FR2931674A1 - Cosmetic composition, useful e.g. for makeup/care of keratin materials e.g. lips, comprises a polymer sequence comprising sequences incompatible with each other and polycondensate obtained by reaction of e.g. at least one polyol, in medium - Google Patents

Abstract

Cosmetic composition comprises, a polymer sequence comprising at least one first sequence and least one second sequence incompatible with each other and having different glass transition temperatures (Tg) and a polycondensate obtained by reaction of: e.g. at least 10-30 wt.% of at least one polyol comprising 3-6 hydroxyl groups; and 30-80 wt.% of at least one non-aromatic, optionally saturated, linear, branched and/or cyclic 6-32C monocarboxylic acid, in a medium. Cosmetic composition comprises, (i) a polymer sequence comprising at least one first sequence and least one second sequence incompatible with each other and having different glass transition temperatures (Tg) and (ii) a polycondensate obtained by reaction of: at least 10-30 wt.%, with respect to the total weight of the polycondensate, of at least one polyol comprising 3-6 hydroxyl groups; 30-80 wt.%, with respect to the total weight of the polycondensate, of at least one non-aromatic, optionally saturated, linear, branched and/or cyclic 6-32C monocarboxylic acid; and 1-40 wt.%, with respect to the total weight of the polycondensate, of at least one optionally saturated or aromatic, linear, branched and/or cyclic polycarboxylic acid, comprising at least 2 carboxylic groups (COOH) and/or a cyclic anhydride of a polycarboxylic acid, and/or lactone comprising at least one COOH group, in a medium.

Description

The present invention relates to novel cosmetic compositions, comprising a combination of at least two particular polymers, so as to obtain cosmetic compositions that are particularly bright and pleasant to wear.

Various types of polymers are conventionally used in cosmetic compositions because of the various properties they can provide. They are for example used in make-up or skincare compositions, lips or integuments, such as nail polishes or compositions for the hair. However, by using within the same composition two incompatible polymers, that is to say immiscible in the same solvent, the formulator is confronted, because of the incompatibility of the polymers, with phase separation problems, even decantation, and generally to obtain a non-homogeneous composition. These problems could hitherto be solved only by the presence in the composition of a compound making it possible to compatibilize the polymers with one another. To overcome this problem, it has been proposed in EP1411069, polymers of particular structure, comprising at least two mutually incompatible sequences and connected by an intermediate sequence which comprises at least one constituent monomer of each of the two sequences. This application mainly describes block polymers prepared from alkyl acrylate and methacrylate monomers, in particular methyl, isobutyl, isobornyl, trifluoroethyl or (meth) acrylic acid monomers. These polymers are generally transportable, especially soluble, in organic solvents such as short esters (butyl or ethyl acetate), short alcohols such as ethanol, or aliphatic alkanes such as isododecane. They make it possible to obtain glossy and low tack films, which are particularly appreciated in certain cosmetic fields.

However, these films have a certain brittle character and a sensitivity to fat, especially over time. However, we seek, especially in the field of makeup, polymers likely to have resistance and resistance to external aggression, including 'aggression' by fat, such as for example by edible oil or sebum.

The object of the present invention is to provide a composition which makes it possible, by means of a particular combination of polymers, to obtain both a glossy and tacky film as those of the prior art, while at the same time being little or no case - Healthy and sufficiently flexible, and advantageously having good resistance to fat.

An object of the present invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, (i) a block polymer comprising at least a first sequence and at least a second sequence which are incompatible with each other and which have temperatures of different glass transition (Tg), (ii) a polycondensate obtainable by reaction of at least: from 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups; from 30 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms; from 1 to 40% by weight, relative to the total weight of the polycondensate, of at least one polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH; and / or a cyclic anhydride of such a polycarboxylic acid; and / or a lactone comprising at least one COOH group.

It has been found that the combination of a block polymer and a polycondensate according to the invention makes it possible to obtain all the desired properties.

The films or deposits obtained are less brittle than those of the prior art. Comfort, flexibility and hold are improved, as well as the holding of the deposit in time. Surprisingly and unexpectedly, they are also not very sticky to the deposit and are less sensitive to oils than those of the prior art. They thus have a better resistance to greasy substances, especially edible oil or sebum. The films or deposits obtained are also comfortable to wear; the film deforms little or not at all during its drying, thus avoiding the problems of tugging.

Moreover, the composition according to the invention makes it possible to obtain a significant gloss of the deposit and / or the film, as well as a good durability in time of this gloss; this can find a particularly advantageous application in the field of lipsticks or nail polish. The cosmetic compositions therefore have good applicability and good coverage; good adhesion to the support, whether on the nail, hair, eyelashes, skin or lips; adequate flexibility and film strength, to avoid cracking, as well as an excellent level of lasting gloss.

The composition according to the invention therefore comprises at least one block polymer comprising at least a first sequence and at least a second sequence, which have different glass transition temperatures (Tg) and which are advantageously incompatible with each other. It is specified that the terms "first" and "second" sequences do not condition the order of said sequences (or blocks) in the polymer structure.

By "sequences incompatible with each other", it is meant that the mixture formed of the polymer corresponding to the first block and the polymer corresponding to the second block, is not miscible in the majority polymerization solvent by weight of the polymer. sequenced, at room temperature (25 ° C.) and atmospheric pressure (105 Pa), for a content of the polymer mixture greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and solvent), being understood that: i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (in weight or in number) equal to that of the sequenced polymer +/- 15%. In the case of a mixture of polymerization solvents, assuming two or more solvents present, said polymer mixture is immiscible in at least one of them. Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent.

Said first and second sequences may advantageously be connected to each other by an intermediate segment comprising at least one constituent monomer ml of the first block and at least one constituent monomer m2 of the second block. Preferably, said intermediate segment forms an intermediate sequence (or block). Preferably, m2 is different from ml. Said segment or intermediate sequence can in particular make it possible to "compatibilize" these first and second sequences.

The block polymer employed in the context of the invention is advantageously a linear ethylenic block polymer, linear, branched or grafted, preferably linear, and capable of forming a deposit, more particularly a film (film-forming). By ethylene polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation. By sequenced polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences; preferably diblocks or triblocks. The polymer according to the invention is linear, branched or grafted; preferably it does not include a monomer or multifunctional compound, added voluntarily, and capable of generating branching and / or crosslinking. The term deposit-forming polymer is understood to mean a polymer capable of forming on its own or in the presence of an auxiliary agent, an adherent deposit on a support, in particular on keratin materials. The term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.

Each block, or block, of the polymer according to the invention is derived from one type of monomer or from several different types of monomer. This means that each sequence may consist of a homopolymer or a copolymer, which may be random, alternating or otherwise. Advantageously, when present, the segment or the intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer. Preferably, said segment or intermediate sequence is derived essentially from monomers constituting the first sequence and the second sequence. By "essentially" is meant at least 85%, preferably at least 90%, better at 95% and even better at 100%.

According to the invention, the first and second sequences have different glass transition temperatures, with a difference generally greater than 5 ° C., preferably greater than 10 ° C., and better still greater than 20 ° C. Advantageously, the intermediate block has a glass transition temperature Tg between the glass transition temperatures of the first and second blocks.

The glass transition temperatures indicated are, unless otherwise indicated, theoretical Tg determined from the theoretical Tg of the monomers constituting each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 4th ed. (Brandrup, Immergut, Grulke), 1999, John Wiley, according to the following relation, called Fox's Law: 30-E () Tg Tgi wi being the mass fraction of the monomer i in the sequence under consideration and Tgi being the glass transition temperature homopolymer of the monomer i (expressed in Kelvin).

The sequenced polymer according to the invention preferably comprises at least one sequence having a Tg greater than or equal to 20 ° C and a sequence having a Tg strictly less than 20 ° C.

Preferably, one of the sequences has a Tg of between 20 ° C and 160 ° C, preferably between 40 ° C and 120 ° C, preferably between 50 ° C and 110 ° C.

Preferably, one of the sequences has a Tg between -150 ° C and 20 ° C (excluded), especially between -100 ° C and 10 ° C, preferably between -50 ° C and 0 ° C.

Preferably, the sequence having the highest Tg is in major amount, by weight, relative to the other sequences.

Preferably, the sequenced polymer according to the invention consists exclusively of a first and a second sequence (it is then a diblock), or exclusively of a first sequence, a second sequence and a second sequence. an intermediate segment which is preferably an intermediate sequence (it can therefore be a triblock).

When the block polymer does not comprise an intermediate sequence or segment (diblock), the sequence with the highest Tg can be present in the block polymer in an amount of 50 to 90% by weight, especially 55 to 80% and more preferably 60 to 75% by weight, based on the total weight of the block polymer and the second block may be present in an amount of 10 to 50% by weight, especially 20 to 45% by weight and more preferably 25 to 40 % by weight, based on the total weight of the sequenced polymer.

When the block polymer comprises an intermediate sequence or segment, the sequence having the highest Tg may be present in the sequenced polymer in an amount of 45 to 90% by weight, especially 50 to 80% and even more preferably 55 to 75%. by weight, based on the total weight of the sequenced polymer; the second block may be present in an amount of 9 to 45% by weight, especially 10 to 40% by weight and more preferably 20 to 35% by weight, relative to the total weight of the sequenced polymer; the segment, or sequence, intermediate can represent 1 to 10% by weight, especially 2 to 7% by weight and more preferably 3 to 5% by weight, of the total weight of the block polymer.

