WO2006106487A1

WO2006106487A1 - Copolymers of polyolefine / phosphorylcholine in cosmetic compositions

Info

Publication number: WO2006106487A1
Application number: PCT/IB2006/051043
Authority: WO
Inventors: Jean Mondet; Xavier Blin; Momoko Shimizu; Yuta Nomura
Original assignee: L'oreal
Priority date: 2005-04-06
Filing date: 2006-04-05
Publication date: 2006-10-12

Abstract

The present invention relates to a cosmetic composition containing at least one polymer comprising at least: - one group of formula (I) in which the groups R5 are identical or different and each is a hydrogen atom or a (C1-C4)alkyl group and e is a natural number ranging from 1 to 4, and - a graft or a block of polyolefinic nature, or a polymeric unit derived from an α-olefin of structure CH2=CR1R2, in which R1 denotes a hydrogen or a methyl radical and R2 denotes a linear or branched (C1-C5o)alkyl group, or a (C1-C7)CyClOaIlCyI group.

Description

COPOLYMERS OF POLYOLEFINE / PHOSPHORYLCHOLINE IN COSMETIC COMPOSITIONS

The present invention relates to cosmetic makeup and/or care compositions intended to be applied to the skin, the lips and/or the integuments, containing novel polymers or copolymers. The present invention is more particularly directed toward proposing an oil or a gum of polyolefinic type, conventionally used for its gloss properties, modified to improve its staying power on keratin materials, and thus toward proposing novel polymers or copolymers.

Specifically, it is known that oils of polyolefinic nature, on account of their apolarity, do not have optimum properties in terms of adhesion, especially to the lips.

WO 93/01221 or US 6 225 431 discloses a polymer comprising pendent groups bearing a center of permanent positive charge and also other pendent groups capable of binding the polymer stably to a surface by physisorption, covalent bonding or ionic interactions. Firstly, the field of application is different than that of the invention. Furthermore, although the polymer described can comprise a zwitterionic monomer, and in particular phosphorylcholine, the necessary presence of a group that provides cosmetic properties of gloss, compatibility with oils and staying power is not desired.

WO 99/63956 discloses a copolymer comprising monomers of the 2- (meth)acryloyloxyethylphosphorylcholine type and of the (meth)acrylic ester type. Such a copolymer may be used in cosmetics, including uses in the field of haircare. However, this copolymer differs from the polymers or copolymers according to the present invention both in terms of structure and in terms of cosmetic properties. These polymers moreover have the drawback of being solid and of being difficult to disperse in oils.

JP- A-2003 -40942 discloses a method for synthesizing a polymer containing phosphorylcholine side groups. The main polymer chain does not itself contain any blocks of polyolefinic nature.

In point of fact, the copolymers described above do not simultaneously have grafts and/or blocks of polyolefinic nature capable of imparting gloss to cosmetic compositions and groups of phosphorylcholine type capable of imparting staying power to cosmetic compositions. Specifically, such properties are commonly imparted by different components, which presents the drawback of introducing constraints in terms of mutual compatibility of the components in particular. There is consequently a need to collectively optimize the gloss and the staying power of cosmetic compositions by adding a modified oil, which is preferably dispersible in the fatty phase.

There is moreover a need to improve the properties of adhesion to the skin and the lips of oils or gums of polyolefinic type.

Finally, there is a need to improve the dispersion of the pigments conventionally present in cosmetic compositions.

The present invention is a novel means that allows facilitated formulation of cosmetic compositions. In other words, in a single addition of the polymer or copolymer according to the present invention, the gloss and staying power properties, in particular the staying power of the gloss over time, may be simultaneously improved. Incidentally, this polymer or copolymer can also afford beneficial effects in terms of moisturization, care and protection.

One subject of the present invention is, more specifically, a cosmetic composition containing at least one polymer comprising at least:

- one group of formula (I):

o- in which the groups R₅ are identical or different and each is a hydrogen atom or a (Ci-C₄)alkyl group and e is a natural number ranging from 1 to 4, and - a graft or a block of polyolefinic nature or a polymeric unit derived from an α-olefin of structure CH₂=CR₁Ri, in which R₁ denotes a hydrogen or a methyl radical and R₂ denotes a linear or branched (C₁-C₅₀)alkyl group, or a (C₁-C₇)cycloalkyl group.

According to yet another of its aspects, the present invention relates to the use of the polymer as defined above in a cosmetic composition. Finally, according to a final aspect, a subject of the present invention is a non- therapeutic process for making up and/or caring for keratin materials, comprising at least one step of applying thereto at least one composition as defined above.

For the purposes of the present invention, the term "polymer" is intended to denote a product consisting of an assembly of macromolecules and characterized by certain properties such as the molecular mass. The term "polymer" means a compound comprising at least two and preferably at least three repeating units.

For the purposes of the present invention, the term "monomer" covers a molecule capable of being converted into a polymer via combination with itself or with other molecules of the same type.

For the purposes of the present invention, the term "copolymer" is intended to denote a polymer derived form at least two types of monomer.

Furthermore, for the purposes of the present invention:

- the term "repeating unit" or "polymer unit" denotes the smallest constitutive unit whose repetition leads to a regular macromolecule,

- the term "constitutive unit" denotes an atom or a group of atoms, including optionally attached atoms or groups of atoms, which constitutes a fundamental part of the structure of a macromolecule,

- the term "polymer chain" or "chain" denotes a macromolecule or a part of a macromolecule comprising a linear or branched sequence of consecutive units located between two limiting consecutive units which may each be an end group, a branching point or a particular feature characteristic of the macromolecule,

- the term "main chain" denotes the longest chain, that is to say the chain comprising the largest number of consecutive units. - the term "block" denotes a part of a macromolecule comprising a linear or branched sequence of polymer units, for example identical polymer units, and which has at least one particular feature of constitution or of configuration that does not appear in the adjacent parts,

- the terms "block polymer" and "block copolymer" cover, respectively, a polymer whose macromolecules consist of linearly linked blocks and a block polymer derived from several species of monomer. They may be regular or irregular,

- the term "graft" denotes a macromolecule comprising a linear or branched sequence of identical or different polymer units linked laterally to the main chain of a polymer via a covalent bond, - the terms "grafted polymer" and "grafted copolymer" cover a polymer composed of macromolecules comprising grafts linked to the main chain; these grafts constitute side chains and have constitution or conformation characteristics that are different than those of the main chain and, respectively, a grafted polymer derived from several species of monomer,

- the term "comb polymer" or "comb copolymer", which is a sub-category of grafted polymers or copolymers, denotes a polymer or a copolymer having a linear main chain of a certain chemical nature and polymer chains known as "side branches", of identical or different chemical nature, which are also linear but significantly shorter than the main chain, attached covalently to said main chain via one of their ends,

- the term "alternating copolymer" covers a copolymer consisting of macromolecules comprising two kinds of monomer units distributed in alternation, - the term "statistical copolymer" covers a copolymer consisting of macromolecules in which the distribution of the monomer units obeys known statistical laws, and the term "random copolymer" covers a copolymer consisting of macromolecules in which the probability of finding a given monomer unit at a given point on the chain is independent of the nature of the adjacent units, - the term "gradient copolymer", which is a sub-category of the statistical copolymers, denotes copolymers presenting a change in the ratio of the various monomers along the chain. The distribution of the comonomers in the polymer chains depends on the change during the synthesis of the relative concentrations of comonomers.

- the term "block copolymer" denotes a copolymer having blocks. In the case of branching comprising a single point of attachment, the polymer is a "star polymer".

In the context of the present invention, a graft, block, sequence, polymer and/or copolymer said to be "of polyolefinic nature" denotes a polymer containing at least two, preferably at least three identical or different repeating units derived from the polymerization of α-olefins.

An α-olefin is a compound of formula CH₂=CR₁R₂ in which R₁ represents a hydrogen or a methyl radical and R₂ represents a linear or branched (C₁-C₅₀)alkyl or a (C₁- C₇)cycloalkyl.

According to one preferred embodiment, the α-olefin is chosen such that the homopolymer obtained from said α-olefin is non-crystalline, i.e. does not exhibit a reversible change of liquid/solid state. Suitable α-olefins for implementing the present invention include, preferably, butene, butylene, isobutene, hexene, octene and their isomers.

In the remainder of the description, and out of concern for simplification, the term "olefinic" is intended to denote an α-olefin as defined above. Moreover, an "olefin polymer unit" denotes a polymeric unit derived from an α-olefinic monomer.

In the context of the present invention, the term "keratin materials" comprises the skin, the lips, the nails, the hair, the eyelashes and the eyebrows, and "keratin fibers" denotes the hair, the eyelashes and the eyebrows. The term "between ... and ..." means that the limits are also described.

The term "staying power" denotes the staying power of the color or the gloss, the reduction in migration and/or the reduction in transfer.

POLYMER: HOMOPOL YMER OR COPOLYMER The polymer may be a homopolymer or a copolymer, which may especially be in block, grafted, statistical or random, alternating, star, comb, gradient or mixed form, or alternatively of the type such as a polymer of polyolefinic nature comprising at least one group of formula (I) as defined above at one or at both of its ends, or alternatively directly on the main polymer chain. The groups of formula (I) as defined above may be linked, independently of each other, to at least one polymer unit of the main chain, to one or both of the ends of the polymer or of the copolymer according to the present invention, or alternatively may be included in at least one chain and/or one block and/or one graft constituting the polymer or the copolymer according to the present invention. It is moreover specified that this group of formula (I) as defined above may be linked directly via covalent bonding or via suitable spacers.

The polymer may be crosslinked. According to one embodiment, the polymer is not crosslinked.

