FR3045372A1

FR3045372A1 - PROCESS FOR TREATING KERATIN FIBERS WITH A MALEIC ANHYDRIDE SEQUENCE POLYMER AND A POLYOL

Info

Publication number: FR3045372A1
Application number: FR1563109A
Authority: FR
Inventors: Bertrand Lion; Julien Portal
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2015-12-22
Filing date: 2015-12-22
Publication date: 2017-06-23
Anticipated expiration: 2035-12-22
Also published as: WO2017108595A1; FR3045372B1

Abstract

L'invention concerne un procédé cosmétique de traitement des fibres kératiniques comprenant l'application sur les fibres kératiniques d'un mélange d'un polymère séquencé d'anhydride maléique, d'un polyol liposoluble et d'un catalyseur aminé ; ledit polymère séquencé comprenant : une première séquence ayant une température de transition vitreuse (Tg) supérieure ou égale à 40°C issue d'un monomère CH2 = C(R1)-COOR2 avec R1 = H ou méthyle, R2 = groupe cycloalkyle C4 à C12 ; et une deuxième séquence ayant une température de transition vitreuse (Tg) inférieure ou égale à 20°C issue d'un monomère anhydride maléique et d'un monomère CH2 = C(R1)-COOR3 avec R1 = H ou méthyle, R3 = groupe alkyle non substitué en C1 à C6, linéaire ou ramifié, à l'exception du groupe tertiobutyle, ou un groupe méthoxyéthyle ; et une étape de chauffage des fibres kératiniques à une température allant de 90 °C à 250 °C. L'invention concerne aussi le polymère réticulé obtenu par la réaction dudit polymère séquencé avec ledit polyol liposoluble. Les fibres kératiniques traitées ont de bonnes propriétés de fixation, rémanentes à l'eau.The invention relates to a cosmetic process for treating keratin fibers, comprising applying to the keratinous fibers a mixture of a block polymer of maleic anhydride, a fat-soluble polyol and an amine catalyst; said sequenced polymer comprising: a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C derived from a monomer CH2 = C (R1) -COOR2 with R1 = H or methyl, R2 = C4 cycloalkyl group; C12; and a second block having a glass transition temperature (Tg) less than or equal to 20 ° C derived from a maleic anhydride monomer and a monomer CH2 = C (R1) -COOR3 with R1 = H or methyl, R3 = group unsubstituted C1-C6 alkyl, linear or branched, except tertiary butyl, or methoxyethyl; and a step of heating the keratinous fibers at a temperature ranging from 90 ° C to 250 ° C. The invention also relates to the crosslinked polymer obtained by reacting said block polymer with said liposoluble polyol. The treated keratin fibers have good fixing properties, which are water-resistant.

Description

The present invention relates to a process for the cosmetic treatment of keratin fibers using a block polymer containing maleic anhydride groups and a liposoluble polyol, and a kit for carrying out said method.

Hair products usually contain film-forming polymers to give hair a hold of the hairstyle. However, the quality of the maintenance of the hair may be impaired during contact with water, for example by rain or during showering: this deterioration may be due to the fact that the deposition of the film-forming polymer on the hair has poor resistance to contact with water and gets rid of over time.

The object of the present invention is to provide a polymer for obtaining a film-forming deposit having good water resistance and suitable for being applied to the hair to obtain good fixing properties.

The inventors have discovered that a particular block polymer of maleic anhydride associated with a particular polyol applied to the hair makes it possible to obtain good hair fixing properties, having good persistence with water.