As mentioned above, said first and / or second sequences may consist of a homopolymer or a copolymer, which may be random, alternating or other, preferably random.

The chemical nature and / or the amount of the monomers constituting each of the sequences can of course be chosen by those skilled in the art, on the basis of his general knowledge, to obtain sequences having the required Tg.

Thus, the monomers constituting all or part of said sequences, in particular first and / or second sequences, may be chosen from, alone or as a mixture, the following monomers: (i) ethylenic hydrocarbons having 2 to 10 carbons, such as ethylene, isoprene, or butadiene; (ii) (meth) acrylates of formula CH2 = CHCOOR3 or CH2 = C (CH3) 0O0R3 in which R3 represents: a linear or branched, saturated or unsaturated alkyl group having 1 to 22 carbon atoms, in particular 4 to 20 or even 6 to 18 carbon atoms, which may optionally comprise, intercalated and / or in substitution, one or more heteroatoms chosen from O, N, S, P and the halogen atoms (Cl, Br, I and F); in particular R3 may be methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, dodecyl, behenyl, stearyl; ethyl-2-perfluorohexyl; or a C1-4 hydroxyalkyl group such as 2-hydroxyethyl, 2-hydroxybutyl and 2-hydroxypropyl; or an alkoxy (C1-4) alkyl (C1-4) group such as methoxyethyl, ethoxyethyl and methoxypropyl; - a C3-C12 cycloalkyl group, such as isobornyl, cyclohexyl, t-butylcyclohexyl, - a C3 aryl group; C 20 -C 20 aralkyl (C 1 -C 8 alkyl group) such as 2-20 phenylethyl, t-butylbenzyl or benzyl, - a 4- to 12-membered heterocyclic group containing one or more heteroatoms selected from O, N, and S, the ring being aromatic or not, - a heterocycloalkyl (alkyl of 1 to 4 C), such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl which may be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms, and linear or branched C1-C4 alkyl groups, which may optionally include, intercalated and / or substituted one or more heteroatoms selected from O, N, S, P and halogen atoms (Cl, Br, I and F); - R3 can also be a group - (C2H4O) m-R, with m = 5 to 150 and R = H or C1 to C30 alkyl, for example -POE-methyl or -POE-behenyl;

(iii) (meth) acrylamides of formula CH 2 = CHCONR 6 R 7 or CH 2 = C (CH 3) CON 35 R 6 R 7 in which R 6 and R 7, which may be identical or different, represent: a hydrogen atom; or a linear or branched, saturated or unsaturated alkyl group having 1 to 22 carbon atoms, especially 4 to 20 or even 6 to 18 carbon atoms, which may optionally comprise, intercalated and / or substituted, one or more heteroatoms selected from O, N, S, P and the halogen atoms (Cl, Br, I and F); in particular R6 and / or R7 may be methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, dodecyl, behenyl, stearyl; ethyl-2-perfluorohexyl; or a C1-4 hydroxyalkyl group such as 2-hydroxyethyl, 2-hydroxybutyl and 2-hydroxypropyl; or a (C1-4) alkoxy (C1-4) alkyl group such as methoxyethyl, ethoxyethyl and methoxypropyl; - a C3-C12 cycloalkyl group, such as isobornyl, cyclohexyl, t-butylcyclohexyl; a C 3 to C 20 aryl group such as phenyl, a C 4 to C 30 aralkyl group (C 1 to C 6 alkyl group) such as 2-phenylethyl, t-butylbenzyl or benzyl, a heterocyclic group of 4 to 12-membered ring containing one or more heteroatoms selected from O, N, and S, the ring being aromatic or non-aromatic, - a heterocycloalkyl (C 1 -C 4) alkyl group, such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl groups heterocyclic or heterocycloalkyl group which may be optionally substituted by one or more substituents selected from hydroxyl groups, halogen atoms, and linear or branched C1-C4 alkyl groups, which may optionally include, intercalated and / or substituted, one or more heteroatoms selected from O, N, S, P and halogen atoms (Cl, Br, I and F); It may especially be mentioned (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N dimethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-octyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N-undecyl (meth) acrylamide and N-2- hydroxypropyl (meth) acrylamide.

(iv) vinyl compounds of formula CH2 = CH-R9, CH2 = CH-CH2-R9 or CH2 = C (CH3) -CH2-R9 in which R9 is a hydroxyl, halogen (Cl or F), NH2 group, OR14 wherein R14 is phenyl or C1-C12 alkyl (the monomer is vinyl or allyl ether); acetamide (NHCOCH3); a group OCOR15 where R15 represents a linear or branched alkyl group of 2 to 12 carbons (the monomer is a vinyl or allyl ester); or a group chosen from: a linear or branched alkyl group of 1 to 22 carbon atoms, in particular 4 to 20 or even 6 to 18 carbon atoms, which may optionally comprise, intercalated and / or in substitution, one or more heteroatoms; selected from O, N, S, P and the halogen atoms (Cl, Br, I and F); a C 3 to C 12 cycloalkyl group such as isobornyl, cyclohexyl, a C 3 to C 20 aryl group such as phenyl, a C 4 to C 30 aralkyl group (C 1 to C 6 alkyl group) such as 2-phenylethyl; benzyl; - a 4- to 12-membered heterocyclic group containing one or more heteroatoms selected from O, N, and S, the ring being aromatic or non aromatic, - a heterocycloalkyl (C 1 -C 4 alkyl) group, such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl groups being optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms and linear or branched C1-C4 alkyl groups, which may optionally comprise , intercalated and / or substituted, one or more heteroatoms selected from O, N, S, P and halogen atoms (Cl, Br, I and F); There may be mentioned vinylcyclohexane, styrene; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate; vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether. (v) monomers containing ethylenic unsaturation (s) comprising at least one carboxylic acid, phosphoric or sulphonic acid function, or anhydride, such as, for example, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and salts thereof,

(vi) monomers containing ethylenic unsaturation (s) comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the salts thereof.

The salts may be formed by neutralization of the anionic groups with the aid of a mineral base, such as LiOH, NaOH, KOH, Ca (OH) 2, NH 4 OH or Zn (OH) 2; or with an organic base such as a primary, secondary or tertiary alkylamine, especially triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and / or oxygen atoms and may therefore comprise, for example, one or more alcohol functions; mention may especially be made of 2-amino-2-methyl-propanol, triethanolamine and 2-dimethylamino propanol. Lysine or 3- (dimethylamino) propylamine may also be mentioned. Mention may also be made of mineral acid salts, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and boric acid. Mention may also be made of organic acid salts, which may comprise one or more carboxylic acid, sulphonic acid or phosphonic acid groups. It may be linear, branched or cyclic aliphatic acids or aromatic acids. These acids may furthermore comprise one or more heteroatoms chosen from 0 and N, for example in the form of hydroxyl groups. These include propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid.

Among the monomers whose homopolymers have a Tg greater than or equal to 20 ° C., which may be used, mention may be made in particular of: methacrylates of formula: CH 2 = C (CH 3) -000 R 1 in which R 1 represents a non-alkyl group; substituted, linear or branched, containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or else R 1 represents a C 4 to C 12 cycloalkyl group, in particular isobornyl; acrylates of formula: ## STR2 ## in which R 2 represents a tert-butyl group or a C 4 to C 12 cycloalkyl group such as an isobornyl group; the (meth) acrylamides of formula: CH2 = CR'-CO-NR'R8 with R 'representing H or CH3, and R, and R8, which may be identical or different, represent a hydrogen atom or a C1-C8 alkyl group; 012 linear or branched, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or else R, represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, methacrylic acid and acrylic acid. Mention may be made in particular of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl (meth) acrylate, (meth) acrylic acid, isobornyl (meth) acrylate, N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dibutylacrylamide, n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, isodecylacrylamide , and their mixtures.

Among the monomers whose homopolymers have a Tg lower than 20 ° C., which may be used, mention may be made in particular of: the acrylates of formula CH 2 CHCHCOOR 3, in which R 3 represents a linear C 1 to O 12 unsubstituted alkyl group, linear or branched, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S, - methacrylates of formula CH2 = C (CH3) -COOR4, in which R4 represents a linear or branched C6 to C12 unsubstituted alkyl group in which one or more heteroatoms selected from O, N and S are optionally intercalated; vinyl esters of formula R 5 -CO-O-CH =CH 2 where R 5 represents a linear or branched C 4 to C 12 alkyl group; (C4-C12alkyl) -vinylethers, especially methylvinylether and ethylvinylether; N- (C4-C12 alkyl) acrylamides, such as N-octylacrylamide, and mixtures thereof.

Mention may especially be made of methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl (meth) acrylate and mixtures thereof.

In a preferred embodiment, the polymer according to the invention comprises in at least one sequence, preferably in each of the sequences, at least one monomer chosen from (meth) acrylic acid esters; optionally, it may further comprise at least one second monomer chosen from acrylic acid and methacrylic acid, or even their mixture. Preferably, all the constituent monomers of the block polymer are chosen from (meth) acrylic acid esters and (meth) acrylic acid.

