 to 30% by weight. By pigments, it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

By nacres, it is necessary to understand particles of any iridescent form, in particular produced by certain molluscs in their shell or else synthesized.

The pigments may be white or colored, inorganic and / or organic, interferential or not. Among the inorganic pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.

The pearlescent pigments may be chosen from white pearlescent pigments such as titanium-coated mica or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with, in particular, blue. ferric or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

The fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, powders of nylon and of polyethylene, ροΐν-β-alanine and polyethylene, Teflon, lauroyl-lysine, starch, nitrile and the like. boron, tetrafluoroethylene polymer powders, hollow microspheres such as Expancel (Nobel Industry), polytrap (Dow Corning), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate. Fat-soluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, Orange DC 5 , yellow quinoline. They may represent 0.01 to 20% of the weight of the composition and better still 0.1 to 6%.

The water-soluble dyes are for example beet juice, methylene blue and may represent 0.01 to 6% of the total weight of the composition.

The composition may further include other ingredients commonly used in cosmetic compositions. Such ingredients may be chosen from antioxidants, perfumes, essential oils, preservatives, cosmetic actives, moisturizers, vitamins, ceramides, sunscreens, surfactants, gelling agents, leveling agents, wetting agents, dispersing agents, defoamers, neutralizers, stabilizers, polymers and in particular liposoluble film-forming polymers, and mixtures thereof. Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition for use according to the invention are not, or not substantially, altered by the addition envisaged. The compositions according to the invention may be in any acceptable and customary form for a cosmetic composition. They can therefore be in the form of a suspension, a dispersion including oil in water with vesicles; an organic or oily solution optionally thickened or even gelled; an oil-in-water, water-in-oil, or multiple emulsion; a gel or a mousse; an oily or emulsified gel; a dispersion of vesicles, in particular lipids; a two-phase or multiphase lotion; a spray; a lotion, a cream, an ointment, a soft paste, an ointment, a solid cast or molded and especially stick or cup, or compacted solid. Those skilled in the art may choose the appropriate dosage form, as well as its method of preparation, on the basis of its general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support. and on the other hand the application envisaged for the composition.

The cosmetic compositions according to the invention can be used for the care or the makeup of keratin materials such as the skin, the eyelashes, the eyebrows, the hair, the nails, the lips, and more particularly for the make-up of the lips, the eyelashes , hair and / or face.

They may therefore be in the form of a care product and / or of the skin of the body or of the face, the lips, the eyelashes, the eyebrows, the hair or the nails; a suntan or self-tanning product; they are advantageously in the form of a make-up composition, in particular mascara, eyeliner, lipstick, lip gloss, blush, eyeliner, foundation, nail varnish. nails or nail care; of a capillary product.

The subject of the invention is also a process for the cosmetic treatment of keratin materials, in particular the skin of the body or of the face, the lips, the nails, the hair and / or the eyelashes, comprising the application on the said materials of a cosmetic composition as defined above.

This process according to the invention makes it possible in particular to care for or make up said keratin materials, in particular the lips and / or the nails, by application of a composition, in particular lipstick or nail polish, according to the invention. vention.

In a particular embodiment of the invention, the functionalized capsules may be used in admixture with the supramolecular polymers. Mention may in particular be made of the polymers as described in applications EP1392222, EP1797867 and EP1797868.

Mention may also be made of supramolecular polymers based on polyalkene.

For the purposes of the present invention, the term supramolecular polymer based on polyalkene, a polymer resulting from the reaction, in particular condensation, of at least one polyalkene polymer functionalized with at least one reactive group, with at least one connecting group functionalized by at least one reactive group capable of reacting with the reactive group or groups of the functionalized polyalkene polymer, said joining group being capable of forming at least 3 H bonds (hydrogen.

Preferably, the functionalized polyalkene polymer capable of forming all or part of the polymeric backbone of the supramolecular polymer according to the invention, is of formula ΗΧ-Ρ-ΧΉ in which:

- XH and ΧΉ are reactive groups, with X and X ', identical or different, selected from O, SH, NH or NR _a , R _a representing a C1-C6 alkyl group; preferably

X and / or X 'denote O; preferentially, X and X 'denote O;

- P represents a homo- or copolymer obtainable by polymerization of one or more alkenes, linear, cyclic and / or branched, mono or polyunsaturated C ₂ -C ₁ 0, preferably C ₂ -C ₄ ; P preferably represents a polyethylene, a polybutylene, a polybutadiene, a polyisoprene or a poly (1, 3

Pentadiene), a polyisobutylene, and copolymers thereof, and especially poly (ethylenebutylene).