More specifically, the subject of the present invention is a process, in particular a cosmetic process, for treating keratinous fibers, comprising: (i) a step of applying to the keratin fibers a mixture (extemporaneous) of a block polymer of maleic anhydride, or a cosmetic composition comprising it, a liposoluble polyol compound or a cosmetic composition containing it, and an aminated catalyst; said block polymer comprising: at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C and obtained from at least one (meth) acrylate monomer of formula CH2 = C (Ri) -COOR2 wherein R 1 is H or methyl, R 2 is C 4 -C 12 cycloalkyl; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one maleic anhydride monomer and at least one (meth) acrylate monomer of formula CH2 = C (R1) -COOR3 wherein R1 is H or methyl, R3 is unsubstituted C1-C6 linear or branched alkyl except tertiary butyl or methoxyethyl. (ii) a step of heating the keratinous fibers at a temperature ranging from 90 ° C to 250 ° C .; steps (i) and (ii) being performed at the same time or separately in order (i) then (ii). The subject of the invention is also a composition, in particular a cosmetic composition, obtained by mixing said block polymer of maleic anhydride, or a composition containing it, comprising a physiologically acceptable medium, a liposoluble polyol compound or a composition containing and comprising a physiologically acceptable medium, and an amine catalyst, as defined below. The subject of the invention is also a kit comprising: a first composition comprising said maleic anhydride block polymer as described above and optionally comprising a physiologically acceptable medium, and a second composition comprising a liposoluble polyol compound as described above and optionally comprising a physiologically acceptable medium, the first composition or the second composition further comprising said amine catalyst, the first and second compositions each being packaged in a separate package. The packaging assembly of the compositions is in a known manner any packaging adapted to store the cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).

Such a kit makes it possible to implement the process for treating keratin materials according to the invention.

The block polymer used according to the invention comprises: at least one first block having a glass transition temperature (Tg) greater than or equal to 40 ° C. and obtained from at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 2 wherein R 1 is H or methyl, R 2 is C 4 -C 12 cycloalkyl; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one maleic anhydride monomer and at least one (meth) acrylate monomer of formula CH2 = C (R1) -COOR3 wherein R1 is H or methyl, R3 is unsubstituted C1-C6 linear or branched alkyl except tertiary butyl or methoxyethyl.

The indicated glass transition temperatures of the first and second sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:

ω, being the mass fraction of the monomer i in the sequence under consideration and Tg, being the glass transition temperature of the homopolymer of the monomer i.

Unless otherwise indicated, the Tg values for the first and second sequences in the present application are theoretical Tg. The difference between the glass transition temperatures of the first and second blocks is generally greater than 20 ° C., preferably greater than 40 ° C., and better still greater than 60 ° C.

In the present invention, the expression "between ... and ..." is intended to denote an interval of values whose mentioned limits are excluded, and "from ... to ..." and "from from ... to ... ", an interval of values whose terminals are included.

The block polymer used according to the invention has a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C, for example a Tg ranging from 40 to 150 ° C, and obtained from at least one (meth) acrylate monomer of formula CH2 = C (R1) -COOR2 wherein R1 is H or methyl, R2 is C4-C12 cycloalkyl, and preferably is isobornyl.

Preferably, said first block has a Tg greater than or equal to 60 ° C, ranging for example from 60 ° C to 140 ° C, in particular ranging from 80 ° C to 120 ° C, preferably ranging from 95 to 110 ° C.

The monomers present in the first block of the polymer and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C., and in particular as described above.

According to a preferred embodiment, the first block of the polymer is obtained from at least one acrylate monomer of formula CH 2 CHCH-COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer. formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 cycloalkyl group at

Ci2.

The first block of the polymer can be obtained exclusively with said acrylate monomer and said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are used, preferably present in mass proportions acrylate / methacrylate between 30: 70 and 70: 30, preferably between 40: 60 and 60: 40, in particular between 45: 55 and 55:45 .

The proportion of the first block in the block polymer is preferably 60 to 80% by weight of the polymer, more preferably 65 to 75%.

According to a preferred embodiment, the first block of the polymer is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

The first block of the polymer may further comprise an additional monomer selected from linear or branched C 1 -C 22 alkyl (meth) acrylates (i.e., including a C 3 -C 22 alkyl group). such as, for example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, behenyl acrylate, behenyl methacrylate, stearyl acrylate, stearyl methacrylate .

Said additional monomer may be present in a content ranging from 0.1 to 15% by weight, relative to the total weight of the monomers of the first block of said block polymer, and preferably ranging from 0.1 to 5%.

According to one embodiment, the first sequence of said sequenced polymer contains no additional monomer.

The block polymer used according to the invention has a second block having a glass transition temperature (Tg) of less than or equal to 20 ° C., for example a Tg ranging from -100 to 20 ° C., and is obtained from from at least one maleic anhydride monomer and at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which H is a methyl radical, R 3 representing a linear or branched C 1 to C 6 unsubstituted alkyl group; with the exception of tertiary butyl or methoxyethyl.