Thus, the monomers chosen, in particular, alone or as a mixture, are chosen from C1-C22 alkyl (meth) acrylates, in particular C4-C20, or even C6-C18, or C3-C12 cycloalkyl, and especially the isobornyl (meth) acrylate, isobutyl (meth) acrylate, ethyl-2-hexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) behenyl acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate; - (meth) acrylic acid. Most preferably from C 1 -C 4 alkyl or C 3 -C 12 cycloalkyl, and especially methyl methacrylate, isobornyl methacrylate, isobutyl methacrylate; tert-butyl acrylates, methyl acrylate, isobutyl acrylate and isobornyl acrylate; acrylic acid and methacrylic acid.

In a preferred embodiment, the block polymer comprises: a first block obtained from at least one acrylate monomer of the formula CH 2 = CH-OOOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C4-C12 cycloalkyl group, and - a second block obtained from a (meth) acrylic acid monomer and at least one monomer whose homopolymer has a Tg of less than or equal to 20 ° C. According to this embodiment, the first block can be obtained exclusively from said acrylate monomer and said methacrylate monomer. The acrylate monomer and the methacrylate monomer are preferably in mass proposals of between 30:70 and 70:30, preferably 40:50 and 50:40, in particular of the order of 50:50. The proportion of the first block is preferably 20 to 90% by weight of the polymer, more preferably 30 to 80% and more preferably 60 to 80%. The first block is preferably obtained by polymerization of isobornyl methacrylate and isobornyl acrylate. The first block may further comprise (meth) acrylic acid, preferably acrylic acid; tert-butyl acrylate; a methacrylate of formula CH2 = C (CH3) -000R1 in which R1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group. According to this embodiment, the second block is preferably obtained from acrylic acid and from a monomer whose homopolymer has a Tg of less than or equal to 20 ° C., in particular isobutyl acrylate.

Each of the first and / or second sequence may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above. The additional monomers may represent 0.5 to 30% by weight of the weight of the polymer. Preferably, in this embodiment, the polymer does not contain any additional monomer and consists exclusively of the monomers indicated above. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block and isobutyl acrylate and acrylic acid monomers in the second block, the first block being able to further represent 50-80% by weight of the polymer.

The weight average molar mass (Mw) of the block polymer according to the invention is preferably between 25,000 and 1,000,000, more preferably between 30,000 and 750,000, or even between 40,000 and 500,000, and preferably between 50,000 and 250000. The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (solvent THF, calibration curve established with linear polystyrene standards, refractometric detector and UV).

Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still from 2.8 to 7. The polydispersity index Ip of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn.

The sequenced polymer can be obtained by radical polymerization in solution according to the following preparation method: a part of the polymerization solvent can be introduced into a suitable reactor, and the mixture is heated until the temperature which is suitable for the polymerization is reached (typically between 60 and 120 ° C.), once this temperature has been reached, the monomers constituting the first sequence may be added in the presence of a part of the polymerization initiator, after a time T corresponding to a conversion rate. preferably up to 90%, the constituent monomers of the second block and the other part of the initiator can be introduced, the mixture is allowed to react for a time T '(in particular from 3 to 6 hours) at the end of which the mixture is brought back to ambient temperature (25 ° C.) so as to obtain the polymer in solution in the polymerization solvent.

"Polymerization solvent" means a solvent, or a mixture of solvents, in particular chosen from ethyl acetate, butyl acetate, C1-C6 alcohols such as isopropanol, ethanol and alkanes. aliphatics such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

Preferably, the block polymer is not water-soluble, that is to say that it is not soluble in water or in a mixture of water and linear or branched monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without any change in pH, at an active ingredient content of at least 10% by weight, at room temperature (25 ° C).

It is possible to use in the composition according to the invention a mixture of block polymers according to the invention.

The block polymer, alone or as a mixture, may represent 50 to 95% by weight, especially 55 to 90% by weight, or even 60 to 85% by weight, of the total weight of the mixture (block polymer + polycondensate). Preferably, said block polymer, alone or as a mixture, may be present in a proportion of 1 to 25% by weight in the composition according to the invention, in particular 2 to 20% by weight, or even 5 to 15% by weight, relative to to the total weight of the composition.

The composition according to the invention also comprises at least one polycondensate that can be obtained by reacting: from 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups ; from 30 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms; from 1 to 40% by weight, relative to the total weight of the polycondensate, of at least one polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH, and or a cyclic anhydride of such a polycarboxylic acid, and / or a lactone comprising at least one COOH group.

The polycondensates according to the invention are advantageously branched (branched); it can be thought that this makes it possible to generate a network by entanglement of the polymer chains, and thus to obtain the desired properties, in particular in terms of improved behavior, improved gloss, and in terms of solubility.

The polycondensates according to the invention are polycondensates of the alkyd type, and are therefore capable of being obtained by esterification / polycondensation, according to the methods known to those skilled in the art, of the constituents described below.

One of the constituents necessary for the preparation of the polycondensates according to the invention is a compound comprising 3 to 6 hydroxyl groups (polyol), in particular 3 to 4 hydroxyl groups. It is of course possible to use a mixture of such polyols. Said polyol may especially be a hydrocarbon compound, in particular linear, branched and / or cyclic, saturated or unsaturated, comprising 3 to 18 carbon atoms, especially 3 to 12 or even 4 to 10 carbon atoms, and 3 to 6 groups. hydroxy (OH), and may further comprise one or more oxygen atoms intercalated in the chain (ether function). Said polyol is preferably a saturated hydrocarbon compound, linear or branched, comprising 3 to 18 carbon atoms, especially 3 to 12 or even 4 to 10 carbon atoms, and 3 to 6 hydroxyl groups (OH). It may be chosen from, alone or as a mixture: triols, such as 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol; tetraols, such as pentaerythritol (tetramethylolmethane), erythritol, di-glycerol or ditrimethylolpropane; pentols such as xylitol, hexols such as sorbitol and mannitol; or dipentaerythritol or triglycerol. Preferably, the polyol is chosen from glycerol, pentaerythritol, diglycerol, sorbitol and their mixtures; and even better is pentaerythritol. The polyol, or polyol mixture, is preferably 10 to 30% by weight, especially 12 to 25% by weight, and more preferably 14 to 22% by weight, of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a saturated or unsaturated, linear, branched and / or cyclic, nonaromatic monocarboxylic acid comprising 6 to 32 carbon atoms, in particular 8 to 28 carbon atoms, and also better 10 to 24 or even 12 to 20 carbon atoms. It is of course possible to use a mixture of such non-aromatic monocarboxylic acids. By non-aromatic monocarboxylic acid is meant a compound of formula RCOOH, in which R is a saturated or unsaturated hydrocarbon radical, linear, branched and / or cyclic, comprising 5 to 31 carbon atoms, in particular 7 to 27 carbon atoms, and still more preferably 9 to 23 carbon atoms, or even 11 to 19 carbon atoms. Preferably, the radical R is saturated. Even better, said radical R is linear or branched, and preferably C5-C31, or even C11-C21. In a particular embodiment of the invention, the nonaromatic monocarboxylic acid has a melting point greater than or equal to 25 ° C, in particular greater than or equal to 28 ° C, or even 30 ° C; it has indeed been found that when such an acid is used, in particular in large quantities, it is possible, on the one hand, to obtain a good gloss and the holding of said gloss, and on the other hand to reduce the quantity of waxes usually present in the composition envisaged.

Among the nonaromatic monocarboxylic acids that may be used, mention may be made, alone or as a mixture, of: saturated monocarboxylic acids such as caproic acid, caprylic acid, isoheptanoic acid, acid ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, acid behenic, cerotic acid (hexacosanoic); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid; unsaturated but nonaromatic monocarboxylic acids, such as caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acid, linderic acid, myristoleic acid, physétérique acid, tsuzuique acid , palmitoleic acid, oleic acid, petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, cetoleic acid, nervonic acid , linoleic acid, linolenic acid, araididonic acid. Among the nonaromatic monocarboxylic acids having a melting point greater than or equal to 25 ° C., mention may be made, alone or as a mixture of: - among the saturated monocarboxylic acids: decanoic acid (capric), lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); - Of unsaturated but nonaromatic monocarboxylic acids: petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, nervonic acid. Preferably, it is possible to use 2-ethylhexanoic acid, isooctanoic acid, lauric acid, myristic acid, isoheptanoic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone. Said nonaromatic monocarboxylic acid, or the mixture of said acids, is preferably 30 to 80% by weight, especially 40 to 75% by weight, or even 45 to 70% by weight, and more preferably 50 to 65% by weight, of the total weight. of the final polycondensate.

An optional component that can be used in the preparation of the polycondensates according to the invention is an aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, optionally further substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and or cyclic, which comprise 1 to 32 carbon atoms, especially 2 to 12, or even 3 to 8 carbon atoms. It is of course possible to use a mixture of such aromatic monocarboxylic acids. By aromatic monocarboxylic acid is meant a compound of formula R'COOH, in which R 'is an aromatic hydrocarbon radical containing 6 to 10 carbon atoms, and in particular the benzoic and naphthoic radicals. Said radical R 'may also be substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, comprising 1 to 32 carbon atoms, especially 2 to 12 or even 3 to 8 carbon atoms; and especially chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, terbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl.