Poly (ethylenebutylene) are copolymers of butene-1 and ethylene. They can be schematized by the following sequence of motifs: [-CH ₂ -CH ₂ -] and

30 [-CH ₂ CH (CH ₂ -CH ₃ ) -]

The polybutadienes may be 1,4-polybutadienes or 1,2-polybutadienes, which may be schematically represented by the following sequences of units:

[-CH ₂ -CH = CH-CH ₂ -] (polybutadienes 1, 4)

[-CH ₂ -CH (CH = CH ₂ ) -] (polybutadienes 1, 2)

Preferably, it is polybutadienes 1, 2.

The polyisoprenes can be schematized by the following sequences of patterns:

40

Of course, it is also possible to use a mixture of the above units in order to form copolymers. Preferably, the functionalized polyalkene polymers have a number-average molecular mass (Mn) greater than or equal to 1000, especially between 1000 and 5000, or even between 1500 and 3500.

Functionalized polyalkene polymers may be totally hydrogenated to avoid the risk of crosslinking.

The supramolecular polymers may further comprise in their structure other units derived from other monomers. As comonomers, mention may in particular be made of styrene or epoxy. In a preferred embodiment, they do not include and therefore consist of polyalkene polymers (100%) to form the polymer backbone.

The polyalkene polymers are functionalized with at least one reactive group, preferably with at least two reactive groups. The functionalization is preferably at the end of chains. We are talking about telechelic polymers. The functionalizing groups, or reactive groups can be attached to the polymer via linkers polyalkene, preferably alkylene Ci-C ₄ linear or branched, or directly by a single bond. As a reactive group, the OH, NH ₂ , NHR, SH or NCO functions may be mentioned.

Among the preferred functionalized polyalkene polymers, mention may be made of poly-dienes, preferably hydrogenated, with hydroxyl functional groups, preferably with hydroxyl ends, and polyolefins with hydroxyl ends.

The polydienes with hydroxyl ends are especially defined for example in FR2782723. They can be chosen from homopolymers and copolymers of polybutadiene, polyisoprene and poly (1,3-pentadiene). Preferably, they have a number-average molecular mass (Mn) of less than 7000, preferably of between 1000 and 5000; and have a functionality in hydroxyl ends of 1, 8 to 3, and preferably close to 2. Mention may be made in particular of the hydroxylated polybutadienes marketed by the company ELF ATOCHEM under the trade marks POLY BD R-45HT and POLY BD R-20 LM, which will preferably be hydrogenated; as well as dihydroxylated (1,2-polybutadienes), such as GI3000 of Mn = 3100, GI2000 (Mn = 2100) and GI1000 (Mn = 1500) marketed by Nisso.

Among the polyolefins with hydroxyl ends, mention may preferably be made of polyolefins, homopolymers or copolymers with α, ω hydroxyl ends, such as polyisobutylenes with α, ω hydroxyl ends; and copolymers of formula:

especially those marketed by Mitsubishi under the POLYTAIL brand.

The supramolecular polymers according to the invention also have in their structure at least one residue of a linking group capable of forming at least 3 H bonds, preferably at least 4 H bonds, said joining group being initially functionalized by at least one reactive group.

The functionalized junction groups capable of reacting with the functionalized polyalkene polymer to give the supramolecular polymer are preferably of the formula:

in which L is a single bond or a divalent (alkylene), saturated or unsaturated, or even aromatic, C1-C20, linear, cyclic and / or branched, optionally comprising 1 to 4 N and / or O heteroatoms, especially under form of substituent NO2, and in particular a phenylene group; 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'-methylene bis-cyclohexylene; tolylene; 2-methyl-1,3-phenylene; 4-methyl-1,3-phenylene; 4,4-biphenylenemethylene; and preferably: -isophorone-; - (CH ₂ ) 2-; - (CH ₂ ) 6-; CH ₂ CH (CH 3) -CH ₂ -C (CH ₃ ) 2 -CH 2 -CH 2; 4,4'-methylene biscyclohexylene; 2-methyl-

1,3-phenylene.

In a preferred embodiment, the supramolecular polymer has the formula:

in which :

- L 'and L "have, independently of each other, the meaning indicated above for L;

X, X 'and P have the meanings indicated above for the functionalized polyalkene polymer.

Preferably, X = X - O.