Preferably, said second block has a Tg of less than or equal to 10 ° C., in particular ranging from -80 ° C. to 10 ° C. and better still less than or equal to 0 ° C., for example ranging from -100 ° C. to 0 ° C. , especially ranging from -30 ° C to 0 ° C.

The monomers present in the second block of the polymer and their proportions are preferably chosen so that the glass transition temperature of the second block is less than or equal to 20 ° C., and in particular as described above.

Monomers having a Tg of less than or equal to 20 ° C are preferred isobutyl acrylate, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate, or mixtures thereof in all proportions, and preferably isobutyl acrylate.

The second block of the polymer can be obtained exclusively with maleic anhydride and said (meth) acrylate monomer.

In the second block, maleic anhydride and the (meth) acrylate monomer are preferably used in proportions by mass (meth) acrylate / maleic anhydride ranging from 1 to 10, preferably ranging from 2 to 9, in particular ranging from 3 to 8. or from 4 to 7.

The proportion of the second block in the block polymer is preferably 20 to 40% by weight of the polymer, more preferably 25 to 35% by weight.

According to a preferred embodiment, the second block of the polymer is obtained by polymerization of maleic anhydride and isobutyl acrylate.

The second block of the polymer may further comprise an additional silicone monomer of formula (I) (hereinafter referred to as silicone monomer):

(I) wherein: - Rs denotes a hydrogen atom or a methyl group; preferably methyl; R 9 denotes a linear or branched divalent hydrocarbon group, preferably linear, having from 1 to 10 carbon atoms, preferably having from 2 to 4 carbon atoms, and optionally containing one or two ether bonds -O-; preferably an ethylene, propylene or butylene group; - R- o denotes a linear or branched alkyl group having 1 to 10 carbon atoms, especially 2 to 8 carbon atoms; preferably methyl, ethyl, propyl, butyl or pentyl; n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200, and preferably ranging from 5 to 100.

The monomer (I) is a polydimethylsiloxane end-group mono (meth) acryloyloxy.

In particular, monomethacryloyloxypropyl polydimethylsiloxanes may be used, such as those sold under the names MCR-M07, MCR-M17, MCR-M11 and MCR-M22 by Gelest Inc or the silicone macromonomers sold under the names X-22-2475 and X-22. -2426, X-22-174DX by Shin Etsu.

The monomer (I) may be present in the second block of the sequenced polymer in a content ranging from 0.1 to 15% by weight, relative to the total weight of the monomers of the second block of said block polymer, and preferably ranging from , 1 to 5%.

According to one embodiment, the second sequence of said sequenced polymer does not contain additional monomer.

Preferably, the polymer used according to the invention comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in the first block and maleic anhydride and isobutyl acrylate monomers in the second block.

Preferably, the polymer comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of from 30: 70 to 70: 30 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of 40:60 to 60:40 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence.

Preferably, the polymer comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of from 30: 70 to 70: 30 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of 40:60 to 60:40 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.

Preferably, the polymer comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of from 30: 70 to 70: 30 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second block, the first block representing between 65 and 75% by weight of the polymer, and especially 70% by weight, and the maleic anhydride representing from 3 to 7% by weight of the polymer.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio of 40:60 to 60:40 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence, the first block representing between 65 and 75% by weight of the polymer, and in particular 70% by weight, and maleic anhydride representing from 3 to 7% by weight of the polymer.

Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and maleic anhydride monomers. in the second sequence, the first block representing between 65 and 75% by weight of the polymer, and in particular 70% by weight, and maleic anhydride representing from 3 to 7% by weight of the polymer.

Said first and second polymer blocks may advantageously be interconnected by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

The intermediate segment is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer makes it possible to "compatibilize" these blocks.

Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.

Preferably, the intermediate sequence is derived essentially from constituent monomers of the first sequence and the second sequence.

By "essentially" is meant at least 85%, preferably at least 90%, better at 95% and even better at 100%.

Advantageously, the intermediate block has a glass transition temperature Tg between the glass transition temperatures of the first and second blocks.

The block polymer used according to the invention is advantageously a film-forming polymer. By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.