Among the aromatic monocarboxylic acids that may be used, mention may be made, alone or as a mixture, of benzoic acid, o-toluic acid, methacrylic acid, p-toluic acid and 1-naphthoic acid. , 2-naphthoic acid, 4-tert-butyl-benzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid.

Preferably, benzoic acid, 4-tert-butyl-benzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic acid can be used alone or in mixtures; and even better, benzoic acid alone. Said aromatic monocarboxylic acid, or the mixture of said acids, when it is present, preferably represents 0.1 to 10% by weight, in particular 0.5 to 9.95% by weight, better still 1 to 9.5% by weight. by weight, or even 1.5 to 8% by weight, of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and / or a cyclic anhydride of such a polycarboxylic acid. It is of course possible to use a mixture of such polycarboxylic acids and / or anhydrides. Said polycarboxylic acid may especially be chosen from: - (i) linear, branched and / or cyclic, saturated or unsaturated or even aromatic polycarboxylic acids comprising 2 to 50, especially 2 to 40, carbon atoms, in particular 3 to 36 or even 3 to 18, and even more preferably 4 to 12 carbon atoms, or even 4 to 10 carbon atoms; said acid comprises at least two carboxylic groups COOH, preferably from 2 to 4 COOH groups; (ii) saturated or unsaturated, linear or branched chain polycarboxylic acids comprising at least one heteroatom selected from O, N and / or S, in particular 1 to 10 identical or different heteroatoms, and / or comprising at least one perfluorinated radical -CF2- or -CF3 and also having at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; (iii) saturated or unsaturated or even aromatic heterocyclic polycarboxylic acids comprising at least one heteroatom chosen from O, N and / or S, in particular 1 to 10, or even 1 to 4 identical or different heteroatoms, and at least one 2 carboxylic groups COOH, in particular 2 to 4 COOH groups; (iv) polycarboxylic acids derived from sugar, obtainable in particular by oxidation of an aldose, and comprising at least 2 carboxylic groups COOH, in particular 2 or 3 COOH groups; (v) polycarboxylic amino acids (including heterocyclic), that is to say linear or branched, and / or cyclic saturated or unsaturated chain polycarboxylic acids optionally comprising at least one heteroatom selected from the group consisting of: N and / or S, especially 1 to 10 identical or different heteroatoms, and / or optionally comprising at least one perfluorinated radical -CF2- or -CF3; and further comprising at least one primary, secondary or tertiary amine function (especially NR1 R2 with R1 and R2, independently of one another selected from H and C1-C12 alkyl), especially 1 to 3 amine functions , identical or different, and also having at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups.

Preferably, said polycarboxylic acid is chosen from: saturated, linear, aliphatic polycarboxylic acids comprising 2 to 36 carbon atoms, especially 3 to 18 carbon atoms, or even 4 to 12 carbon atoms; or aromatic compounds comprising 8 to 12 carbon atoms. It preferably comprises 2 to 4 COOH groups; and linear, branched and / or cyclic, saturated or unsaturated or even aromatic polycarboxylic acids comprising 4 to 50, especially 5 to 40, carbon atoms, in particular 5 to 36 or even 5 to 18, and even better 5 to 12 carbon atoms; said acid comprising at least two carboxylic groups COOH, preferably 2 to 4 COOH groups and 1 to 10 heteroatoms, preferably 1 to 6, identical or different, selected from O, N, S, and / or 1 to 2 perfluorinated radicals; CF2 and / or CF3.

Said cyclic anhydride of such a polycarboxylic acid may in particular correspond to one of the following formulas:

Wherein the groups A and B are independently of each other: - a hydrogen atom, - a saturated or unsaturated, linear, branched and / or cyclic, or aromatic, carbon, aliphatic radical; comprising 1 to 16 carbon atoms, especially 2 to 10 carbon atoms, or even 4 to 8 carbon atoms, especially methyl or ethyl; or A and B taken together form a ring comprising in total 5 to 14, in particular 6 to 10 carbon atoms, saturated or unsaturated, or even aromatic. Preferably, A and B represent a hydrogen atom or together form an aromatic ring comprising in total 6 to 10 carbon atoms.

It is also possible to use a lactone comprising at least one carboxylic group, in particular 1, 2 or 3 COOH groups. Preferably, the lactones comprise 5 to 14 carbon atoms, in particular 6 to 13 or even 6 to 12 carbon atoms.

Among the polycarboxylic acids, anhydrides and lactones which may be used, mention may be made, alone or as a mixture: dicarboxylic acids such as decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid , malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid, sebacic acid, azelaic acid , glutaric acid, adipic acid, fumaric acid, maleic acid, itaconic acid, fatty acid dimers (especially C36), such as the products sold under the names Pripol 1006, 1009, 1013 and 1017, by Uniqema; tricarboxylic acids such as cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; tetracarboxylic acids such as butanetetracarboxylic acid and pyromellitic acid; cyclic anhydrides of these acids, especially phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride. - itaconic anhydride; 1,4,5,8-naphthalenetetracarboxylic acid 1,4-monoanhydride; 2,2'-sulfinylbis-acetic acid, 2,2'-[methylenebis (sulphonyl)] bis-acetic acid, N, N '- (1,3-dioxo-1,3-propanediyl) bisglycine 2,5-Furanedicarboxylic acid, D-Tartaric acid, DLartartic acid, L-Tartaric acid, Galactaric acid, L-glutamic acid, L-aspartic acid; tetrahydro-5-oxo-2,3-furandicarboxylic acid, 1,3-dihydro-3-oxo-4-isobenzofurancarboxylic acid, 1,3-dihydro-1-oxo-5-isobenzofurancarboxylic acid, tetrahydro-5-oxo-2-phenyl-3-furanecarboxylic acid, lactone of isocitric acid, 5-oxo-2-tetrahydrofurancarboxylic acid.

Preferably, adipic acid, sebacic acid, isophthalic acid and mixtures thereof may be used, and even more preferably isophthalic acid alone. Said polycarboxylic acid, anhydride and / or lactone is preferably 1 to 40% by weight, especially 5 to 30% by weight, and more preferably 10 to 25% by weight, of the total weight of the final polycondensate.

The polycondensate according to the invention may further comprise a hydroxyl functional silicone (OH) and / or carboxylic acid (COOH). It can comprise 1 to 3 hydroxyl and / or carboxylic functions, and preferably comprises two hydroxyl functions or two carboxylic functions. These functions can be located at the end of the chain or in the chain, but advantageously at the end of the chain. Silicones having a weight average molecular weight (Mw) of between 300 and 20000, in particular 400 and 10,000, or even 800 and 4,000, are preferably used. This silicone may be of formula: R 3 R 5 1. +1. m Siù0 Si_R '~ W'

R4 R6 from each other, OH or COOH; preferably R1 W_R) [i_o R2 in which: - W and W 'are independently W = W'; p and q are, independently of one another, equal to 0 or 1, R and R 'are, independently of one another, a divalent carbon radical, in particular hydrocarbon radical, saturated or unsaturated, or aromatic, linear, branched and / or cyclic; comprising 1 to 12 carbon atoms, especially 2 to 8 carbon atoms, and optionally further comprising 1 or more heteroatoms selected from O, S and N, especially O (ether); in particular, R and / or R 'may be of the formula - (CH 2) a - with a = 1-12, and especially methylene, ethylene, propylene or phenylene; or of formula û [(CH 2) X O] Z with x = 1, 2 or 3 and z = 1-10; in particular x = 2 or 3 and z = 1-4; and better x = 3 and z = 1. - R1 to R6 are, independently of one another, a linear carbon radical, rami-fie and / or cyclic, saturated or unsaturated or aromatic; comprising 1 to 20 carbon atoms, especially 2 to 12 carbon atoms; preferably, R 1 to R 6 are saturated or aromatic, and can in particular be chosen from alkyl radicals, in particular the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals, cycloalkyl radicals, in particular the cyclohexyl radical, aryl radicals, especially phenyl and naphthyl radicals, arylalkyl radicals, in particular benzyl and phenylethyl radicals, as well as tolyl and xylyl radicals. M and n are, independently of one another, integers between 1 and 140, and are such that the weight average molecular weight (Mw) of the silicone is between 300 and 20,000, especially between 400 and 10,000 or even between 800 and 4000. Particularly suitable are the α,--diol or α,--dicarboxylic polyalkylsiloxanes, and especially the α,--diol polydimethylsiloxanes and the α, d-carboxylic polydimethylsiloxanes; α,--diol or α,--dicarboxylic polyarylsiloxanes and in particular α,--diol or α,--dicarboxylic polyphenylsiloxanes; silanol-functional polyarylsiloxanes such as polyphenylsiloxane; silanol-functional polyalkylsiloxanes such as polydimethylsiloxane; silanol functional polyaryl / alkylsiloxanes such as polyphenyl / methylsiloxane or polyphenyl / propylsiloxane. In particular, the α,--diol polydimethylsiloxanes having a weight-average molecular weight (Mw) of between 400 and 10,000, and even between 500 and 5,000, and especially between 800 and 4000, will be used. may preferably represent 0.1 to 15% by weight, especially 1 to 10% by weight, or even 2 to 8% by weight, of the weight of the polycondensate.