As illustrations of the various structures that may be adopted by the polymer or copolymer according to the present invention, mention may be made most particularly of those in which all or part of the polymer or copolymer is: - in the form of grafted copolymers comprising a main chain comprising at least one block of polyolefinic nature and whose grafts comprise at least one group of formula (I) as defined above, and preferably phosphorylcholine,

- in the form of grafted copolymers comprising a main chain comprising at least one block comprising at least one group of formula (I), as defined above and whose grafts comprise identical or different blocks of polyolefinic nature,

- in the form of block copolymers, for example diblock or triblock copolymers, comprising linearly linked blocks of polyolefinic nature and at least one block comprising at least one group of formula (I) as defined above, and preferably phosphorylcholine, - in the form of a statistical or random copolymer comprising linearly linked polymer units derived from α-olefins and polymer units, at least one of which comprises at least one group of formula (I) as defined above, and preferably phosphorylcholine, or

- in the form of a homopolymer or copolymer of α-olefins which is functionalized at at least one of its ends by at least one group of formula (I) as defined above, and preferably phosphorylcholine:

- in the form of a copolymer comprising linearly linked, identical or different blocks of polyolefinic nature and comprising at one or both of its ends at least one group of formula (I) as defined above, and preferably phosphorylcholine, or

- in the form of a polymer of polyolefinic nature comprising at least one group of formula (I) as defined above, at one or both of its ends, or

- in the form of a mixed copolymer comprising at least one graft and/or block of polyolefinic nature, comprising at least one group of formula (I) as defined above, and preferably phosphorylcholine.

The term "mixed copolymer" means a copolymer comprising polymer chains of different nature, i.e. statistical, random, alternating, block, grafted, star or gradient polymers.

Needless to say, polymers and copolymers in which several types of variants listed above and/or detailed below are combined together, either as has been described above for the mixed copolymers, by combination of chains or blocks of more than two different types, or in the form of a mixture of different polymers or copolymers, are also included in the context of the present invention. The polymer or copolymer according to the present invention may also comprise one or more groups comprising a center of positive charge, or zwitterionic group different than the group of formula (I) as defined above.

The polymer or copolymer according to the present invention is preferably liposoluble or dispersible in a fatty phase. Thus, according to one preferred embodiment, it is in the form of an oil of variable viscosity. When the oil has a very high viscosity, it may also be referred to as a gum.

The polymer or copolymer according to the present invention may have a viscosity ranging from 0.5 to 10⁹ cP, for example from about 10 to 10⁵ cP. The polymer or copolymer according to the present invention preferably has a weight-average molecular mass (or molecular mass at the crest of the GPC peak) of between 500 and 10⁶, preferably between 1000 and 500 000 and even more preferably between 3000 and 250 000 g/mol.

According to one preferred embodiment of the invention, the polymer or copolymer according to the present invention may comprise polymer units, chains, blocks and/or grafts derived from monomers which are different than the chains, blocks and/or grafts of different polyolefinic nature and from the optional chains, blocks and/or grafts comprising the group of formula (I). The monomers from which these additional units, chains, blocks and/or grafts are derived may advantageously be chosen from lipophilic monomers capable of copolymerizing with monomers bearing a group of formula (I), known as monomers (A) and macromonomers of polyolefinic nature. Such monomers are referred to in the description hereinbelow as monomers of formula (C).

Among the monomers that may be chosen as monomers of formula (C), mention may be made of alkyl (meth)acrylates, linear, branched or cyclic C₄-C₄₀ alkyl (meth)acrylates, N-alkyl(meth)acrylamides, N,N'-dialkyl(meth)acrylamides, alkyl vinyl esters, alkyl vinyl ethers and alkyl alkyl esters, the alkyl groups of these monomers being

C₄-C₄₀ and linear, branched or cyclic.

It is preferred that the polymer chains, blocks and/or grafts obtained from the monomers (C) are not crystallizable. According to one preferred embodiment of the invention, at least one of the monomers (C) is chosen from C₄-C₄₀ alkyl (meth)acrylates, for example C₁₂-C₂₄ alkyl (meth)acrylates. Among the latter, mention may be made especially of butyl, isobutyl, tert- butyl, hexyl, tert-hexyl, octyl, 2-ethylhexyl, tert-octyl, decyl, undecyl, dodecyl, isononyl or isostearyl (meth)acrylate.

The presence of polymer units, blocks and/or grafts derived from the polymerization of such monomers (C) in the polymers or copolymers according to the present invention may be particularly advantageous for adjusting the lipophilicity of the polymer or copolymer obtained. It may also have the advantage of limiting the emulsifying nature of the polymer or copolymer that might be obtained as a result of the charges included in the groups of formula (I).

As regards the preparation of the copolymers according to the present invention, it may be performed via any conventional polymerization technique. The choice of the method is generally made by taking into account the desired structure for the copolymer, that is to say, for example, grafted copolymer or sequenced copolymer, and as a function of the reactivity and of the preferred mode of polymerization of the monomers present. Several embodiments of the polymers according to the present invention are detailed below.

GRAFTED COPOLYMER

According to one embodiment of the invention, the polymer as defined above is chosen from grafted polymers.

A grafted copolymer according to the present invention may have a main chain comprising at least one polymer unit derived from the monomer of formula (A) defined below and/or may comprise a monomer of formula (A) at at least one of its ends.

According to one particular embodiment of the invention, the grafts are derived from macromonomers of polyolefinic type comprising an end that is copolymerizable with the monomers of formula (A) and/or the other possible monomers forming the main chain. These polyolefins may advantageously comprise polybutene isomers detailed below.

Thus, according to one of its aspects, a subject of the present invention is more particularly a grafted copolymer comprising at least: - a main chain comprising at least one polymer unit derived from a monomer of formula (A):

Y-B-X (A) - X takes the formula (I):

in which the groups R₅ are identical or different and each is a hydrogen atom or a (Ci-C₄)alkyl group and e is a natural number ranging from 1 to 4, - B represents a linear or branched divalent alkylene, oxyalkylene or oligo- oxyalkylene group possibly containing one or more hetero atoms, and

- Y represents an unsaturated and free-radical-polymerizable monovalent group, and

- a graft of polyolefinic nature. The grafted copolymer may also comprise polymer units or polymer chains derived from monomers other than that of formula (A). Such other monomers may be monomers (C) as defined above.

The grafted copolymers according to the present invention may have weight- average molecular masses (or molecular masses at the crest of the GPC peak) of between 500 and 10⁶, preferably between 1000 and 500 000 and even more preferably between 3000 and 250 000 g/mol.

According to one preferred embodiment of the invention, the copolymer comprises a weight content of polymer units derived from the monomers of formula (A) of less than or equal to 50% and preferably 30% relative to the total weight of the copolymer. The copolymer then has the advantage of conserving its oil-soluble or oil-dispersible nature.

According to another embodiment, the macromonomer of polyolefinic nature is preferably within a weight content of less than or equal to 80% and preferably less than 50% relative to the total weight of the copolymer. Specifically, the macromonomer of polyolefinic nature is difficult to homopolymerize.

Finally, according to yet another embodiment of the invention, the composition of polymer units derived from the monomers of formula (A), of the macromonomers of polyolefinic nature and of the optional monomers (C) in the copolymer may be expressed in the following manner: - the weight content relative to the total weight of the copolymer in polymer units derived from the monomers of formula (A) is between 1% and 50%, preferably between 3% and 30% and more preferably between 5% and 25%,

- the weight content relative to the total weight of the copolymer in polymer units derived from the macromonomers of polyolefinic nature is between 10% and 80%, preferably between 15% and 50% and more preferably between 15% and 30%, and/or

- the weight content relative to the total weight of the copolymer in polymer units derived from the monomers (C) is between 0 and 89%, preferentially between 20% and 87% and preferably between 30% and 80%. According to one preferred embodiment of the invention, the amounts expressed above are simultaneously borne out.

Monomer of formula (A)

The monomer of formula (A) may especially be as described in document WO 93/01221 or US 6 225 431.

More specifically, the monomer of formula (A) may be represented by the general formula:

Y-B-X (A) in which: - X takes the formula (I) :

0)

in which the groups R₅ are identical or different and each is a hydrogen atom or a (Ci-C₄)alkyl group and e is a natural number ranging from 1 to 4, - B is a linear or branched alkylene group, an oxyalkylene group or an oligo- oxyalkylene group optionally containing one or more hetero atoms or a covalent bond, and

- Y is an unsaturated ethylenic polymerizable group chosen from: R

CH₂-C C A _or

O ^K"

(IV) (V)

in which:

- R is a hydrogen atom or a (Ci-C₄)alkyl group,

- A is a group -O- or -NR₁ in which R₁ is a hydrogen atom or a (Ci-C₄)alkyl group or R₁ is a group -B-X in which B and X are as defined above, and

- K is a group -(CH₂)_POC(O)-, -(CH₂)_PC(O)O-, -(CH₂)_POC(O)O-, -(CH₂)_PNR₂-, -(CH₂)_PNR₂C(O)-, -(CH₂)_PC(O)NR₂, -(CH₂)_PNR₂C(O)O-, -(CH₂)_POC(O)NR₂-, -(CH₂)_PNR₂C(O)NR₂- (in which the group R₂ is identical or different), -(CH₂)_PO- or -(CH₂)_PSO₃-, or optionally in combination with B, a covalent bond and p is a natural number between 1 and 12 and R₂ is a hydrogen atom or a (Ci-C₄)alkyl group.

Preferably, the groups R₅ of formula (I) are identical. It is also preferable for at least one of the groups R₅ to be a methyl group, and even more preferably for all of the groups R₅ to be a methyl group.

Preferably, e is a natural number equal to 2 or 3 and even more preferably equal to 2.

The preferred monomers of formula (A) are consequently of general formula (II) or (III)

R CH₂- C

C-A-B-X (D) K B X (πi)

O in which R, A, B, K and X are as defined in formula (I). Preferably, in the compound of formula (II), R is a hydrogen atom or a methyl or ethyl group, and more preferably a methyl group, such that the compound of formula (II) is an acrylic, methacrylic or ethacrylic acid, or derivatives thereof.

In the compound of formula (III), K may be a covalent bond and B a group, K may be a group and B a covalent bond, K and B may simultaneously be groups, or K and B may simultaneously be covalent bonds. Preferably, B is a group whereas K is a covalent bond. When K is a group, then p is preferably a natural number from 1 to 6, more preferably 1, 2 or 3 and even more preferably p is equal to 1. When K is a group

-(CH₂)_PNR₂-, -(CH₂)_PNR₂C(O)-, -(CH₂)_PC(O)NR₂, -(CH₂)_PNR₂C(O), -(CH₂)_POC(O)NR₂- or -(CH₂)_PNR₂C(O)NR₂-, then R₂ is preferably a hydrogen atom or a methyl or ethyl group and even more preferably a hydrogen atom.

In the compounds of formula (III), the vinyl group is preferably in the para position relative to the group -K-B-X.