Advantageously, the block polymer has a polydispersity index greater than 2. The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn.

The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The weight average mass (Mw) of the sequenced polymer is preferably less than or equal to 300,000, for example from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol.

The number average mass (Mn) of the sequenced polymer is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 50,000 g / mol.

Preferably, the polydispersity index of the sequenced polymer is greater than 2, for example ranging from 3 to 11, preferably greater than or equal to 4, for example ranging from 4 to 10. The subject of the invention is also a process for preparation of a sequenced polymer, comprising mixing, in the same reactor, a polymerization solvent, an initiator, a maleic anhydride monomer, at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which R 1 represents H or a methyl radical, R3 represents a linear or branched C1-C6 unsubstituted alkyl group, with the exception of the tert-butyl group, or a methoxyethyl group, at least one (meth) acrylate monomer of formula CH2 = C ( R 1) -COOR 2 in which R 1 represents H or a methyl radical, R 2 represents a C 4 to C 12 cycloalkyl group, according to the following sequence of steps: a portion of the polymerization solvent and a portion of the polymer are poured into the reactor; initiator, mel which is heated to a reaction temperature of between 60 ° and 120 ° C., the at least one monomer (meth) acrylate of the formula CH 2 = C (R 1) - COOR 2 is then poured in a first casting. is allowed to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, in a second casting, again the polymerization initiator, the maleic anhydride monomer and said (meth) acrylate of formula CH 2 = C 1 R 1 -COOR 2 which is allowed to react for a period T after which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought back to ambient temperature.

By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, C 8 -C 16 branched alkanes such as C 8 -C 16 isoalkanes such as isododecane, isodecane and isohexadecane. and their mixtures. Preferably, the polymerization solvent is isododecane.

According to another embodiment, the subject of the invention is a process for preparing a polymer, comprising mixing, in the same reactor, a polymerization solvent, an initiator, a maleic anhydride monomer, at least one monomer (meth) acrylate of formula CH2 = C (R1) -COOR3 wherein R1 is H or methyl, R3 is unsubstituted C1-C6 linear or branched alkyl, with the exception of tert-butyl, or methoxyethyl group, at least one (meth) acrylate monomer of the formula CH 2 = C (R 1) -COOR 2 in which R! represents H or a methyl radical, R2 represents a C4 to C12 cycloalkyl group, according to the following sequence of steps: - part of the polymerization solvent and part of the initiator, a mixture which is mixed into the reactor, are poured into the reactor; heated to a reaction temperature of between 60 and 120 ° C., the maleic anhydride monomer and said (meth) acrylate of formula CH 2 = C (Ri) -COOR 3, which is left to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, in a second casting, again the polymerization initiator, said at least one monomer (meth) acrylate of formula CH 2 = C (R 1) -COOR 2, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature.

The polymerization temperature is preferably between 85 and 95 ° C, in particular of the order of 90 ° C.

The reaction time after the second casting is preferably between 3 and 6 hours.

The monomers used in this process and their proportions may be those described above.

The polymerization is especially carried out in the presence of a radical initiator, in particular of the peroxide type (for example tert-Butyl peroxy-2-ethylhexanoate: Trigonox 21S, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel) or azo for example (AIBN: azobisisobutyronitrile; V50: 2,2'-azo-bis (2-amidinopropane) dihydrochloride). The subject of the invention is also, as novel polymer, the block polymer described above.

The block polymer used according to the invention may be used in a composition comprising a physiologically acceptable medium, in particular in a cosmetic composition.

By physiologically acceptable medium is meant a medium compatible with keratinous fibers of human beings, in particular with the hair.

By cosmetic composition is meant a composition compatible with keratin materials, which has a pleasant color, odor and feel, and which does not generate unacceptable discomfort (tingling, tightness, redness), likely to distract the consumer .

The block polymer of maleic anhydride as defined above may be present in the composition used according to the invention, resulting from the mixture described above (extemporaneous mixing), in a content ranging from 0.1 to 40% by weight, relative to total weight of the composition resulting from extemporaneous mixing, preferably from 0.5% to 35% by weight, and preferably from 1% to 30% by weight, and more preferably from 10% to 30% by weight. The subject of the invention is also a composition comprising said block polymer, in particular in a physiologically acceptable medium.