In a preferred embodiment of the invention, the aromatic monocarboxylic acid, when present, is present in molar amounts less than or equal to that of the nonaromatic monocarboxylic acid; in particular the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of nonaromatic monocarboxylic acid is preferably between 0.08 and 0.70, in particular between 0.10 and 0.60, in particular between 0.12 and 0.40. It has been found that this makes it possible in particular to obtain a polymer that is advantageously soluble in the oily media generally used to formulate cosmetic compositions such as lipsticks or foundations.

Preferably, the polycondensate according to the invention is obtainable by reaction of: at least one polyol chosen from, alone or as a mixture, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol ; pentaerythritol, erythritol, diglycerol, ditrimethylolpropane; xylitol, sorbitol, mannitol, dipentaerythritol and / or triglycerol; at least one nonaromatic monocarboxylic acid chosen from, alone or as a mixture, caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid; at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butyl benzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid; and at least one polycarboxylic acid or one of its anhydrides chosen from, alone or as a mixture, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid and cyclobutannedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid; cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; butanetetracarboxylic acid, pyromellitic acid, phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride.

Preferably, the polycondensate according to the invention has: an acid number, expressed in mg of potassium hydroxide per g of polycondensate, greater than or equal to 1; in particular between 2 and 30, and even better between 2.5 and 15; and / or - a hydroxyl number expressed in mg of potassium hydroxide per g of polycondensate, greater than or equal to 40; in particular between 40 and 120, and even better between 45 and 80.

These acid and hydroxyl numbers can be easily determined by those skilled in the art by the usual analytical methods.

Preferably, the polycondensate according to the invention has a weight average molecular weight (Mw) of between 1500 and 300 000, or even between 2000 and 10 200 000, and especially between 3000 and 100 000. The average molecular weight can be determined by gel permeation or light scattering chromatography, depending on the solubility of the polymer in question.

Preferably, the polycondensate according to the invention has a viscosity, measured at 110 ° C., of between 20 and 4000 mPa.s, in particular between 30 and 3500 mPa.s, even between 40 and 3000 mPa.s and even better between 50 and 2500 mPa.s. This viscosity is measured as described before the examples.

Furthermore, the polycondensate is advantageously soluble in the oily cosmetic media usually used, and in particular in vegetable oils, alkanes, fatty esters, fatty alcohols, silicone oils, and more particularly in media comprising isododecane, Parleam, isononyl isononanoate, octyldodecanol, phenyl trimethicone, C12-C15 alkyl benzoate and / or D5 (decamethylcyclopentasiloxane). "Soluble" means that the polymer forms a clear solution in at least one solvent chosen from isododecane, Parleam, isononyl isononanoate, octyldodecanol and C12-C15 alkyl benzoate, at least 50% by weight at 70 ° C. Some compounds even have a particularly advantageous solubility in certain fields of application, namely solubility in at least one of the solvents mentioned above, at least 50% by weight, at 25 ° C.

The polycondensate according to the invention can be prepared by the esterification / polycondensation processes usually employed by those skilled in the art. By way of illustration, a general method of preparation consists in: - mixing the polyol and the aromatic and nonaromatic monocarboxylic acids, - heating the mixture under an inert atmosphere, first up to the melting temperature (generally 100.degree. -130 ° C) and then at a temperature between 150 and 220 ° C until complete consumption of the monocarboxylic acids (reached when the acid number is less than or equal to 1), preferably by distilling as and to measure the water formed, then - to optionally cool the mixture to a temperature between 90 and 150 ° C, - to add the polycarboxylic acid and / or the cyclic anhydride, and optionally the silicone with hydroxyl or carboxylic functions , at once or sequentially, and then - to heat again at a temperature of less than or equal to 220 ° C., in particular between 170 and 220 ° C., preferably while continuing to eliminate the water formed. , until the required characteristics are obtained in terms of acid number, viscosity, hydroxyl number and solubility. It is possible to add conventional esterification catalysts, for example of the sulfonic acid type (especially at a concentration by weight of between 1 and 10%) or titanate type (in particular at a concentration by weight of between 5 and 100 ppm). It is also possible to effect the reaction, in whole or in part, in an inert solvent such as xylene and / or under reduced pressure, to facilitate the removal of water. Advantageously, no catalyst or solvent is used. The preparation process may also comprise a step of adding at least one antioxidant agent to the reaction medium, in particular at a concentration by weight of between 0.01 and 1%, relative to the total weight of monomers, so as to limit any degradations related to prolonged heating.

It is possible to use a mixture of polycondensates according to the invention. They may be present in the composition in solubilized form or in the form of a dispersion, for example in an oil or an organic carbon and / or silicone solvent, or a mixture. The polycondensate, alone or as a mixture, may represent 5 to 50% by weight, especially 10 to 45% by weight, or even 15 to 40% by weight, of the total weight of the mixture (block polymer + polycondensate).

Preferably, said polycondensate, alone or as a mixture, may be present from 0.1 to 10% by weight in the composition according to the invention, in particular from 0.2 to 5% by weight, or even from 0.4 to 4% by weight, relative to the total weight of the composition.

The cosmetic compositions according to the invention comprise, besides said polymers, a physiologically acceptable medium, in particular a cosmetically or pharmaceutically acceptable medium, that is to say a medium that is compatible with keratin materials such as the skin of the face or of the body, the lips , hair, eyelashes, eyebrows and nails.

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 origin, animal, vegetable or synthetic, carbonaceous, hydrocarbon, 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 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg) By contrast, the term "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'1-COO-R'2 where: R'1 represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably from 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 heteroatoms chosen 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, which may be substituted and The hydrocarbon chain may be interrupted by one or more heteroatoms selected from N and O and / or one or more carbonyl functions. By "optionally substituted" it is meant that R'1 and / or R'2 may carry one or more substituents chosen, for example, from groups comprising one or more heteroatoms chosen from O and / or N, such as amino or amine. , alkoxy, hydroxyl. Examples of the R'l groups are those derived from preferably higher fatty acids selected from the group consisting of acetic, propionic, butyric, caproic, caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, arachidic. , behenic, oleic, linolenic, linoleic, oleostearic, arachidonic, erucic, and their mixtures. Preferably, R'l is an unsubstituted branched alkyl group of 4 to 14 carbon atoms, preferably 8 to 10 carbon atoms, and R2 is an unsubstituted branched alkyl group of 5 to 15 carbon atoms, preferably 9 to 11 carbon atoms.

In particular, mention may be made, preferably, of C8-C48 esters, optionally incorporating in their hydrocarbon chain one or more heteroatoms of 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. 2 / hydrocarbon vegetable oils with a high triglyceride content consisting of esters of fatty acids and of glycerol, the fatty acids of which may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils include wheat germ, corn, sunflower, shea, castor oil, sweet almond, macamassia, apricot, soya, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape seed or black currant, evening primrose, millet, barley, quinoa, olive, rye, safflower, of bancoulier, passionflower, muscat rose, jojoba, palm, calophyllum; or caprylic / capric acid triglycerides 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, per- hydrosqualene and their mixtures. It is more particularly possible to mention linear, branched and / or cyclic C5-C48 alkanes, and preferably C8-C16 branched alkanes such as C8-C16 isoalkanes of petroleum or non-petroleum origin (also known as isoparaffins); especially decane, heptane, undecane, dodecane, tridecane, cyclohexane; as well as isododecane, isodecane, isohexadecane; and their mixtures.

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 1 to 22 carbon atoms; and in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, 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. 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 volatile oil, preferably carbonated, and in particular an oil chosen from, alone or as a mixture, isododecane, undecane , dodecane, tridecane, hexadecane, D4 (octamethylcyclotetrasiloxane), D5 (decamethylcyclopentasiloxane), D6 (dodecamethylcyclohexasiloxane).

The volatile oil makes it possible on the one hand to obtain a deposit, after evaporation of the support, and on the other hand makes it possible to make the sequenced polymer and the polycondensate compatible.

In a preferred embodiment, the volatile oils, in particular carbon oils, alone or as a mixture, are present in the composition in an amount of between 30 and 80% by weight, in particular 35 to 75% by weight, or even 40 to 70% by weight. weight, relative to the total weight of the composition.

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 perlorodecalin, perlorodamantanes, monoesters, diesters and triesters of perfluoroalkylphosphates and fluorinated ester oils; - oils of animal origin; - C6 to C40 ethers, 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; 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 ambient temperature, such as benzaldehyde and acetaldehyde.

The liquid fatty phase may represent 5 to 90% by weight of the composition, in particular from 10 to 75% by weight, in particular from 15 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 also comprise one or more physiologically acceptable organic solvents. These solvents may be generally present in a content ranging from 0.1 to 90%, preferably from 0.5 to 85%, more preferably from 10 to 80% by weight, relative to the total weight of the composition, and better from 30 to 50%. Mention may in particular be made, in addition to the hydrophilic organic solvents mentioned above, ketones that are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; 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; short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, isopentyl; ethers which are liquid at 25 ° C., such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes liquid at 25 ° C such as decane, heptane, dodecane, isododecane, cyclohexane; aromatic cyclic compounds liquid at 25 ° C such as toluene and xylene; aldehydes liquid at 25 ° C such as benzaldehyde, acetaldehyde and mixtures thereof.