Preferably, B is:

- an alkylene group of formula -(C(R₃ )₂)_a-, in which the groups -(C(R₃ )₂)- are identical or different, and in each group -(C(R₃ )₂)- the groups R₃ are identical or different and each group R₃ is a hydrogen atom or a (Ci-C₄)alkyl group, preferably a hydrogen atom, and a is a natural number ranging from 1 to 12 and preferably from 1 to 6,

- an oxyalkylene group such as an alkoxyalkyl group containing from 1 to 6 carbon atoms in each alkyl unit, even more preferably -CH₂O(CH₂)₄- or - an oligo-oxyalkylene group of formula

-[(C(R4)₂)bO]c(C(R4)₂)b- in which the groups -(C(R^₂)- are identical or different and in each group

-(C(R4)₂)- the groups R₄ are identical or different and each group R₄ is a hydrogen atom or a (Ci-C₄)alkyl group, preferably a hydrogen atom, and b is a natural number ranging from 1 to 6 and preferably from 2 to 3, and c is a natural number ranging from 2 to 11 and preferably from 2 to 5; or

- a covalent bond.

The preferred groups B may be an alkylene group, an oxyalkylene group and an oligo-oxyalkylene group of up to 12 carbon atoms. B may preferably be an alkylene group, an oxyalkylene group or an oligo-oxyalkylene group.

In the compounds of formula (III), it is preferred for K and B to contain up to 12 carbon atoms in total.

Whether the monomer of formula (A) takes the general formula (II) or (III), B is preferably a group of formula -(C(R₃ )₂)- or -(C(R₃ )₂)₂, for example -(CH₂)- or -(CH₂- CH₂)-.

According to one preferred embodiment of the invention, the monomer of formula (A) Y-B-X is a phosphorylcholine (meth)acrylate and more particularly 2- (methacryloyloxyethyl)-2'-(trimethylammonium)ethyl phosphate, which will also be referred to by its abbreviation "MPC" in the description hereinbelow:

H₁C=C C — 0-(CH,)₂— 0-P-O-(CH₂)- N-(CH₃)₃

O °

The synthesis of this monomer is known and described especially in the article by K. Ishihara, Polym. J., 22, 335 (1990).

Various polymerization routes are described below, which are not limiting.

Copolymcrization of a macromonomer of polyolcfinic type with a monomer of formula (A), in the presence or absence of at least one monomer of formula (C)

The copolymerization of a monomer of formula (A) with a monomer of formula (C) is especially described in:

- T. Ueda, Polymer J., Vol. 24, No. 11, pages 1259-69 (1992) in particular when the monomer of formula (C) is a tert-butyl, n-hexyl, n-dodecyl or n-stearyl methacrylate. The chosen solvents are then ethanol or an ethanol/THF mixture.

- documents US 6 225 431 and WO 93/01221 already cited illustrate other suitable solvent mixtures such as 5/9 methanol/THF and 50/50 isopropanol/ethyl acetate for 2-(methacryloyloxyethyl)-2'-(trimethylammonium)ethyl phosphate/dodecyl methacrylate copolymers in respective ratios expressed as weight of monomer (A)/monomer (C) of 1/2 and 1/4. These same documents illustrate a 35.5/14.5 isopropanol/ethyl acetate mixture for a 2-(methacryloyloxyethyl)-2'-(trimethyl- ammonium)ethyl phosphate/hexadecyl methacrylate copolymer in a ratio expressed as weight of monomer (A)/monomer (C) of 1/2 or a 30/70 methanol/THF mixture for a 2-

(methacryloyloxyethyl)-2'-(trimethylammonium)ethyl phosphate/octadecyl methacrylate copolymer in a ratio expressed as weight of monomer (A)/monomer (C) of 1/2.

The term "THF" denotes tetrahydrofuran.

Such mixtures of methanol/THF and isopropanol/ethyl acetate solvents are suitable for copolymerization and make it possible to obtain the copolymers according to the present invention. It is possible, for example, to use an isopropanol/ethyl acetate mixture in proportions possibly ranging from 50/50 to 20/80. The process is thus preferably performed under solvent, temperature, nature of initiators and polymerization time conditions as described in US 6 225 431, column 28, lines 28 to 53. Thus, the solvent used may be, for example, acetonitrile, dimethylformamide, chloroform, dichloromethane, ethyl acetate, dimethyl sulfoxide, dioxane, benzene, toluene or tetrahydrofuran, or a mixture thereof.

The polymerization may be performed in the presence of at least one polymerization initiator, such as benzoyl peroxide, 2,2'-azobis(2-methylpropionitrile) or benzoin methyl ether. Other polymerization initiators may be used, such as those described in "Polymer Handbook", 3^rd edition, Ed. J. Brandrup, and E.H. Immergut, pub. Wiley InterScience New York, 1989.

The copolymerization may be performed for a time ranging from 1 to 72 hours, preferably from 8 to 48 hours or alternatively from 16 to 24 hours, and preferably under an inert atmosphere, for example of nitrogen or argon. The polymer may be purified by dialysis, precipitation in a nonsolvent (for example diethyl ether or acetone) or via ultrafiltration.

The polymer derived from the reaction may generally be dried under vacuum.

2,2'-Azobis(2-methylpropionitrile) is preferred as polymerization initiator.

Graft of polyo lefinic nature The grafts of polyolefinic nature may be derived from macromonomers of polyolefinic nature with a weight-average molecular mass of between 300 and 30 000, preferably between 500 and 20 000 and more preferably between 1000 and 10 000 g/mol, and comprise an end that is polymerizable with the monomer of formula (A). These grafts preferably have the characteristic of not being crystallizable, that is to say do not have a reversible liquid/solid change of state.

The grafts of polyolefinic nature may be derived from macromonomers comprising olefinic polymer units, and therefore be of homopolyolefin or copolyolefin type, and comprise an end that is copolymerizable with the monomers of formula (A) and/or the other possible monomers forming the main chain. These polyolefins may advantageously comprise polybutene isomers. Among the polybutene isomers, the following units are suitable: -(CH₂-CH₂-CH₂-CH₂)-

H₂C -CH,

-(CH₇ — CH)-

CH₃ CH₃ -(CH CH)-

CH, (CH₂- — -CH₂ - -CH)- and

CH₃ (CH₂ C ) isobutene

CH.

In other words, the grafts of polyolefinic type may advantageously comprise at least one unit chosen from the five units described above.

Preferably, the graft of polyolefinic nature is polyisobutene, which will also be referred to as "PIB" in the description hereinbelow.

It will be noted that the term "polyisobutylene" is equivalent to the term "polyisobutene".

The grafts may thus have a molecular mass of between 300 and 30 000, and preferably between 500 and 10 000 g/mol. As macromonomer which may lead to a graft of polyolefinic nature according to the invention, mention may be made in particular of those formed from polyisobutene, and comprising one end of (meth)acrylic, vinyl, hydroxyl or styrene nature, and capable of copolymerizing with a monomer of formula (A).

Thus, the grafts of polyolefinic nature may comprise polymeric units based on homopolyolefin or copolyolefins, said polyolefins possibly comprising polybutene isomers, and in particular polyisobutenes.

According to one variant, this end is a (meth)acrylic ester R

— O— C C =CH₂

O

in which R is a hydrogen atom or a methyl group. According to another variant, this end is an OH hydroxyl.

Synthesis of the macromonomer useful for obtaining a graft of yolyoleHnic nature

The macromonomer useful for obtaining a graft of polyolefinic nature is preferably a polyisobutylene with an end that is copolymerizable with the monomer of formula (A) chosen from (meth)acrylate, vinyl and styryl.

According to one embodiment, the end is a (meth)acrylate and the macromonomer has the formula (1):

CH₃ CH₃ R

CH₃ - C CH₂ (C CH₂) B O C C ^CH₂

CH, CH₁ O

(1)

in which:

- R is a hydrogen atom or a methyl group,

- n ranges from 5 to 600, preferably from 9 to 360 and more preferably from 18 to 180, and

- B is as defined above.

The synthesis of such macromonomers containing a meth(acrylic) ester reactive end is especially described in the article by K. Maenz, Ang. Makromol. Chem., 242, 183-197 (1996).

Several synthetic routes are described therein. All begin with commercial polyisobutene oligomers, the "Glissopal^®" products from BASF. These Glissopal^® oligomers have only one unsaturated end, but are unreactive with respect to a subsequent polymerization,

in which n ranges from 5 to 600, preferably from 9 to 360 and more preferably from 18 to 180.

In the text hereinbelow, -PIB denotes the radical having the following formula:

Among the routes described in this article, for converting these Glissopal^ oligomers into PIB with a (meth)acrylate end, the ones described below are preferred.

Alkylation of one end with a phenol followed by esterification with a (meth)acryloyl chloride

Scheme 1 below in particular summarizes pages 187-188 of article.

(1)

(2)

Scheme 1

"BF₃-OEt₂" denotes boron trifluoride etherate. "CF₃SO₃H" denotes trifluoromethanesulfonic acid. "CH₂Cl₂" denotes dichloromethane. The final purification of the macromonomer (with respect to those which have not reacted at the (meth)acrylic ester end) may be performed by elution on a column of silica of the PIB containing a phenol end before reaction with the acid chloride.

Epoxidation of an end, opening and formation of an alcohol, and then esterification with a (meth)acryloyl chloride

Scheme 2 below in particular summarizes pages 189-190 of the abovementioned article.

(i)

O CH₂ R-COOH

PIB- CH₁ C _f - PlB-CH₂ C-CH₂

² CH₃ CHC1_V45 °C

3 epoxidation peracetic acid (for example)

in which R represents an alkyl, cycloalkyl or benzyl radical in which "CHCl₃" denotes trichloromethane. Next, reductive hydroxylation with lithium aluminum hydride LiAlH₄

(2)

O CH₃

PIB -CH₂ C CH₂ ⁴ » PIB CH C — OH

THF,65 °C ²

CH₃ CH₃

followed by esterification with a (meth)acryloyl chloride (3)

CH, CH,

PIB — CH₂ C-OH -Cl C C =CH₂ -

CH₃ O _f, CH,

PIB CH, C-O — C C =CH,

Scheme 2 "THF" denotes tetrahydroiuran.

The synthesis of PIB macromonomers containing a (meth)acrylic ester end according to one of the synthetic routes described in Schemes 1 and 2 above is also described in the article by K. Maenz, Ang. Makromol. Chem., 258, 69-73 (1998). This second article also describes the corresponding copolymers, of these PIB

(meth)acrylates with methyl methacrylate or methyl acrylate in toluene with free-radical initiation with 2,2'-azobisisobutyronitrile.