The process according to the invention uses a liposoluble polyol compound.

By liposoluble polyol is meant a polyhydroxy compound soluble or miscible with at least 1% by weight in isododecane at 25 ° C.

The polyol used in the process according to the invention is an organic compound comprising at least 2 alcohol functions (that is to say two hydroxyl groups). This compound may comprise other non-reactive chemical functions such as the ester, amide, ketone and urethane functions.

It is possible to use a mixture of different polyols.

According to a first embodiment of the invention, the polyol compound is a non-polymeric organic compound of formula (II): W (OH) n (II) in which n denotes an integer greater than or equal to 2, preferably included between 2 and 10, preferably between 2 and 5 (limits included) and W denotes a multivalent (at least divalent) C8-C30 radical, linear or branched or (hetero) cyclic, saturated or unsaturated, W being able to further one or several functions chosen from ether, thioether, ester, ketone and amide functions.

By non-polymeric compound is meant a compound which is not directly obtained by a polymerization reaction of monomers. The polyol compound is preferably a diol compound.

Preferably, W denotes a multivalent Cs-C-iq- radical, in particular linear. Preferably, the liposoluble polyol is a C 1 -C 10 diol. especially linear. Advantageously, the Cs-C-iq chain is a hydrocarbon chain (formed of carbon and hydrogen).

In particular, the liposoluble polyol is a linear diol C 8 -C 18, especially Ciq-C 14.

As polyol of formula (II), there may be mentioned 1,8-octanediol, 1-10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18 -octadécanediol. Preferably, 1-10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol are used. Preferentially, 1,12-dodecanediol is used.

According to a second embodiment of the invention, the polyol compound is a polymeric compound of formula (II): ## STR2 ## in which n denotes an integer greater than or equal to 2, and POL denotes a polymeric radical carbon or silicone, POL may additionally contain one or more heteroatoms such as O, N, S, and / or one or more functions chosen from esters, ketones, amides, ureas, carbamates, and / or be substituted by one or several linear or branched C- | -C-> alkyl groups, linear or branched C -C alkoxy groups, it being understood that when POL is substituted, the hydroxyl functions may be carried by the substituent (s) .

The average molecular weight in molar weight of the compounds of formula (III) is generally between 500 and 400,000, preferably between 500 and 150,000.

Preferably, the polyol polymers may be diol polymers, especially polyolefin diols, polydimethylsiloxane diols, polyester diols.

The polyolefin diols may be hydroxyl end polydienes, for example those described in FR-A-2782723. They may be chosen from diols derived from homopolymers and copolymers of polybutadiene, polyisoprene and poly (1,3-pentadiene). Preferably, they have a number-average molecular weight (Mn) of less than 7000, preferably of between 1000 and 5000. Mention may be made in particular of the hydroxylated polybutadienes sold by the company Cray Valley under the trade marks POLY BD R45HTLO, POLY BD R45V, and POLY BD R-20 LM, which will preferably be hydrogenated; as well as dihydroxylated hydrogenated 1,2-polybutadienes, such as GI3000 of Mn = 3100, GI2000 (Mn = 2100) and GI1000 (Mn = 1500) marketed by Nisso.

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

especially those marketed by Mitsubishi under the POLYTAIL brand.

Polybutadienes hydrogenated diols are preferably used.

The polydimethylsiloxane diols can be those of formula (IV):

(IV) in which: R1 = divalent C2-C0 alkylene group X = covalent bond or -O-R2- group with R2 = C2-C0 alkylene n = 1 to 100, preferably 5 to 50, and preferably 10 at 30

As polydimethylsiloxane diols, those sold under the names KF-6000, KF-6001, KF-6002 and KF-6003 can be used by Shin-Etsu Chemicals.

The polydimethylsiloxane diol of formula (IVa) is preferably used:

(IVa)

It is also possible to use dimethiconols which are polydimethylsiloxanes having terminal OH functions. For example, those sold under the name "XIAMETER PMX-1502 FLUID" by Dow Corning.