The composition may also comprise solid fatty substances at ambient temperature such as waxes, pasty fatty substances, gums and mixtures thereof. They can be of animal, vegetable, mineral or synthetic origin. For the purposes of the present invention, the term "wax" means a lipophilic compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting point of greater than or equal to 25 ° C. at 120 ° C. By bringing the wax to the liquid state (melting), it is possible to render it miscible with the oils that may be present and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, recrystallization of the mixture is obtained. wax in the oils of the mixture. The melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METLER. The waxes may be hydrocarbon-based, fluorinated and / or silicone-based and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting point of greater than 30 ° C. and better still greater than 45 ° C. As waxes that can be used in the composition of the invention, mention may be made of beeswax, carnauba or candelilla wax, paraffin wax, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene or Fischer Tropsch waxes, silicone waxes such as alkyl or alkoxydimethicone containing from 16 to 45 carbon atoms. The gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and the pasty substances are generally hydrocarbon compounds such as lanolines and their derivatives or else PDMSs.

Pasty fat means a viscous product containing a liquid fraction and a solid fraction. In particular, it is meant fats having a melting point ranging from 20 to 55 ° C. and / or a viscosity at 40 ° C. ranging from 0.1 to 40 Pa.s (1 to 400 poise) as measured by Contraves TV or Rheomat 80. The person skilled in the art can choose the mobile device for measuring the viscosity, among the MS-r3 and MS-r4 mobiles, on the basis of his general knowledge, so as to be able to measure the viscosity of the pasty compound tested. The melting point values correspond, according to the invention, to the melting peak measured by the "Differential Scanning Calorimetry" method with a rise in temperature of 5 or 10 ° C./min. Preferably, these fatty substances are hydrocarbon compounds (containing mainly carbon and hydrogen atoms and optionally ester groups), possibly of polymeric type; they may also be chosen from silicone and / or fluorinated compounds; they may also be in the form of a mixture of hydrocarbon compounds and / or silicone and / or fluorinated. In the case of a mixture of different pasty fatty substances, the pasty hydrocarbon compounds are preferably used in major proportion. Among the pasty compounds which may be used in the composition according to the invention, mention may be made of lanolins and lanolin derivatives such as acetylated lanolines or oxypropylenated lanolins or isopropyl lanolate; esters of fatty acids or alcohols, in particular those having 20 to 65 carbon atoms, for example triisostearyl citrate or cetyl citrate; arachidyl propionate; vinyl polylaurate; esters of cholesterol such as triglycerides of plant origin such as hydrogenated vegetable oils, viscous polyesters such as poly (12-hydroxystearic acid) and mixtures thereof.

As triglycerides of plant origin, the hydrogenated castor oil derivatives can be used. Mention may also be made of silicone pasty fatty substances such as polydimethylsiloxanes (PDMSs) having pendant chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, such as stearyl dimethicones.

The nature and quantity of the solid bodies depend on the mechanical properties and textures sought. As an indication, the composition may contain from 0.1 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.

The composition may also comprise a hydrophilic medium comprising water or a mixture of water and one or more hydrophilic organic solvents such as alcohols and in particular lower linear or branched monoalcohols having from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol; polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol; polyethylene glycols, or else C 2 ethers and C 2 -C 4 aldehydes hydrophilic. The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content of 10 to 80% by weight, relative to the total weight of the composition. The composition may also be anhydrous.

The composition according to the invention may also comprise one or more dyestuffs chosen from pulverulent compounds such as pigments, fillers, nacres and flakes, and / or fat-soluble or water-soluble dyes.

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, hydrogen chromium drate 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 mica coated with titanium, or bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with especially 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 polyethylene, poly-3-alanine and polyethylene, Teflon, lauroyl-lysine, ami-don, nitrile boron, tetrafluoroethylene polymer powders, hollow microspheres such as Expancel (Nobel Industry), polytrap (Dow Corning) and silicone resin microspheres (Toshiba Tospearls, for example), calcium carbonate precipitate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, metallic soaps derived from organic carboxylic acids having from 8 to 22 atoms carbon, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate. Liposoluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, 13-carotene, soybean oil, Sudan Brown, DC Yellow, 11, DC Violet 2, DC Orange 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 according to the invention may also comprise, in addition, one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 02% to 30% by weight. By fillers, it is necessary to include colorless or white particles, mineral or synthetic, lamellar or non-lamellar, intended to give the body or rigidity to the composition, and / or softness, dullness and uniformity make-up. The fillers can be mineral or organic of any shape, platelet, spherical or oblong. Mention may be made of talc, mica, silica, kaolin, polyamide (nylon), poly-3-alanine and polyethylene powders, tetrafluoroethylene (Teflon) polymer powders, lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel (Nobel Industry), acrylic acid copolymers (Polytrap from Dow Corning) and silicone resin microbeads (Toshiba Tospearls, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads of Maprecos), glass microcapsules or ceramic, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium or lithium, zinc laurate, magnesium myristate.

The composition may further comprise an additional polymer such as a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials. Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures, in particular acrylic polymers, polyurethanes , polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.

The composition according to the invention may also comprise ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, auxiliary filtering agents, or 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 according to the invention are not, or not substantially, impaired by the addition envisaged.

The composition according to the invention may be in the form of a suspension, in particular a dispersion of oil in water by means of vesicles; an aqueous or oily solution optionally thickened or 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 biphase or multiphase lotion; a spray; a loose powder, compact or cast; an anhydrous paste. This composition may have the appearance of a lotion, a cream, an ointment, a soft paste, an ointment, a mousse, a solid cast or molded and especially stick or in a dish, 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, of the application envisaged for the composition.

In a particular mode of preparation of the composition according to the invention, it is possible, in a first step, to prepare the block polymer, which can be obtained in solution in the volatile carbonaceous oil, and then, in a second time, to add, optionally to hot and / or with stirring, the polycondensate with said solution of sequenced polymer, and finally introducing the remainder of the constituents of the cosmetic composition, according to a usual procedure, determined by the person skilled in the art on the basis of his general knowledge.

The cosmetic composition according to the invention may be in the form of a care product and / or makeup of the skin of the body or face, lips, nails, eyelashes, eyebrows and / or hair, a suntan or self-tanning product, a hair product for care, treatment, shaping, makeup or hair coloring. It may thus be in the form of a make-up composition, in particular a product for the complexion such as a foundation, a blush or an eyeshadow; a lip product such as lipstick, lip gloss or lip care; a concealer product; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip pencil or an eye pencil; nail product such as nail polish or nail care; a body make-up product; a hair makeup product (mascara or hairspray). It may also be in the form of a composition for protecting or caring for the skin of the face, neck, hands or body, in particular an anti-wrinkle composition, a moisturizing or treating composition; a composition of sun or artificial tanning (self-tanning).

It may also be in the form of a hair product, especially for coloring, maintaining the hairstyle, shaping the hair, care, treatment or cleaning of the hair, such as shampoos, gels, styling lotions, blow-drying lotions, fixing and styling compositions such as lacquers or spray.

Preferably, the cosmetic composition according to the invention is in the form of a makeup product, especially a lipstick, a mascara, a nail polish, a foundation, or a care product such as a facial care cream or a sun product.

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

The invention is illustrated in more detail in the following examples.

Brilliance measured on a glossy meter on a dry polymer deposit Gloss can be measured using a gloss meter, conventionally by the following method. On a LENETA brand contrast card and PENOPAC FORM 1A reference, a layer of 50 .mu.m thick of polymer or mixture of test polymers, in solution in isododecane, is spread with the aid of a spreader. The layer covers at least the black background of the card. The deposit is allowed to dry for 24 hours at a temperature of 25.degree. C., then the gloss is measured at 20.degree. On the black background using a glossmeter of the DR LANGE brand, REF03. The brightness at 60 ° is also measured as before.

Maintenance with olive oil by measurement of the sticky appearance It is determined with a drop of olive oil placed on a dry polymer film. A polymer film is made from a solution obtained by dilution with isododecane, so as to have a concentration of 20% by weight of polymer sequenced either in the mixture 'block polymer / polycondensate / isododecane' (invention), or in the mixture 'block polymer / isododecane' (comparative); 0.5 ml is spread on a 2.5 x 7.5 cm glass plate and allowed to dry at room temperature (25 ° C) for 24 hours. Then 1 ml of olive oil is spread on the film. After the desired time (1 or 2 hours), the excess oil is wiped off the film and the tacky appearance is evaluated to the touch. A + note is given when the pantyhose is noticeable after a short press (about 1 second) with the finger. A note - is given when no stickiness is detected, after a short press with the finger. Sticky reflects the sensitivity of the polymer to olive oil. The more important it is, the more the polymer is sensitive to the oil and therefore the more the deposit will be easily altered, for example during meals (in the presence of edible oil) or sebum. This results in a poorer behavior of the polymer on the skin. It also results in a reduction of comfort: the more the film is sticky, the more the composition is uncomfortable to wear.