Another route for synthesizing these PIB (meth)acrylates is also described in document DE 103 17 863. Scheme 3 below details a third alternative synthetic route for obtaining PIB macromonomers containing a (meth)acrylic ester end.

The process again begins with a Glissopal^® containing an unsaturated end

PIB — CX

CH₃

onto which is added a molecule of maleic anhydride to give a compound o

CH₁ CH,

O

PIB C C CH

H_{2 c}

O

comprising a succinic anhydride end (also described in E. Walch, Polymer, Vol. 35, No. 8, 1774-78 (1994)).

If it is then reacted with 2-hydroxyethyl methacrylate, the following is obtained:

O CH,

PIB CH₀-CH-C O (CH₂), O — C CH,

O

CH, O

COOH

Scheme 3

Example 4 of the cited patent describes this synthesis.

If 2-hydroxyethyl acrylate is used instead of the methacrylate, reference may be made to the description of the synthesis of the macromonomers in Examples 1, 2 and 3 of the same patent.

Irrespective of synthetic route, the macromonomers obtained are soluble only in solvents of medium to low polarity. Their copolymerization with a hydrophilic and highly polar monomer such as the monomer of formula (A) can therefore take place only in suitable solvent media as outlined above.

According to another embodiment, the macromonomer is a polyisobutylene with an OH end that is copolymerizable with the monomer of formula (A), of formula (2):

CIL CH,

CIL

CH, — C -CH, - (C CH,) CH₂ C CH, OH

CH₁ CH, H

(2)

in which n is as defined above for formula (1).

The synthesis of such macromonomers containing a hydroxyl reactive end is especially described in the article "Terminally Functionalized Polyisobutylene Oligomers as Soluble Supports in Catalysis", D.E. Bergbreiter and J. Li, (Chem. Commun. (Camb.) 2004. Jan. 7;(1): 42-3. Epub. 2003 Nov. 27). This synthesis begins with a commercial "Glissopal^®" oligomer from BASF as described above.

According to this article, the Glissopal^® oligomers are oxidized according the scheme below:

PT-T

CH₂ 1) BF -OEt₂ n-hexane γⁿ3

PIB CH, C → PIB^{^}CTL CH₂-OH

2 CH 2) NAOH, cthanol, H₂O₂

PIB-OH

The PIB-OH may also be obtained according to the first part of Scheme 2 above.

According to another embodiment, the macromonomer is a polyisobutylene with a thiophene end that is copolymerizable with the monomer of formula (A) or a polymer obtained from the monomer (A).

The synthesis of such macromonomers containing a thiophenyl reactive end is especially described in the article Macromolecules 2003, 36, 6985-6994. This synthesis is illustrated in Scheme 4 below.

CH₃ CH₃ ( H₃

TiCl₄/-78 ⁰C

CH₃ C- CH₂- - c α + CH₂ ^~ C -CH₂

CH₃ CH₃ l-chloro^^^-tπmcthyl-i -pentane lsobutene (IB) Hexane/CH₂C1₂ (TMPCl) (BASF)

60/40 (Fluka) 2,6-Di-tert-butylpyπdine (DtBP)

2-polyisobutγlenyl-thιopene (PIB-T) Scheme 4

In this scheme, n has the same meaning as previously.

Other routes for synthesizing a polymer comprising polymer units comprising a group of formula (T) and polyolefinic grafts

The groups of formula (I) are preferably introduced in the form of a monomer (A) as described above, especially a phosphorylcholine (meth)acrylate (MPC).

According to a first other synthetic route, the MPC may be reacted, for example, with a monomer capable of reacting with a macromonomer of polyolefinic nature as described above, such as a polyisobutene containing a (meth)acrylate, vinyl, styrene, hydroxyl or thiophene end. In this embodiment, the polyisobutene containing a hydroxyl end (PIB-OH) whose preparation is described above is preferred.

According to one variant, the preparation of the copolymer comprising polymer units comprising a group of formula (I) and grafts of polyolefinic nature may be performed by free-radical polymerization of a MPC monomer with a p-nitrophenyloxycarbonyl poly(ethylene glycol) methacrylate (MEONP) monomer described in the article Biomacromolecules 2004, 5, 342-347, the content of which is incorporated into the present patent application by way of reference. Scheme 5 below illustrates this alternative route for synthesizing a grafted copolymer according to the invention.

MPC MEONP

MEONP

MPC

Poly (MPC-MEONP) Poly (MPC-MEONP) + PIB - OH

_j_

Poly MPC-graft-Poly IB (PMPC-graft-PIB)

PoljPCM graft-Poly IB (PMPC-graft-PIB)

Scheme 5

In this scheme, n has the same meaning as previously and n₅ and m₅ are natural numbers; p5 may be between 1 and 10 and preferably equal to 4 or 5. According to a second other synthetic route, the grafted copolymer is obtained by reacting a macromonomer initiator containing at least one group of formula (I) with olefinic monomers.

For example, a statistical copolymer obtained by reaction of monomer (A), for example MPC, with a vinyl monomer comprising a halogen atom, is prepared. Such a synthetic route is illustrated according to the scheme below and is based on the results described especially by the article Macromolecular Rapid Communications, 2002, 23, 809- 813, according to the scheme below:

PMPC-bloc-PCMS

Schema 6

The grafted copolymer according to the present invention may have a main chain comprising at least one block of polyolefinic nature and grafts comprising at least one group of formula (I) as defined above, and preferably phosphorylcholine. The main chain of polyolefinic nature may comprise identical or different blocks.

AIBN represents 2,2'-azoisobutyronitrile.

DPE represents 1,1-diphenylethylene. n<₅ and Hi₆ are natural numbers and n is as defined above. Thus, according to one of its aspects, a subject of the present invention is more particularly a copolymer whose main chain contains blocks of polyolefinic nature, and which is grafted with at least one graft containing at least one group of formula (I).

According to this embodiment, it is possible, for example, to react a monomer of olefinic nature with at least one vinyl monomer comprising a halogen atom to obtain a macroinitiator that will then be reacted with monomers of formula (A) as defined above. A commercial product corresponding to this macroinitiator is sold under the reference

Exxpro 3035.

This embodiment may be illustrated by the synthesis described according to the following scheme. This synthetic route is performed by ATRP polymerization (Atom Transfer Radical Polymerization), the principle of which is described in the article

Macromolecule Chem. Phys., 2001, 202(17), 3392-3402, which may be summarized according to Scheme 7 below:

Poly(isobutene-co-(p-methyl-styrene)-co-(p-bromomethylstyrene) (commercial product EXXPRO 3035)

(CH₃),

Scheme 7

In this scheme, n is a natural number as described above and m₇, p₇ and I₇ are natural numbers.

SEOUENCED COPOLYMER

A sequenced copolymer according to the present invention may contain one or more blocks comprising at least one polymer unit or alternatively a group of polymer units containing a group of formula (I), preferably comprising a phosphorylcholine group and/or at its end a monomer containing a group of formula (I), at least one block comprising at least one polymer unit derived from a macromonomer of polyolefinic nature and, finally, optionally at least one block derived from the polymerization or copolymerization of monomers (C), the monomer of formula (C) being as defined above in the context of the grafted copolymer.

Thus, the polymer comprises at least one block consisting of polyolefinic units, i.e. homopolyolefins or copolyolefins. These polyolefins may advantageously comprise polybutene, and preferably polyisobutene in the same manner as the grafts of polyolefinic nature described above.

The monomer comprising at least one polymer unit or alternatively a group containing a group of formula (I) may advantageously be a monomer of formula (A) as defined above in the context of the description of the grafted copolymers, and thus typically such a monomer may be MPC.

These block, or "radial", or star polymers may be copolymers in diblock, triblock or multiblock or in star form comprising at least one block based on units (A) and at least one block based on polyolefin units (B).

These block polymers may be obtained in various ways. Mention is made, for example, of the cationic polymerization of isobutylene followed by conversion of a PIB chain end into a group

CH₃

-O C -C-Br O CII₃

and then a controlled free-radical polymerization (ATRP) of the other sequence which comprises, in the monomer mixture, a monomer comprising a group of formula (I) such as a phosphorylcholine (meth)acrylate. This synthetic route is especially described in Z. Fang,

Polymer Preprints, 2002, 43(2), 36-37. In this specific case, a diblock copolymer of structure "A-B" is obtained.

Still according to the same type of procedure consisting of cationic homopolymerization of isobutylene followed by a living free-radical polymerization, triblock copolymers of structure "A-B-A" may be constructed as described in Coca, S., J.

Polym. Sci. Part A = Polym. Chem., 35, (16) 3595-3601 (1997).

Thus, a polyisobutylene containing dysfunctional α,ω ends is converted into α, co-chlorinated ends that can each initiate the ATRP polymerization of a monomer mixture containing a monomer (A) comprising a group of formula (I) and optionally a monomer of formula (C).

Triblock copolymers of structure "A-B-A" may be prepared via the method described in the article by M.K. Mishra, Macromol. Symp. 107, 243-53 (1996), in which:

- a polyisobutylene macroinitiator containing a central azo group that can subsequently trigger a free-radical polymerization is prepared,

- this polyisobutylene macroinitiator is then used to trigger the polymerization of a monomer mixture containing a monomer (A) comprising a group of formula (I) and optionally a monomer of formula (C),

- the polyisobutylene macroinitiator containing a central azo group is prepared by polymerization of isobutylene initiated with a couple: tertiary diether containing a central azo group in the presence of a Lewis acid catalyst, according to Scheme 8 below:

CH, CH₃ CH₁ CH,

Lewis

_{H c}^o — C CH₂ C N^{^}N C— CH₂ — C-OCH₃ + isobutylene acid

CH, CH, CH, CH,

CII, CH, CH, CH,

Cl — PIB- C- CH, C N^N C CH, — C — PIB CI

CII, CH₃ CH, CH,

PIB Macroinitiator

By the action of temperature and in the presence of a monomer mixture comprising a group of formula (I) and of monomers (C).