The polyester diols may be chosen from those resulting from the condensation reaction of a C 8 -C 30 diol, preferably C 8 -C 10 diol, such as 1,8-octanediol, 1,9-nonane diol, 2-methyl-1,8-octanediol, 1-10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol; and a 4-0-12 carboxylic acid diacid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, trimellitic acid, azelaic acid, succinic acid, glutaric acid.

Polyester polyols are in particular described in patents US6136880 and EP0960355.

Examples of polyester diols that may be mentioned include copolymers of 1,9-nonanediol / adipic acid such as those sold under the name KURAPOL N-2010 by the company Kuraray.

The polyester polyols are preferably chosen from hydrogenated polybutadienes diols and polydimethylsiloxane diols of formula (IV), (IVa) described above.

Advantageously, the liposoluble polyol compound is used in a molar ratio OH group of the liposoluble polyol / maleic anhydride group of the acrylic polymer ranging from 0.01 to 10, preferably ranging from 0.1 to 5, preferably ranging from 0.1. at 2, and more preferably ranging from 0.1 to 1.

The polyol compound used reacts with the maleic anhydride group present in the sequenced polymer, for example as follows:

*

Such a crosslinked polymer is new and is therefore also the object of the present invention.

The crosslinked polymer is thus capable of being obtained by reacting said liposoluble polyol compound with the acrylic maleic anhydride polymer described above, especially in the presence of said amine catalyst. Some or all of the anhydride groups react with the OH group of the polyl compound and form a unit having an ester group and a carboxylic acid group as previously described.

The amine catalyst used in the process according to the invention may be chosen from catalysts with primary amine function or aminidine function or with guanidine function.

The tertiary amine functional catalyst may be chosen from triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, methyldibutylamine, N-methyldicyclohexylamine, Ν, Ν-dimethylcyclohexylamine, ethyldiisopropylamine, Ν, Ν-diethylcyclohexylamine, pyridine, 4-dimethylaminopyridine, N-methylpiperidine, N-ethylpiperidine, Nn-butylpiperidine, 1,2-dimethylpiperidine, N-methylpyrrolidine, 1,2-dimethylpyrrolidine, dimethylaniline, picoline, N, N-dimethylbenzylamine, bis-2-dimethylaminoethyl ether, Ν, Ν, Ν ', Ν', Ν "-pentamethyldiethylene triamine, Ν, Ν, Ν ', Ν" tetramethylethylenediamine, N-methyl morpholine, N-ethyl morpholine, 1,4-diazabicyclo [2.2.2] octane and mixtures thereof.

Diisopropylethylamine is preferably used.

The aminidine-functional catalysts are, for example, 1,5-diazabicyclo [4.3.0] non-5-ene (or DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (or DBU).

The guanidine functional catalysts may be chosen from compounds of formula (V) below:

in which R 1, R 2, R 3, R 4 and R 5 represent, independently, a hydrogen atom or a linear or branched C 1 -C 4 alkyl or alkenyl radical, when R 1, R 2 and R 3 and R 4 represent a hydrogen atom R5 may also indicate an acetyl radical; carboxamide; methoxy; ethoxy; 1,2,4-triazolyl; cyclopentyl; methoxycarbonyl; ethoxycarbonyl; phenyl; benzyl; thiazolidone; benzimidazole; benzoxazole; benzothiazole; or C (= NH) -NR6R7 wherein R6 and R7 denote, independently of one another, a hydrogen atom or a linear or branched C1-C4 lower alkyl radical; or a phenyl radical, when R1 = R2 = R3 = H, R4 and R5 can also form, with the nitrogen atom which carries them, a pyrrolidine, piperidine, pyrazole or 1,2,4-triazole ring, when R1 = R2 = H, and R4 = H or methyl, R3 and R5 may also together form a 5-membered ring optionally containing an oxo group, and their organic or inorganic salts.

As salts, there may be mentioned salts of hydrochloride, sulfate, sulfamate, carbonate, bicarbonate, phosphate, acetate.