Determination of brittleness On a LENETA brand contrast card and reference FORM 1A PENOPAC, a layer of 50 .mu.m thick of polymer or mixture of test polymers, in solution in isododecane, is spread with the aid of a spreader. The layer covers at least the black background of the card. The deposit is allowed to dry for 24 hours at a temperature of 25 ° C. We curve the map and observe the formation of cracks. A rating +++ means that the film is very brittle, the pieces are off the map, the film cracks without even the card is bent.

A note + means that the film is not very brittle, some cracks appear, the film remains cohesive.

Method for Measuring the Viscosity of the Polycondensates The viscosity at 80 ° C. or at 110 ° C. of the polycondensate is measured using a BROOKFIELD CAP 1000+ flat cone screw-costimeter. The adapted cone-plane is determined by the person skilled in the art, on the basis of his knowledge; in particular: - between 50 and 500 mPa.s, one can use a cone 02 - between 500 and 1000 mPa.s: cone 03 30 - between 1000 and 4000 mPa.s: cone 05 - between 4000 and 10000 mPa.s: cone 06

Method for Measuring the Viscosity of the Block Polymers The viscosity at 25 ° C. of the block polymer is measured using a BROOKFIELD DV-I + cylindrical viscometer.

EXAMPLE 1 Preparation of a Block Polymer of Poly (Isobornyl Acrylate / Isobornyl Methacrylate / Isobutyl Acrylate / Acrylic Acid) 300 g of isododecane are introduced into a 1-liter reactor, and the temperature is then increased to go from room temperature (25 ° C) to 90 ° C in 1 hour. 105 g of isobornyl methacrylate, 105 g of isobornyl acrylate and 1.8 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane are added at 90 ° C. and over 1 hour. (Trigonox ° 141 from Akzo Nobel). The mixture is maintained for 1 h 30 at 90 ° C. 75 g of isobutyl acrylate, 15 g of acrylic acid and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2 are then introduced into the above mixture, still at 90 ° C. and over 30 minutes. , 5-dimethylhexane. The mixture is kept at 90 ° C. for 3 hours, then the mixture is cooled. A 50% solution of polymer solids in isododecane is obtained. The polymer comprises a first poly (isobornyl acrylate / isobornyl methacrylate) block having a Tg of 110 ° C, a second poly (isobutyl acrylate / acrylic acid) block having a Tg of -9 ° C and a sequence of intermediate which is a statistical polymer isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate / acrylic acid. The 50% by weight solution of polymer in isododecane has a viscosity of 30,000 cps at 25 ° C.

EXAMPLE 2 Preparation of a Block Polymer of Poly (Isobornyl Acrylate / Isobornyl Methacrylate / Isobutyl Acrylate) 100 g of isododecane are introduced into a 1-liter reactor, and the temperature is then increased in order to pass from room temperature (25 ° C) at 90 ° C in 1 hour. 105 g of isobornyl methacrylate, 105 g of isobornyl acrylate, 110 g of isododecane and 1.8 g of 2,5-bis (2-ethylhexanoylperoxy) are added at 90 ° C. and over 1 hour. -2,5-dimethylhexane (Trigonox ° 141). The mixture is maintained for 1 h 30 at 90 ° C. 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2 are then introduced into the preceding mixture, still at 90 ° C. and over 30 minutes, 5-dimethylhexane. The mixture is kept at 90 ° C. for 3 hours, then the mixture is cooled. A 50% solution of polymer solids in isododecane is obtained. The polymer comprises a first poly (isobornyl acrylate / isobornyl methacrylate) block having a Tg of 110 ° C, a second poly (isobutyl acrylate) block having a Tg of -20 ° C and an intermediate block which is a random isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate polymer.

Example 3 Synthesis of pentaerythritylbenzoate / isophthalate / isostearate / PDMS In a reactor equipped with mechanical stirring, an inlet of argon and a distillation system, 32 g of benzoic acid, 504 g isostearic acid and 136 g of pentaerythritol, and then gradually heated under a gentle stream of argon at 110-130 ° C to obtain a homogeneous solution. The temperature is then gradually increased to 180 ° C and held for about 2 hours. The temperature is again raised to 220 ° C and maintained until an acid number of less than or equal to 1 is obtained, which takes about 9 hours. The mixture is cooled to a temperature of between 100 and 130 ° C., then 144 g of isophthalic acid and 80 g of Shin-Etsu Silicon A, W Diol X22-160AS are introduced and the mixture is heated again gradually to 220 ° C. for about 15 hours. 750 g of pentaerythrityl benzoate / isophthalate / isostearate / PDMS polycondensate are thus obtained in the form of an oil.

The polycondensate has the following characteristics: 10 - soluble to 50% by weight, at 25 ° C, in the Parléam - Mw = 11700 - 1180 ° c = 798 mPa.s - n11o ° c = 190 mPa.s

EXAMPLE 4 Synthesis of pentaerythritol benzoate / isophthalate / isostearate In a reactor equipped with mechanical stirring, an argon inlet and a distillation system, 20 g of benzoic acid, 280 g of isostearic acid and 100 g of pentaerythritol, and then heated gradually, under a gentle stream of argon, at 110-130 ° C to obtain a homogeneous solution. The temperature is then gradually increased to 180 ° C. and held for about 2 hours. The temperature is again raised to 220 ° C and maintained until an acid number of less than or equal to 1 is obtained, which takes about 11 hours. The mixture is cooled to a temperature between 100 and 130 ° C., then 100 g of isophthalic acid are introduced and heated again gradually to 220 ° C. for about 11 hours. 405 g of pentaerythrityl benzoate / isophthalate / isostearate polycondensate are thus obtained in the form of a very thick oil.

The polycondensate has the following characteristics: Soluble at 50% by weight, at 25 ° C, in the Parléam - Mw = 59400 - Hilo ° c = 1510 mPa.s

Example 5 Synthesis of pentaerythrityl benzoate / isophthalate / isostearate / PDMS In a reactor equipped with mechanical stirring, an inlet of argon and a distillation system, 14 g of benzoic acid, 255 g of isostearic acid and 75 g of pentaerythritol, and is then gradually heated under a gentle stream of argon at 110-130 ° C to obtain a homogeneous solution. The temperature is then gradually raised to 180 ° C. and held for about 2 hours. The temperature is again raised to 220 ° C and maintained until an acid number of less than or equal to 1 is obtained, which takes about 7 hours. The mixture is cooled to a temperature of between 100 and 130 ° C. and then 65 g of isophthalic acid and 38 g of Tegomer C-Si 2342 (Goldschmidt) α-Dicarboxy Silicone are introduced and the mixture is gradually heated again. 220 ° C for about 15 hours.

There is thus obtained 375 g of pentaerythrityl benzoate / isophthalate / isostearate / PDMS polycondensate in the form of a thick oil.

The polycondensate has the following characteristics: - soluble at 50% by weight, at 25 ° C, in the Parleam - r8o ° c = 1332 mPa.s

Example 6 Synthesis of pentaerythritol benzoate / isophthalate / isostearate / PDMS In a reactor equipped with mechanical stirring, an inlet of argon and a distillation system, 16 g of benzoic acid, 252 g isostearic acid and 68 g of pentaerythritol, and then heated gradually under a gentle stream of argon at 110-130 ° C to obtain a homogeneous solution. The temperature is then gradually increased to 180 ° C and held for about 2 hours. The temperature is again raised to 220 ° C and maintained until an acid number of less than or equal to 1 is obtained, which takes about 9 hours. The mixture is cooled to a temperature of between 100 and 130 ° C. and then 40 g of isophthalic acid and 40 g of Shin-Etsu Silicon A, W diol X22-160AS are introduced and the mixture is heated again gradually to 220 ° C. for about 7 hours.

There is thus obtained 345 g of pentaerythrityl benzoate / isophthalate / isostearate / PDMS polycondensate in the form of an oil.

The polycondensate has the following characteristics: - soluble to 50% by weight, at 25 ° C, in the Parleam 30 - Mw = 3600 - n8o ° c = 125 mPa.s

EXAMPLE 7 Synthesis of pentaerythritol benzoate / isophthalate / stearate In a reactor equipped with mechanical stirring, an inlet of argon and a distillation system, 10 g of benzoic acid, 370 g of stearic acid and 95 g of pentaerythritol and then gradually heated under a gentle stream of argon at 110-130 ° C to obtain a homogeneous solution. The temperature is then gradually increased to 180 ° C and held for about 2 hours. The temperature is again raised to 220 ° C and maintained until an acid number of less than or equal to 1 is reached, which takes about 11 hours. The mixture is cooled to between 100.degree. And 130.degree. C., after which 90 g of isophthalic acid are introduced and heated again gradually to 220.degree. C. for about 11 hours. 430 g of pentaerythrityl benzoate / isophthalate / stearate polycondensate are thus obtained in the form of a very thick oil which crystallizes on cooling. After grinding with the mixer, a beige powder is obtained. The polycondensate has the following characteristics: - soluble to 50% by weight, at 70 ° C., in the Parléam - Mw = 8800 - 1180 ° C. = 360 mPa.s Example 8 In a 1 liter reactor, 393 g are charged of a 46.4% by weight solution of the block polymer solids of Example 1 in isododecane. 43 g of polycondensate prepared in Example 4, preheated in an oven at 110 ° C. for one night, are introduced. The reactor is heated to 90 ° C. and stirred so that the medium is homogeneous. A change in appearance of the reaction medium is observed, which changes from a colorless appearance to a pale yellow appearance. The reaction medium is cooled to 60 ° C.