CH, CH, CH, CH,

Cl- PIB- C ~ CH, - C-N=N C -CIL ^{^} C PIB -Cl

CH₃ CH, CH, CH,

I⁰C

CH, CH,

2 Cl — PIB- C ^{^}CH, - C* 4 N₂ CH, CH, Scheme 8

The radical obtained allows initiation of the polymerization starting with the monomer comprising a group of formula (I) and a monomer of formula (C).

Diblocks of structure "polyA-polyB" or, depending on the mode of determination of the polymerization of the monomer (A), triblocks polyB-polyA-polyB, will thus rather be obtained.

Another route for obtaining a diblock copolymer of the PIB-polyMPC type is described in the article Macromolecules, 2003, 36, 6985-6994. This route may be summarized by Scheme 9 below:

2-polyisobutylenyl-thiσpene (PIB-T)

2-polyisobutylenyl-tMophenyl-poly MPC

Scheme 9

n has the same meaning as above. According to this synthesis, the PIB-T may be prepared, still according to the teaching of this article, according to Scheme 10 below.

Triblock copolymers of "A-B-A" structure may also be prepared via the method described in Macromolecules 2003, 36, 6985-6994, by preparing a PIB block bearing a thiophene at each of its ends. This route may be presented in the major lines as in Scheme 10 below:

(DtBP)

Ref. J. Macromolc Sci Chem 1983, Al 8, 1367-1382 Macromol Rapid Comim 1997, 18, 417-425 (1997)

(EHBP)

Ref. J. Macromole. Sci. Chem. 1983, A18, 1367-1382. Macromol. Rapid Comun. 1997, 18, 417-425. (1997)

α,ω-Dithiophene-Ended PIB (CH₃)₃

(CH₃)₃

Scheme 10

n has the same meaning as above and ml O is a natural number.

STATISTICAL OR RANDOM COPOLYMER

A statistical or random copolymer according to the present invention randomly contains in its main chain olefinic polymer units and polymer units containing a group of formula (I).

To prepare this copolymer, a monomer containing a group of formula (I), advantageously a monomer of formula (A) as defined above in the context of the description of the grafted copolymers, may be used, and thus typically such a monomer may be MPC.

The monomer containing a group of formula (I) may be reacted with an olefin, preferably an olefin of at least four carbon atoms, more preferably butene and all its isomers as described above.

Random copolymers derived on the one hand from monomers containing a group of formula (I) and on the other hand from monomers other than of α-olefinic type as defined above, for example of (meth)acrylic ester, styrene, or acrylamide type are excluded from the scope of the present invention.

According to the teaching of patent application JP-2002-363 223, the olefin (typically isobutene) and MPC are reacted together in THF, in the presence of a Lewis acid and 2,2'-azobis-2,4-dimethylvaleronitrile. POLYOLEFIN HAVING PHOSPHORYLCHOLINE END(S)

Such a copolymer may be in the form of a copolymer comprising linearly linked blocks of identical or different polyolefinic nature and comprising, at one or both of its ends at least one group of formula (I) as defined above, or in the form of a polymer of polyolefinic nature comprising at least one group of formula (I) as defined above at one or both of its ends, or alternatively linked to the main polymer chain.

Synthesis of a PIB bearing a phosphorylcholine end

The reaction Scheme 11 is as follows: a) maleinization of the unsaturated end of a PIB chain

CH₃- 250 "C

PIB chain Maleic anhydride

O

CH, CH

CII₁ CH

CH₁ -C l CH₂ - C CH, CH,

CH, CH,

Polyisobutylene succinic monoanhydride

b) esterification of the anhydride end with glycerophosphorylcholine

glycerophosphorylcholinated

PIB-PC

Scheme 11

n has the same meaning as above.

Glycerophosphorylcholine is especially described in Japanese patent JP 2003-040 942.

As regards the maleinization reaction of the PIB in step a), it is described in the notice of the commercial "Glissopal^®" PIB products. According to an alternative, it is also possible to add, by forcing the reaction, two molecules of maleic anhydride to the unsaturated end of the PIB below, according to the following Scheme 12:

CH. CH CH

CH, - CH 200 250 ⁰C

CH, - C CH, C CH

2- 1OH

CH, CII, — C CH -

Polyisobutylene succinic monoanhydride

O ₀ O

CH, CII, CII CII CH,

CH_j C -CH₂- C

TH,

Scheme 12

n has the same meaning as above.

PIBBSA: polyisobutylenebis(succinic anhydride) This bis "adduct" may then be reacted with two moles of glycerophosphorylcholine, which will esterify on each anhydride group. A PIB with two phosphorylcholine groups at one end is thus obtained, i.e.:

PIB-(PC)₂, i.e. a PIB with two PC groups at one end.

COSMETIC COMPOSITION

A cosmetic composition according to the present invention may contain one or more copolymer(s) according to the present invention in a content ranging from 1% to 80% by weight, preferably 3% to 30% by weight and more preferably from 5% to 25% by weight relative to the total weight of the composition.

Physiologically acceptable medium

The term "physiologically acceptable medium" denotes a nontoxic medium that may be applied to human skin, lips or keratin materials. The physiologically acceptable medium is generally suited to the nature of the support onto which the composition is to be applied, and also to the aspect in which the composition is intended to be packaged.

The physiologically acceptable medium may comprise an aqueous phase and/or a fatty phase. According to one particular embodiment, the aqueous phase or the fatty phase may form the continuous phase of the composition.

In particular, the composition may contain, for example, a continuous fatty phase, which may contain less than 10% by weight of water, especially less than 5% by weight of water or even less than 1% by weight of water relative to the total weight of the composition.

Fatty phase

The cosmetic compositions in accordance with the present invention may comprise a fatty phase especially comprising oils, especially waxes, and fatty substances that are solid at room temperature (20-25°C) and atmospheric pressure.

The term "oil" means any fatty substance that is in liquid form at room temperature (20-25°C) and atmospheric pressure. The liquid fatty phase may also contain, besides oils, other compounds dissolved in the oils, such as gelling agents and/or structuring agents.

When the polymer or the copolymer according to the present invention is in the form of an oil, the cosmetic composition according to the present invention may comprise this sole oil as fatty phase, or alternatively may comprise one or more additional oils in which the polymer or copolymer according to the invention may be dissolved or dispersed.

The different oil(s) of the copolymer according to the present invention may be present in a proportion of from 0.1% to 99% by weight, in particular from at least 1% to

90% by weight, more particularly from 5% to 70% by weight, especially from 10% to 60% by weight or even from 20% to 50% by weight, relative to the total weight of the cosmetic composition according to the invention.

The additional and/or different oils of the copolymer according to the present invention that are suitable for preparing the cosmetic compositions according to the invention may be volatile or nonvolatile, silicone or nonsilicone oils. For the purposes of the present invention, the term "volatile oil" means an oil

(or nonaqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a nonzero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10^~3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to lOO mmHg) and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to

10 mmHg).

For the purposes of the present invention, the term "nonvolatile oil" means an

011 having a vapor pressure of less than 0.13 Pa. The volatile or nonvolatile oils may be hydrocarbon-based oils especially of animal or plant origin, synthetic oils, silicone oils or fluoro oils, or mixtures thereof.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom and especially at least one Si-O group.

The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and/or phosphorus atoms.

The volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched C₈-C₁₆ alkanes (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopars^® or Permethyls^®.

Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity < 8 centistokes

(8 x 10^~6 mVs) and especially containing from 2 to 10 silicon atoms and in particular from

2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of dimethicones with a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclo- hexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl- disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpenta- siloxane, and mixtures thereof.

Volatile fluoro oils such as nonafluoromethoxybutane or perfluoro- methylcyclopentane, and mixtures thereof, may also be used.

The fatty phase of the cosmetic compositions according to the present invention may also comprise at least one volatile oil.

The fatty phase of the cosmetic compositions according to the present invention may also comprise at least one nonvolatile oil. The nonvolatile oils may be chosen especially from hydrocarbon-based oils and, where appropriate, fluoro oils and/or nonvolatile silicone oils.

Nonvolatile hydrocarbon-based oils that may especially be mentioned include:

- hydrocarbon-based oils of animal origin,

- hydrocarbon-based oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (Ajinomoto, Eldew PS203), triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C₄ to C₂₄, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially heptanoic or octanoic triglycerides, wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cotton seed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, cancUenut oil, passion flower oil or musk rose oil; shea butter; or caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810^®, 812^® and 818^® by the company Dynamit Nobel, - synthetic ethers containing from 10 to 40 carbon atoms;

- linear or branched hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and squalane, and mixtures thereof, and in particular hydrogenated polyisobutene,

- synthetic esters, for instance oils of formula R₁COOR₂ in which R₁ represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R₂ represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that R₁ + R₂ > 10.

The esters may be chosen especially from fatty acid esters, for example:

- cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate or isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4- diheptanoate and palmitate, alkylbenzoate, polyethylene glycol diheptanoate, propylene glycol 2-diethylhexanoate and mixtures thereof, C₁₂ to C₁₅ alcohol benzoates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate and octyldodecyl neopentanoate, isononanoic acid esters, for instance isononyl isononanoate, isotridecyl isononanoate and octyl isononanoate, and hydroxylated esters, for instance isostearyl lactate and diisostearyl malate;

- polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate;

- esters of diol dimers and diacid dimers such as Lusplan DD-DA5^® and Lusplan DD-D A7^®, sold by the company Nippon Fine Chemical and described in patent application FR 03/02809 filed on March 6, 2003, the content of which is incorporated into the present patent application by way of reference; - fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2- octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol; - higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof; and

- dialkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC^® by Cognis.

The nonvolatile silicone oils that may be used in the composition according to the invention may be nonvolatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates, and dimethicones or phenyltrimethicones with a viscosity of less than or equal to 100 cSt, and mixtures thereof.

According to one particular embodiment, the cosmetic compositions in accordance with the invention may also comprise at least one silicone oil chosen from volatile silicone oils and nonvolatile silicone oils, and mixtures thereof. The nonvolatile oils may be present in the compositions according to the invention in a content ranging from 20% to 99% by weight, especially from 30% to 80% by weight and in particular from 40% to 80% by weight relative to the total weight of the composition.

Aqueous phase According to certain aspects of the present invention, the composition according to the invention may comprise at least one aqueous medium, constituting an aqueous phase, which may form the continuous phase of the composition. The aqueous phase may consist essentially of water.