Preferably, L 'and L "represent a divalent (alkylene), saturated or unsaturated, C1-C20, linear, cyclic and / or branched carbon group, and in particular an -isophorone- (CH ₂ ) ₂ - group; - (CH ₂ ) ₆ -; CH ₂ CH (CH 3) -CH ₂ -C (CH 3) 2 -CH ₂ -CH ₂ ; 4,4'-methylene biscyclohexylene; 2-methyl-1,3-phenylene.

Preferably, P represents a polyethylene, a polybutylene, a polybutadiene, polyisoprene, poly (1,3-pentadiene), polyisobutylene, or a copolymer thereof, especially poly (ethylene-butylene).

The supramolecular polymer based on polyalkene, alone or as a mixture, may be present in the cosmetic composition in a proportion of 0.1 to 70% by weight, preferably from 0.2 to 40% by weight, preferably from 0.5 to 15% by weight, relative to the total weight of the composition.

The invention is illustrated in more detail in the following exemplary embodiments. Example 1 Synthesis of Polyurethane Capsules by Interfacial Polymerization

In a reactor, 12 g of diphenylmethane 4,4'-diisocyanate and 2.8 g of isododecane are mixed and stirred with ultraturax at 13500 rpm. A solution previously cooled in an ice bath (10 ° C.) comprising 320 g of water at 5% of PVA (polyvinyl alcohol) hydrolysed at 98%, in the presence of 3.4 g of surfactant, is added all at once. Poloxamer 188; it is stirred with ultraturax for 1 hour.

A solution comprising 4 g of diethylene glycol, 1.4 g of pentaerythritol and 80 g of 5% PVA water is then added.

The mixture is mechanically stirred and heated to 65 ° C. Polymerization was followed by light microscopy and then the heating and stirring was stopped after 23 hours. The reaction mixture is centrifuged for 30 minutes; after removing the supernatant, the solid is washed with water 3 times, filtered on filter paper and left for 3 hours in a neutralizing solution of isocyanates. The powder is washed again with water, filtered and dried.

8.87 g of capsules with a hydroxyl number measured at 28 are obtained.

2.84 g of the capsules prepared above are suspended in 6 ml of toluene under argon in the presence of 3 microliters of dibutyltin dilaurate. The mixture is brought to 100 ° C., and 0.44 g of dendron ureidopyrimidone of structure represented below (SupraPolix), previously dissolved in 15 ml of toluene, is added. The solution is refluxed for 22 hours: the reaction medium becomes viscous. The monitoring of the reactivity is done by infrared spectroscopy, with the disappearance of the isocyanate characteristic band at 2260 cm ^-1 The capsules are filtered on filter paper, washed three times with 75 ml of CH 2 Cl 2, dispersed in a decontaminant solution, washed with ethanol, refiltered on filter paper and dried.

Dendron:

1.75 g of functionalized capsules are obtained (yield 61%). Example 2 Cosmetic Composition

An anhydrous composition comprising (% by weight) is prepared:

- Capsules prepared in Example 1 10%

- Disteardimonium hectorite (10%) and propylene carbonate (3%)

in isododecane (Bentone Gel ISD V) 20%

- Isododecane qs 100%

All constituents are placed in a beaker, mixing is done using a Rayneri mixer. Example 3 Cosmetic Composition

An aqueous composition is prepared comprising (% by weight):

- Capsules prepared in Example 1 10%

- benzyl alcohol 0.8%

- 2% xanthan gum

- Water qs 100%

Water and benzyl alcohol are mixed in a Rayneri mixer and then the xanthan gum is added with vigorous stirring. Total dilution of xanthan is expected before introducing the capsules. Stirring is allowed for 10 minutes.

Claims

1. Cosmetic composition comprising, in a cosmetically acceptable medium, a capsule functionalized on the surface by at least one linking group, obtainable by reaction between:

at least one capsule carrying at least one reactive function, and

at least one linking group capable of establishing hydrogen bonds with one or more partner joining groups, each pairing of a linking group involving at least 3 hydrogen bonds, said linking group carrying at least one reactive function capable of to react with the reactive function carried by the capsule, said joining group further comprising at least one unit of formula (I) or (II):

O) (he)

in which :

R 1 and R 3, which may be identical or different, represent a divalent carbon radical chosen from (i) a linear or branched C ₁ -C 32 alkyl group, (ii) a C ₄ -C ₆ cycloalkyl group and (iii) a C 5 aryl group. ₄ -C16; optionally comprising 1 to 8 heteroatoms selected from O, N, S, F, Si and P; and / or optionally substituted with an ester, amide or a C1-C12 alkyl radical; or a mixture of these groups;

R 2 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, C 1 -C 32 hydrocarbon (alkyl) radical, which may comprise one or more heteroatoms selected from O, N; , S, F, Si and P.