The characteristics of the mixture obtained are as follows: 42% by weight of block polymer, 48% by weight of isododecane and 10% by weight of polycondensate. The viscosity of the mixture is 65,000 cps at 25 ° C., measured using a BROOKFIELD DV-I + cylindrical viscometer.

Example 9 In a 1 liter reactor, 361 g of the mixture prepared in Example 8 above was charged. 45 g of polycondensate prepared in Example 4 preheated in an oven at 110 ° C. overnight are introduced. The mixture is heated to 90 ° C. and stirred so that the medium is homogeneous. There is a change in appearance of the reaction medium, which takes on a more and more yellow and viscous appearance. The reaction medium is cooled to 60 ° C.

The characteristics of the mixture obtained are as follows: 37% by weight of block polymer, 43% by weight of isododecane and 20% by weight of polycondensate. The viscosity of the mixture is greater than 100,000 cps at 25 ° C., measured using a BROOKFIELD DV-I + type cylindrical viscometer.

Example 10 In a 1 liter reactor, 290 g of a 46.4% by weight solution of the sequenced polymer solids of Example 1 are charged to isododecane. 15 g of prepared polycondensate are introduced. in Example 4, previously heated in an oven at 110 ° C overnight. The reactor is heated to 90 ° C. and stirred so that the medium is homogeneous. A change in appearance of the reaction medium is observed, which changes from a colorless appearance to a pale yellow appearance. The reaction medium is cooled to 60 ° C.

The characteristics of the mixture obtained are as follows: 44% by weight of block polymer, 51% by weight of isododecane and 5% by weight of polycondensate. The viscosity of the mixture is 50,000 cps at 25 ° C., measured using a BROOKFIELD DV-I + cylindrical viscometer.

EXAMPLE 11 The gloss, tackiness and brittleness of the blends prepared in Examples 8, 9 and 10 were determined in comparison with a block polymer alone. Example 1 Example 8 Example 9 Example 10 (except inv.) Viscosity (25 ° C) 30,000cps 65,000cps> 100,000cps 50,000cps of the solution 0/0 of polymer - 80% 65% 90% sequenced * Dry extract 50% by weight 52% by weight 57% by weight 49% by theoretical weight of the mixture Appearance of the film Brilliant shiny gloss Shine 20 ° = 80 20 ° = 77.1 20 ° = 51.8 20 ° = 77.8 60 ° = 87.2 60 ° = 87.6 60 ° = 80.2 60 ° = 89.3 Tights (sensi- 1 hour: - 1 hour: - 1 hour: - 1 hour: - bility in oil 2 hours: + 2 hours: - 2 hours: - 2 hours: - of olive) Brittle +++ ++ + ++ *% by weight of polymer sequenced in the polymer block + polycondensate mixture Example 12: Stick of lipstick following lipstick composition: polyethylene wax 15%, blend of Example 8 20% (ie approximately 10% DM), hydrogenated polyisobutene (Parléam de Nippon Oil Fats) 26%, pigments 8.6%, Isododecane qs 100%

Example 13 Lip Gloss A gloss having the following composition is prepared: - Mixture of Example 9 28% (ie approximately 16% by weight) - Polybutene 34% - isononyl isonononate 40% - octyldodecanol 10 0/0 - silica (Aerosil R972) 5 0/0 - tridecyl trimellitate qs 100%

After applying to the lips, a glossy film is obtained which remains at least 2 hours.

EXAMPLE 14 Lipstick A lipstick is prepared having the following composition: - Mixture of Example 10 30% (ie about 15% DM) - polyethylene wax II% - pigments and fillers 7% - Parleam (hydrogenated isoparaffin) ) qsp 100% is obtained after application to the lips, a colored film and gloss, which remains bright at least 2 hours.

Claims (16)

REVENDICATIONS1. Cosmetic composition comprising, in a cosmetically acceptable medium, (i) a block polymer comprising at least a first sequence and at least a second sequence incompatible with each other and having different glass transition temperatures (Tg), (ii) a polycondensate obtainable by reaction of at least: from 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups; from 30 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms; from 1 to 40% by weight, relative to the total weight of the polycondensate, of at least one polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH; and / or a cyclic anhydride of such a polycarboxylic acid; and / or a lactone comprising at least one COOH group. 2. Composition according to claim 1, wherein, in the sequenced polymer, said first and second sequences are interconnected by an intermediate segment, or even an intermediate sequence, comprising at least one constituent monomer of the first block and at least one monomer. constituent of the second sequence. 3. Composition according to one of the preceding claims, wherein one of the sequences has a Tg between 20 ° C and 160 ° C, and one of the sequences has a Tg between -150 ° C and 20 ° C (excluded). 4. Composition according to one of the preceding claims, wherein the block polymer comprises in at least one sequence, preferably in each of the sequences, at least one monomer selected from (meth) acrylic acid esters; and optionally, furthermore comprises at least one second monomer chosen from acrylic acid and methacrylic acid, or even their mixture. 5. Composition according to one of the preceding claims, in which the block polymer, alone or as a mixture, represents 50 to 95% by weight, in particular 55 to 90% by weight, or even 60 to 85% by weight, by weight. total of the mixture (block polymer + polycondensate). 6. Composition according to one of the preceding claims, wherein the block polymer, alone or in mixture, is present in a proportion of 1 to 25% by weight in the composition according to the invention, especially 2 to 20% by weight, or 5 to 15% by weight, relative to the total weight of the composition. 7. Composition according to one of the preceding claims, wherein the polycondensate according to the invention is obtainable by reaction of: - at least one polyol selected from, alone or in a mixture, 1,2,6- hexanetriol, trimethylolethane, trimethylolpropane, glycerol; pentaerythritol, erythritol, diglycerol, ditrimethylolpropane; xylitol, sorbitol, mannitol, dipentaerythritol and / or triglycerol; at least one nonaromatic monocarboxylic acid chosen from, alone or as a mixture, caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid; at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butyl benzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid; and at least one polycarboxylic acid or one of its anhydrides chosen from, alone or as a mixture, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid , phthalic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid ; cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; butanetetracarboxylic acid, pyromellitic acid, phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride. 8. Composition according to one of the preceding claims, wherein the polycondensate according to the invention has a viscosity, measured at 110 ° C, between 20 and 4000 mPa.s, in particular between 30 and 3500 mPa.s, or between 40 and 3000 mPa.s and even better between 50 and 2500 mPa.s. 9. Composition according to one of the preceding claims, wherein the polycondensate, alone or in mixture, represents 5 to 50% by weight, in particular 10 to 45% by weight, or even 15 to 40% by weight, of the total weight of the mixture. (Sequential polymer + polycondensate). 10. Composition according to one of the preceding claims, wherein the polycondensate, alone or in mixture, is present in a proportion of 0.1 to 10% by weight, in particular 0.2 to 5% by weight, or even 0.4 to 4% by weight, relative to the total weight of the composition. 11. Composition according to one of the preceding claims, wherein the cosmetically acceptable medium comprises at least one ingredient selected from oils and / or solvents of mineral, animal, plant or synthetic origin, carbon, hydrocarbon, fluorinated and / or or silicone, volatile or non-volatile; solid fats solid at room temperature such as waxes, pasty fatty substances, gums; some water; hydrophilic organic solvents; dyestuffs chosen from pulverulent compounds such as pigments, fillers, pearlescent agents and flakes, and / or fat-soluble or water-soluble dyes; the charges; additional polymers such as a film-forming polymer; vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, auxiliary film-forming agents, and mixtures thereof. 12. Composition according to one of the preceding claims, comprising at least one volatile oil, in particular chosen from, alone or as a mixture, isododecane, undecane, dodecane, tridecane, hexadecane, D4 (octa- methylcyclotetrasiloxane), D5 (decamethylcyclopentasiloxane), D6 (dodecamethylcyclohexasiloxane). 13. Composition according to claim 12, in which the volatile oils, alone or as a mixture, are present in an amount of between 30 to 80% by weight, in particular 35 to 75% by weight, or even 40 to 70% by weight, by weight. relative to the total weight of the composition. 14. Composition according to one of the preceding claims, in the form of a care product and / or make-up of the skin of the body or face, lips, nails, eyelashes, eyebrows and / or hair, a sun product or self-tanning, a hair product for the care, treatment, shaping, makeup or hair coloring. 15. Composition according to one of the preceding claims, in the form of a makeup product, in particular a lipstick, a mascara, a nail polish, a foundation, or a care product such as a facial care cream or a sun product. 16. Cosmetic treatment process, especially for make-up or care, keratin materials such as the skin of the body or of the face, lips, nails, hair, eyebrows and / or eyelashes, comprising the application on said materials of a cosmetic composition as defined in one of claims 1 to 15.