It may also comprise a mixture of water and of water-miscible organic solvent (miscibility in water of greater than 50% by weight at 25°C), for instance lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol or isopropanol, glycols containing from 2 to 8 carbon atoms, such as propylene glycol, ethylene glycol, 1,3- butylene glycol or dipropylene glycol, C₃-C₄ ketones and C₂-C₄ aldehydes.

The aqueous phase (water and optionally the water-miscible organic solvent) may be present in a content ranging from 0.1% to 40% by weight, especially ranging from 0.1% to 20% by weight and in particular 0.1% to 10% by weight relative to the total weight of the composition.

Additives

The cosmetic compositions according to the invention may also comprise any additive commonly used in the field under consideration, chosen from gelling agents, antioxidants, essential oils, preserving agents, fragrances, neutralizers, moisturizers, antiseptics, vitamins such as vitamin B3 or E and derivatives thereof, and anti-UV agents.

Needless to say, a person skilled in the art will take care to select the optional additive(s) added to the cosmetic composition according to the invention such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition.

Formulation The composition according to the invention may be used for making up and/or caring for human keratin materials such as the skin (of the face, the body, the scalp or the lips), mucous membranes (inner edge of the eyelids), the hair, the nails, the eyelashes and the eyebrows.

The cosmetic composition according to the invention may be in the form of a makeup or care product for keratin materials and in particular for the skin, in particular in the form of a foundation, and for the lips, in particular a lipstick or a lip balm.

The composition thus finds a particular application as a body or facial care composition; a body or facial makeup composition such as a foundation, a lipstick, a lipcare product, a nail varnish, a nailcare product, a mascara or an eyeliner; a fragrancing composition; an antisun composition; a deodorant composition and a haircare composition.

A subject of the present invention is also a cosmetic composition containing at least one polymer as defined above, and characterized in that it simultaneously has improved gloss and staying power properties, in particular the staying power of the gloss over time.

According to another of its aspects, the present invention relates to the use, in a cosmetic composition, of the polymer as defined above, for simultaneously improving the gloss and staying power properties, in particular the staying power of the gloss over time.

A subject of the present invention is also a nontherapeutic cosmetic process for making up and/or caring for keratin materials, comprising at least the step of applying to these keratin materials at least one cosmetic composition as defined above.

The examples below are given by way of illustration and with no limiting nature on the invention.

Example 1: Synthesis of a copolymer of MPC, isostearyl acrylate and PIB methacrylate

- The polyisobutylene methacrylate macromonomer is synthesized from PIB containing an unsaturated end, Glissopal 93039^®, with a number-average molecular mass equal to 2040, sold by BASF. The synthesis of the corresponding PIB methacrylate is performed by epoxidation, reduction at the -OH end, and then esterification with methacryloyl chloride according to the article by K. Maenz, Angew. Makromol. Chem. 242, 183-97 (1997). A methacrylate-iunctionalized macromonomer with a number-average molecular mass equal to 2050 is obtained.

- The polymerization is then performed under the following conditions:

Reagents

- 2-(Methacryloyloxyethyl)-2'-(trimethylammonium)ethyl phosphate = MPC = 1O g.

- PIB methacrylate (according to above) = 50 g, and

- isostearyl acrylate (sold by Prochema) = 40 g. The 100 g of monomers indicated are introduced into a 2-liter round-bottomed flask with a central stirrer, a condenser and a nitrogen sparge tube, followed by successive addition of 435 ml of isopropanol and 435 ml of ethyl acetate. The mixture is stirred at room temperature, at 250 rpm, under a stream of nitrogen until dissolution is complete. 0.25 g of 2,2'-azobis(2-methylpropionitrile) is then added and the temperature is raised gradually to 65°C, while continuing the stirring and the sparging with nitrogen. The mixture is left to react at 65°C under these conditions for 40 hours. It is then cooled to room temperature. The cooled mixture is filtered under vacuum. The filtrate obtained is concentrated on a rotary evaporator, under partial vacuum, to remove the isopropanol/ethyl acetate solvent mixture.

The residue is taken up in 300 ml of dichloromethane for dissolution and then purified by precipitation from 5 liters of acetone. The product is dried under vacuum to constant weight.

The copolymer is obtained in a yield of 70% (70 g).

Example 2: Preparation of a MPC copolymer grafted with PIBs

In a first stage, two monomers MPC and p-nitrophenyloxycarbonyl poly(ethylene glycol) methacrylate (MEONP) are reacted together via free-radical polymerization conventionally with azobisisobutyronitrile (AIBN) as initiator, and the PIB chains are then grafted onto the pendent chain of the MEONP units of the MPC/MEONP copolymer obtained by using a PIB with a hydroxyl end.

Synthesis of MEONP: The synthesis of MEONP is described in the article Biomacromolecules 2004,

5, 342-347, the content of which is incorporated into the present patent application by way of reference.

The poly(ethylene glycol) monomethacrylate (MeOnOH) was obtained from NOF Co. Ltd, Tokyo, under the reference Blenmer PE-200. The average number of ethylene oxide units in the MeOnOH, determined by NMR, was 4.5.

Blenmer PE-200 (22.2 g) and triethylamine (TEA) (7.9 g) were placed in a 300 ml four-necked round-bottomed flask equipped with a thermometer and a magnetic stirrer, and 50 ml of chloroform were then added to the mixture. Next, the solution was cooled to -30°C, p-nitrophenyl chloroformate (15.7 g) dissolved in 40 ml of chloroform were added drop wise to the stirred solution over one hour. The temperature of the mixture was maintained at -30°C for two hours. The precipitate formed in the mixture was triethylamine hydrochloride (TEAC), which was then filtered off. The filtered solvent was evaporated under reduced pressure. A small amount of diethyl ether was added to the residue in order to remove the dissolved TEAC, followed by filtration. By evaporation of the filtrate under pressure, MEONP was obtained in the form of an oily yellow liquid.

IR(cm-l): 3081(p-Ar), 2870 (CH3-,-CH2-), 1770 (Ar-CO-O-R), 1720 (CdO), 1637 (CdC), 1348 (Ar-NO2), 860 (Ar-NO2)

Synthesis of a PIB functionalized with an OH group

The oligomer is synthesized according to the teaching of the document "Terminally Functionalized Polyisobutylene Oligomers as Soluble Supports in Catalysis", reported by D.E. Bergbreiter and J. Li. (Chem. Commun. (Camb.) 2004 Jan. 7;(l):42-3. Epub. 2003 Nov. 27).

50 g (50 mmol) of a polyisobutene oligomer bearing a vinyl group at the end of the chain (M_w = 1000 or 2300 degree of polymerization of about 18-41), which are obtained from BASF under the reference Glissopal 1000 or Glissopal 2300, are dissolved in 100 ml of hexane and then reacted with 17 mmol OfBH₃-SMe.

After a reaction time of 24 hours, the mixture is cooled in an ice bath, and 40 ml of ethanol and 12 ml of 4 N NaOH are then added.

8 ml of 30% H2O2 are then added dropwise, and the oxidation reaction is then left to continue for 2 hours. At the end of this time, 300 ml of water are added. The solution is extracted with hexane (5 x 100 ml) and then washed with water (3 x 50 ml) and with brine (1 x 50 ml). The organic phase is dried over MgSO₄ and then filtered. The organic solvents are extracted under reduced pressure.

52 g of PIB-OH are obtained after drying under vacuum for 24 hours. ¹H NMR (300 MHz, CDCl₃, δ): 0.75-1.46 (m, 180H), 3.26-3.32 (dd, J = 7.5 Hz, IH), 3.44-3.49 (dd, J = 5.4 Hz, IH).

Reaction of PIB-OH with the copolymer MPC/p-nitrophenyloxycarbonyl polyfethylene glycol) methacrylate (MEONP)

The PIB-OH and the MPC/MEONP copolymer are dissolved in THF. The mixture is stirred at 4°C. After conjugation, the solvent is removed under vacuum. The final product is precipitated from methanol. Example 3: Preparation of a MPC copolymer grafted with PIB chains

According to the teaching of the article "Macromolecular Rapid Communications 2002, 23, 809-813", a copolymer obtained from MPC and from chloromethylstyrene (CMS) is prepared, and is then used as initiator to polymerize an olefin.

Synthesis of the PMPC-block-PCMS polvfor PMPC-ran-PCMS) fPMPC- macro initiator)

The MPC was degassed by three cycles of freezing-thawing. Next, the AIBN and the DPE were added to the monomer and the mixture was stirred at 80°C for two hours. The resulting polymer was precipitated from hexane, reprecipitated from CHCl₃ in hexane and dried under vacuum. The PMPC and the CMS were dissolved in toluene. The polymerization was initiated by heating the mixture to 85°C. After three hours, the solution was cooled to room temperature. The polymer was precipitated from cyclohexane, reprecipitated twice from CHCl₃ in cyclohexane and freeze-dried.

Synthesis of PMPC-block-PCMS-graft-PIB fPMPC-macroinitiatof) [Poly(methyl methacrylate)-block-poly(4-chloromethylstyrene)]-graft- polyisobutylene (PMMA-block-PCMS)-graft-PIB). The copolymerizations by grafting were studied in an "MBraun Glovebox" protective cabin under an argon atmosphere at 80°C. The humidity and the oxygen were regulated continuously and maintained under 1 ppm. A typical sample was prepared according to the following procedure: the PMPC-block-PCMS in CH2CI2 were taken from a base solution and added to a precooled (-8O⁰C) mixture of hexane and CH2CI2. A defined amount of IB was added and the graft copolymerization was initiated by adding a precooled solution of DEAC in hexane. The reaction was stopped after one hour by addition of precooled methanol.

Example 4: Preparation of a MPC copolymer grafted with PIB chains This copolymer may be prepared according to the teaching of the article

Macromolecule Chem. Phys., 2001, 202(17), 3392-3402. Poly(isobutene-co-(p-methylstyrene)-co-(bromomethylstyrene) (commercial product EXXPRO 3035) is dissolved in chlorobenzene or THF.

A measured amount of catalyst and of dNbpya was placed in a Schlenk tube followed by degassing under vacuum and filling three times with N₂. MPC was added to the Schlenk tube after degassing by sparging with N₂ for thirty minutes. The catalyst and the monomer solution were transferred into the PIB/chlorobenzene (or THF) solution at room temperature under N₂. The polymerization reactor was immersed in an oil bath preset at a specific reaction temperature (90°C). The kinetic samples were taken from the tube at regular intervals using a syringe. The samples were diluted with tetrahydroiuran (THF) and then passed through a column filled with neutral Al₂O₃ for the analyses such as gas chromatography (GC) and gel permeation chromatography (GPC). After a certain polymerization time, the polymerization system was removed from the oil bath and cooled to room temperature. The solution was diluted with THF and then passed through a column filled with neutral Al₂O₃ and precipitated from methanol. The resulting polymer was dried under vacuum at 60°C.