2. Composition according to claim 1, wherein the capsule is of the polyurethane, polyurea and / or polyurethane / polyurea type, and crosslinked.

3. Composition according to claim 2, in which the capsule is obtained by reacting at least two reagents, one of isocyanate type and the other of alcohol and / or amine type, at least one of these reagents bearing at least at least 3 functions, identical or different, chosen for one of the isocyanate functions, and for the other of the hydroxyl and amine functions.

4. Composition according to one of claims 2 to 3, wherein the capsule is obtained by interfacial polymerization.

5. Composition according to claim 1, in which the capsule is of polyurethane, polyester, polyamide, polycarbonate, polysiloxane, polysaccharide, cellulosic, polyether, polyamine, polypeptide, protein, polyvinylalcohol and polyvinyl acetate, or poly (meth) type. C1-C16 alkyl acrylate, polystyrene or copolymers thereof.

6. Composition according to claim 1, in which the capsule is totally or partially inorganic, for example of silica, ΤΊΟ2, ΖΓΟ ₂ , alumina,

SnO2, iron oxide, or mixtures thereof; or of clay type, sepiolite, montmorillonite, or mixtures thereof.

7. Composition according to one of the preceding claims, wherein the containment comprises an encapsulated active.

8. Composition according to claim 7, wherein said encapsulated active agent is chosen from dyestuffs, gases, oils and cosmetic waxes, cosmetic active agents, and mixtures thereof.

9. Composition according to one of the preceding claims, wherein the unit is of formula (I) with:

- Ri = -isophorone-, R2 = methyl, which leads to the unit of formula:

- (CH ₂ ) 6-, R2 = methyl, which leads to the formula unit

- Ri = - (CH ₂ ) 6-, R 2 = isopropyl, which leads to the unit of formula:

or R 1 = 4,4'-methylenebiscyclohexylene and R 2 = methyl, which leads to the unit of formula:

10. Composition according to one of claims 1 to 8, wherein the pattern is of formula (II), with R1 representing the radical -isophorone-, R2 = methyl and R3 = - (CH ₂₎ ₂ OCO-NH-isophorone -, which leads to the divalent formula:

1 1. Composition according to one of the preceding claims, in which the linking group is chosen from the following groups:

12. Composition according to one of the preceding claims, wherein the functionalized capsules are present in an amount of between 5 and 80% by weight, preferably between 10 and 75% by weight, especially between 20 and 70% by weight, or even between 25 and 65% by weight, and better still between 30 and 60% by weight, relative to the weight of the final cosmetic composition.

13. Composition according to one of the preceding claims, wherein the cosmetically acceptable medium comprises at least one constituent selected from oils and / or solvents of mineral, animal, vegetable or synthetic origin, carbon, hydrocarbon, fluorinated and / or silicone volatile or non-volatile; thickening agents; waxes of vegetable, animal, mineral or synthetic origin, or even silicone; dyestuffs; antioxidants, perfumes, essential oils, preservatives, cosmetic active ingredients, moisturizers, vitamins, ceramides, sunscreens, surfactants, gelling agents, leveling agents, wetting agents, dispersing agents, anti-foams, neutralizers, stabilizers, polymers, and mixtures thereof.

14. Composition according to one of the preceding claims, further comprising at least one supramolecular polymer.

15. Composition according to one of the preceding claims, being in the form of a care product and / or make-up of the skin of the body or face, lips, eyelashes, eyebrows, hair or nails. ; a suntan or self-tanning product; a hair product; a makeup composition.

16. Process for the cosmetic treatment of keratinous substances, especially the skin of the body or of the face, lips, nails, hair and / or eyelashes, comprising the application to said materials of a cosmetic composition as defined in one of claims 1 to 15.

17. Capsule functionalized on the surface by at least one joining group, obtainable by reaction between:

at least one capsule carrying at least one reactive function, and

(D (he)

in which :

R1 and R3, which may be identical or different, represent a divalent carbon radical chosen if from (i) a linear alkyl group or branched C1-C32, (ii) a cycloalkyl group having ₄ -Ci6 and (iii) aryl C ₄ -Ci6; optionally comprising 1 to 8 heteroatoms selected from O, N, S, F, Si and P; and / or optionally substituted with an ester, amide or a C1-C12 alkyl radical; or a mixture of these groups;

R 2 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, optionally aromatic, C 1 -C 32 hydrocarbon (alkyl) radical, which may comprise one or more heteroatoms chosen from O, N, S; , F, Si and P.