Example 5: Preparation of a PIB/pMPC diblock copolymer

This copolymer is synthesized according to the teaching of the article Macromolecules 2003, 36, 6985-6994, by reacting the monomer 2-(methacryl- oyloxyethyl)-2'-(trimethylammonium)ethyl phosphate = MPC with 2-polyisobutenyl- thiophene.

Preparation of the 2-polyisobutenyl-thiophene (PIB-T)

The synthesis of PIB-T was performed under a dry atmosphere of nitrogen in a protective cabin. The living polymerizations of IB with TMPCl as initiator were performed according to the following procedure: 240 ml Of CH₃Cl, 404 ml of n-hexane and 0.355 ml (0.302 g, 1.58 mmol) of DtBP were added to a one-liter three-necked round-bottomed flask equipped with a septum, a magnetic stirrer and a nitrogen sparge tube, and the mixture was then cooled to -78°C. 15 ml (10.57 g, 0.188 mol) of IB were injected into the reactor using a syringe. After stirring for ten minutes, 0.6 ml (0.525 g, 3.53 mmol) of TMPCl was transferred into the reactor using a transfer needle. After stirring for five minutes, 1.5 ml (2.68 g, 0.014 mol) Of TiCl₄ were transferred into the reactor using a transfer needle. One hour later, 28.3 ml (29.7 g, 0.35 mol) of T (thiophene) were added to the polymerization system; the color of the solution changed from slightly yellow to red. T was able to react by virtue of the living chain ends for 60 minutes. Finally, the reaction was terminated by adding 30 ml (23.55 g, 0.75 mol) of precooled methanol. The crude product was dissolved in n-hexane and the mixture was filtered in order to remove the mineral precipitates. Next, the hexane phase was isolated and cleaned once with NH₃(aq) and then with water to neutral pH. The organic phase was separated out and dried over MgSO₄ for about two hours. Next, the solution was filtered and the solvent was removed in a rotary evaporator. Next, the polymer was dissolved in a small amount of n-hexane and precipitated two or three times from acetone in order to remove the excess thiophene.

Reaction of 2-polyisobutenyl-thiophene with MPC

The copolymerization is performed in a one-liter glass reactor with stirring equipped with thermostatically maintained cooling, steel capillary connections for introducing the gases and solvents, and machines for measuring the temperature and pressure. The solvents were introduced directly from the distillation apparatus into the reactor. The monomer was introduced from the glass vials using a spherical junction or with a dry syringe. The solutions of n-BuLi and the macroinitiator (PIB-T) are handled by syringe. In a typical procedure, 5 ml (8 mmol) of a solution of n-BuLi are added to 400 ml of purified THF and maintained at room temperature overnight. The next day, the macroinitiator, the monomer and the n-BuLi were introduced and cooled to -40°C. 1.21 g (0.355 mmol) of PIB-T (Mn) 3.40 103 g/mol) were freeze-dried from a benzene solution for eight hours and then dried for more than ten hours. In the vacuum line, the dried PIB-T was dissolved in THF and the mixture was then added to the glass reactor with continued stirring and cooled to -40°C. 0.23 ml (0.368 mmol) of a solution of n-BuLi was then added using a dried syringe. The reaction was maintained at -40°C for one hour and 5.34 g (0.037 mol) of MPC were then added by volume to the macroinitiator solution. After two and a half hours, the polymerization was terminated with methanol. Finally, the polymer was precipitated from 2-propanol and dried under vacuum at room temperature. In a second experiment, a four fold excess of n-BuLi was used and the unchanged BuLi was destroyed by heating it to +40°C for one hour. Example 6: pMPC/PIB/pMPC triblock copolymer

This triblock copolymer is prepared according to the teaching of article Macromolecules 2003, 36, 6985-6994.

The polymerizations were initiated with the difunctional initiator 5-tert-butyl- l,3-bis(l-chloro-l-methylethyl)benzene (tBuDiCumCl). After performing the polymerization of IB, equivalent volumes of the polymer solution in the reactor were placed in culture tubes. For each culture tube, an additional amount of TiCl₄ or DtBP was added in order to vary the ratio of [TiCl₄] to [tBuDiCumCl] or of [DtBP] to [tBuDiCumCl] in the polymer solution. The functionalization of the PIB was performed via two different methods: addition of a solution of T/CH₃C1 to the polymer solution (T to the polymer) and addition of the polymer solution to a solution of T/CH₃C1 (polymer to T). A total of two hundred equivalents of T was used for the functionalization of the PIB. After one hour, the reaction of the mixture was terminated with precooled methanol and dispersed in methanol. The polymer was purified by precipitation of the polymer solution from methanol, followed by drying under vacuum.

Example 7: Isobutcnc/MPC statistical copolymer

This copolymer is obtained according to the teaching of document JP 2002-363 223. Under an argon atmosphere, a solution of ethylaluminum chloride in toluene is added dropwise. The solution is then warmed to room temperature and stirred for 30 minutes. After stirring, the mixture is again cooled to -78°C and the 2,2'-azobis-2,4- dimethylvaleronitrile is added. The copolymerization then continues for 24 hours with stirring at a pressure of 0.1 MPa of isobutene and at a temperature of 25°C.

The reaction mixture is then poured into a mixture of IN hydrochloric acid and methanol. The precipitate is filtered off to isolate a white solid, which is washed with the same mixture and then dried under reduced pressure.

Example 8: Preparation of a PIB with only one phosphorylcholine end a) Preparation of the PIB containing a succinic anhydride end PIB used - Glissonal 1000 from BASF, Mn = 1000 i.e.: CH,

CH,

(CHJ₃ C% (CH₂ - C σt

16 CH,

CH,

(18 isobutylene units of MW = 56)

1 kg of PIB (Glissopal 1000) are introduced into a two-liter autoclave and heated to 150°C. The vacuum is then applied to remove the air from the autoclave, the traces of humidity and the slight fractions of PIB (i.e. the fractions of PIB dimers, trimers, etc.). 1 mol of maleic anhydride, i.e. 98 g, heated so as to be liquefied is then introduced directly into the autoclave containing the PIB heated to 70°C. The autoclave is reclosed and heated with stirring at 190°C for 5 hours, under the autogenous pressure of the mixture. At the end of the reaction, the temperature is lowered to 130°C and the vacuum is again applied to remove the residues of unreacted maleic anhydride. The autoclave is then opened and the compound obtained is filtered off at 110°C.

Weight obtained: 1050 g, i.e. 0.96 mol of PIB succinic monoanhydride.

b) Esterification with glycerophosphorylcho line

The 1050 g of the above compound and 1000 g of methyl ethyl ketone are introduced into a five-liter reactor with a central stirrer. The mixture is heated to reflux point of the solvent (78°C) and 0.96 mol of glycerophosphorylcholine (MW 256 g), i.e.

245 g of glycerophosphorylcholine, is added portionwise. The mixture is reacted at 78°C with stirring for seven hours. The solvent is then evaporated off on a rotary evaporator to obtain 1290 g of the compound.

Example 9: Lipstick

Claims

1. A cosmetic composition containing at least one polymer comprising at least: - one group of formula (I)

O

— 0-P-O— (CH₂)- N⁺(R₅>3 0) O- in which the groups R₅ are identical or different and each is a hydrogen atom or a (Ci-C₄)alkyl group and e is a natural number ranging from 1 to 4, and

-a graft or a block of polyolefinic nature or a polymeric unit derived from an α-olefin of structure CH₂=CR₁Ri, in which R₁ denotes a hydrogen or a methyl radical and R₂ denotes a linear or branched (Ci-C₅o)alkyl group, or a (C₁-C₇)CyClOaIlCyI group.

2. The cosmetic composition as claimed in claim 1, characterized in that the polymer is liposoluble or dispersible in a fatty phase.

3. The cosmetic composition as claimed in claim 1 or 2, characterized in that the polymer is in the form of an oil.

4. The cosmetic composition as claimed in any one of the preceding claims, characterized in that the polymer is chosen from homopolymers and copolymers, which may be in statistical, alternating, block, grafted, star, comb, gradient or mixed form.

5. The cosmetic composition as claimed in claim 4, characterized in that the polymer is chosen from grafted copolymers.

6. The cosmetic composition as claimed in claim 5, characterized in that the polymer is chosen from grafted copolymers comprising a main chain comprising at least one block of polyolefinic nature and the grafts of which comprise at least one group of formula (I) as defined in claim 1, and preferably phosphorylcholine.

7. The cosmetic composition as claimed in claim 5, characterized in that the polymer is chosen from grafted copolymers comprising a main chain comprising at least one block comprising at least one group of formula (I) as defined in claim 1, and whose grafts comprise identical or different blocks of polyolefinic nature.

8. The cosmetic composition as claimed in claim 4, characterized in that the polymer is chosen from block copolymers, for example diblock or triblock copolymers, comprising, linearly linked, at least one block of polyolefinic nature and at least one block comprising at least one group of formula (I) as defined in claim 1, and preferably phosphorylcholine.

9. The cosmetic composition as claimed in claim 4, characterized in that the polymer is chosen from statistical or random copolymers comprising linearly linked polymer units derived from α-olefins and polymer units, at least one of which comprises at least one group of formula (I) as defined in claim 1, and preferably phosphorylcholine.

10. The cosmetic composition as claimed in claim 4, characterized in that the polymer is a homo- or copolymer of α-olefins which is functionalized at at least one of its ends by at least one group of formula (I) as defined in claim 1, and preferably phosphorylcholine:

- in the form of a copolymer comprising linearly linked, identical or different blocks of polyolefinic nature and comprising at one or both of its ends at least one group of formula (I) as defined in claim 1, and preferably phosphorylcholine, or

- in the form of a polymer of polyolefinic nature comprising at least one group of formula (I) as defined in claim 1, at one or both of its ends.

11. The cosmetic composition as claimed in one of claims 1 to 4, characterized in that the group of formula (I) is linked to at least one polymer unit of the main chain or to at least one of the two ends of the polymer, or alternatively is in at least one chain and/or block and/or graft constituting the polymer, said group of formula (I) possibly being linked directly via a covalent bond or via a spacer.

12. The cosmetic composition as claimed in any one of the preceding claims, characterized in that the polymer also comprises polymer units, chains, blocks and/or grafts derived from at least one monomer (C) which are different than the chains, blocks and/or grafts of polyolefinic nature, and different than the optional chains, blocks and/or grafts comprising the group of formula (I) as defined according to claim 1.

13. The cosmetic composition as claimed in claim 12, characterized in that the monomer (C) is a lipophilic monomer chosen from linear, branched or cyclic C₄-C₄₀ alkyl (meth)acrylates, N-alkyl(meth)acrylamides, N,N'-dialkyl(meth)acrylamides, alkyl vinyl esters, alkyl vinyl ethers and alkyl alkyl esters.

14. The cosmetic composition as claimed in claim 12, characterized in that the monomer (C) is chosen from C₄-C₄₀ alkyl (meth)acrylates such as butyl, isobutyl, tert- butyl, hexyl, tert-hexyl, octyl, 2-ethylhexyl, tert-octyl, decyl, undecyl, dodecyl, isononyl or isostearyl (meth)acrylate.

15. The cosmetic composition as claimed in any one of claims 12 to 14, characterized in that the polymer chains, blocks and/or grafts obtained from the monomers (C) are not crystallizable.

16. The cosmetic composition as claimed in any one of claims 12 to 15, characterized in that the monomer (C) is chosen from C₁₂-C₂₄ alkyl (meth)acrylates.

17. The cosmetic composition as claimed in claim 7, characterized in that the polymer is a grafted copolymer comprising at least:

- a main chain comprising at least one polymer unit derived from a monomer of formula (A):

Y-B-X (A) - X takes the formula (I):

in which the groups R₅ are identical or different and each is a hydrogen atom or a (C₁-C₄)alkyl group and e is a natural number ranging from 1 to 4,

- B represents a linear or branched divalent alkylene, oxyalkylene or oligo- oxyalkylene group possibly containing one or more hetero atoms, and

- a graft of polyolefinic nature.

18. The cosmetic composition as claimed in claim 17, characterized in that Y is an unsaturated ethylenic polymerizable group chosen from:

R CH₂- C C A _Qr I j

O K-

(TV) (V) in which:

- R is a hydrogen atom or a (Ci-C₄)alkyl group,

- A is a group -O- or -NR₁ in which R₁ is a hydrogen atom or a (Ci-C₄)alkyl group or R₁ is a group -B-X in which B and X are as defined above, and - K is a group -(CH₂)_POC(O)-, -(CH₂)_PC(O)O-, -(CH₂)_POC(O)O-,

-(CH₂)_PNR₂-, -(CH₂)_PNR₂C(O)-, -(CH₂)_PC(O)NR₂, -(CH₂)_PNR₂C(O)O-,

-(CH₂)pOC(O)NR₂-, -(CH₂)_PNR₂C(O)NR₂- (in which the group R₂ is identical or different), -(CH₂)_PO- or -(CH₂)_PSO₃-, or optionally in combination with B, a covalent bond and p is a natural number between 1 and 12 and R₂ is a hydrogen atom or a (Ci-C₄)alkyl group.

19. The cosmetic composition as claimed in either of claims 17 and 18, characterized in that the groups R₅ are identical.

20. The cosmetic composition as claimed in any one of claims 17 to 19, characterized in that at least one of the groups R₅ is a methyl group and preferably all of the groups R₅ are methyl groups.

21. The composition as claimed in any one of claims 17 to 20, characterized in that e is a natural number equal to 2 or 3 and preferably equal to 2.

22. The cosmetic composition as claimed in any one of claims 17 to 21, characterized in that the monomer of formula (A) takes the formula (II)

R

I

C-A-B-X (H) ° in which:

- R is a hydrogen atom or a methyl or ethyl group and more preferably a methyl group.

23. The cosmetic composition as claimed in any one of claims 17 to 21, characterized in that the monomer of formula (A) takes the general form (III)

(III) - K is a group and B is a covalent bond, or alternatively K and B are simultaneously groups, or alternatively K and B are simultaneously covalent bonds, or alternatively B is a group and K is a covalent bond, and when K is a group, then p is preferably a natural number from 1 to 6, more preferably 1, 2 or 3 and even more preferably p is equal to 1,

- B is an alkylene group of formula -(C(R₃ )₂)_a-, in which the groups -(C(R₃ )₂)- are identical or different, and in each group -(C(R₃)2)- the groups R₃ are identical or different and each group R₃ is a hydrogen atom or a (Ci-C₄)alkyl group, preferably a hydrogen atom, and a is a natural number ranging from 1 to 12 and preferably from 1 to 6; an oxyalkylene group such as an alkoxyalkyl group containing from 1 to 6 carbon atoms in each alkyl unit, even more preferably -CH₂O(CHi)₄- or an oligo-oxyalkylene group of formula -[(C(R4)₂)_bO]_c(C(R4)₂)_b- in which the groups -(C(R₄)I)- are identical or different and in each group -(C(R₄)I)- the groups R₄ are identical or different and each group R₄ is a hydrogen atom or a (Ci-C₄)alkyl group, preferably a hydrogen atom, and b is a natural number ranging from 1 to 6 and preferably from 2 to 3, and c is a natural number ranging from 2 to 11 and preferably from 2 to 5, or alternatively a covalent bond.

24. The cosmetic composition as claimed in claim 23, characterized in that K is a group -(CH₂)_PNR₂-, -(CH₂)_PNR₂C(O)-, -(CH₂)_PC(O)NR₂, -(CH₂)_PNR₂C(O), -(CH₂)_POC(O)NR₂- or -(CH₂)_PNR₂C(O)NR2-, and then R₂ is preferably a hydrogen atom or a methyl or ethyl group and even more preferably a hydrogen atom.

25. The cosmetic composition as claimed in any one of claims 17 to 24, characterized in that B is a group of formula -(C(R₃ )₂)- or -(C(R₃)₂)₂- such as -(CH₂)- or -(CH₂-CH₂)-, in which R₃ is as defined according to claim 23.

26. The cosmetic composition as claimed in any one of claims 17 to 25, characterized in that the monomer of formula (A) is a phosphorylcholine (meth)acrylate.

27. The cosmetic composition as claimed in any one of claims 17 to 26, characterized in that the grafts of polyolefinic nature are derived from macromonomers of polyolefinic nature with a weight-average molecular mass of between 300 and 30 000, preferably between 500 and 20 000 and more preferably between 1000 and 10 000 g/mol, and comprising an end that is polymerizable with the monomer of formula (A).

28. The cosmetic composition as claimed in any one of claims 17 to 27, characterized in that the grafts of polyolefinic nature are not crystallizable.

29. The cosmetic composition as claimed in any one of claims 17 to 28, characterized in that the grafts of polyolefinic nature comprise polymer units based on homopolyolefin or copolyolefϊns and in that these polyolefins comprise polybutene isomers.

30. The cosmetic composition as claimed in claim 29, characterized in that the polybutene isomers are polyisobutenes.

31. The cosmetic composition as claimed in any one of claims 17 to 30, characterized in that the molecular mass of the grafts is between 300 and 30 000, and preferably between 500 and 10 000 g/mol.

32. The cosmetic composition as claimed in any one of claims 17 to 31, characterized in that the macromonomers used to lead to the grafts of polyolefinic nature are formed from polyisobutene and comprise one end of (meth)acrylic, vinyl or styrene nature capable of copolymerizing with the monomer of formula (A).

33. The cosmetic composition as claimed in any one of claims 17 to 32, characterized in that the polymer comprises polymer units or polymer chains derived from monomers (C) as defined according to any one of claims 12 to 16.

34. The cosmetic composition as claimed in claim 8 or any one of the claims dependent thereon, characterized in that the polymer is a sequenced block copolymer comprising at least one polymer unit or alternatively a group containing a group of formula (I), as defined in claim 1 and/or at its end a monomer containing a group of formula (I) as defined in claim 1, at least one block comprising at least one polymer unit derived from a macromonomer of polyolefinic nature and optionally at least one block derived from the polymerization of monomers (C), the monomer of formula (C) being as defined according to any one of claims 12 to 16.

35. The cosmetic composition as claimed in claim 34, characterized in that the macromonomer of polyolefinic nature comprises polymer units based on homopolyolefins or copolyolefins comprising polybutene and preferably polyisobutene.

36. The cosmetic composition as claimed in claim 34 or 35, characterized in that the monomer comprising at least one polymer unit or alternatively a group containing a group of formula (I) is a monomer of formula (A) as defined in any one of claims 17 to 26.

37. The cosmetic composition as claimed in claim 9, characterized in that the monomer comprising at least one polymer unit or alternatively a group containing a group of formula (I) is a monomer of formula (A) as defined in any one of claims 17 to 26.

38. The cosmetic composition as claimed in claim 9 or 37, characterized in that said α-olefins comprise at least four carbon atoms, and are preferably butene and its isomers.

39. The cosmetic composition as claimed in any one of claims 1 to 38, characterized in that the polymer has a weight-average molecular mass (or molecular mass at the crest of the GPC peak) of between 500 and 10⁶, preferably between 1000 and 500 000 and even more preferably between 3000 and 250 000 g/mol.

40. The cosmetic composition as claimed in any one of the preceding claims, characterized in that it comprises a fatty phase in which the polymer is dissolved or dispersed.

41. The composition as claimed in the preceding claim, characterized in that the fatty phase contains at least one compound chosen from waxes, pasty iatty substances and oils.

42. The composition as claimed in any one of the preceding claims, characterized in that it is a makeup and/or care composition for the lips and/or the skin, in particular a lipstick or a foundation.

43. The composition as claimed in any one of the preceding claims, characterized in that it simultaneously has improved gloss and staying power properties, in particular the staying power of the gloss over time.

44. The use of the polymer defined as claimed in any one of claims 1 to 39, in a cosmetic composition.

45. The use as claimed in the preceding claim for simultaneously improving the gloss and staying power properties, in particular the staying power of the gloss over time.

46. A nontherapeutic process for making up and/or caring for keratin materials, comprising at least one step of applying thereto at least one composition as claimed in any one of claims 1 to 43.