Among the compounds of formula (V), mention may notably be made of the following compounds: guanidine, aminoguanidine, 1-acetylguanidine, guanylurea, phenylguanidine, 1,1-dimethylguanidine, 1-ethylguanidine, 1, 1-diethylguanidine, creatine, agmatine, biguanide, N-methyl biguanide, N-ethyl biguanide, N-propyl biguanide, N-butylbiguanide, 1,1-dimethylbiguanide, 1-phenylbiguanide, 1.1.3.3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1H-pyrazole-1-carboxamidine, 5-hydroxy-3-methyl-1H-pyrazole-1-carboximidamide, 3,5-diamino-1H-1,2,4-triazole-1-carboximidamide, 2-guanidone-4-thiazolidone, 2-guanidinobenzimidazole, 2-guanidinobenzoxazole, 2-guanidinobenzothiazole, 1.1.3.3-Tetramethylguanidine (or TMG), 1,5,7-Triazabicyclo [4.4.0] dec-5-ene (or TBD), 7-Methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (or MTBD).

The aminated catalyst may be present in a content ranging from 0.1 to 0.5% by weight, relative to the total weight of the composition resulting from the mixture described above (extemporaneous mixing), preferably ranging from 0.1 to 0, 2% by weight.

The process for treating keratinous fibers, in particular human keratinous fibers such as the hair, comprises: (i) a step of applying to the keratinous fibers of a mixture (extemporaneous) of the block polymer of maleic anhydride, or of a cosmetic composition comprising it, liposoluble polyol compound or a cosmetic composition containing it, and aminated catalyst as defined above; (ii) a step of heating the keratin fibers at a temperature ranging from 90 ° C. to 250 ° C., the steps (i) and (ii) being carried out simultaneously or separately in the order of step (i) and then step (ii) .

According to one embodiment of the process according to the invention, the mixture of the composition comprising the block polymer of maleic anhydride and of the liposoluble polyol, or of the composition containing it, and the aminated catalyst, is carried out in a time between 1 minute and 24 hours before application to the keratinous fibers, and preferably between 5 and 30 minutes.

The method according to the invention comprises a step (ii) of heating the keratin fibers at a temperature ranging from 90 ° C to 250 ° C, preferably ranging from 100 to 230 ° C. Preferably, the step of heating the keratinous fibers is carried out at a temperature ranging from 170 to 250 ° C., preferably ranging from 180 ° C. to 240 ° C., preferably ranging from 190 ° C. to 230 ° C., in particular ranging from 200 ° C to 230 ° C.

This heating step is advantageously carried out by means of an iron. The heating step is necessary to optimize the effects of the process.

By "iron" is meant, in the sense of the present invention, a device for heating the keratinous fibers contacting said fibers and the heating device. The end of the iron coming into contact with the keratin fibers generally has two flat surfaces. These two surfaces can be metallic or ceramic. In particular, these two surfaces can be smooth or notched or curved. The heating step may be carried out by means of a straightening iron, a curling iron, a crimping iron. Preferably, the heating step is performed by means of a smoothing iron. By way of example of irons that can be used in the smoothing process according to the invention, mention may be made of all types of flat iron, and in particular, in a nonlimiting manner, those described in patents US 5,957,140 and US 5,046,516. The iron can be applied by successive separate keys of a few seconds, or by progressive displacement or sliding along wicks of keratinous fibers, especially human keratinous fibers such as the hair.

Preferably, the application of iron in the process according to the invention is in continuous movement from the root to the tip of the hair, in one or more passages, in particular in two to twenty passages. The duration of each passage of the iron can go from 2 seconds to 1 minute.

The method according to the invention may also comprise an additional step of drying the keratinous fibers after the step (i) of applying the block polymer or of the composition containing it and before the step (ii) of heating the keratinous fibers carried out at a temperature ranging from 90 ° C to 250 ° C. The drying step can be carried out by means of a hair dryer, a helmet or by drying in the open air. The drying step is advantageously carried out at a temperature ranging from 20 to 70 ° C.

After the heating step, the keratin fibers may be optionally rinsed with water or washed with a shampoo. The keratinous fibers are then optionally dried by means of a hairdryer or a helmet or in the open air.

According to one embodiment, the method according to the invention is implemented on natural keratinous fibers or damaged or sensitized, possibly colored and / or having undergone prior treatment of shaping durable or temporary.

Damaged fibers are for example dry fibers or rough or brittle or forked or soft.

Sensitized fibers are for example discolored fibers, stripped or permed.

The method according to the invention is preferably implemented on dry keratinous fibers, that is to say non-wet fibers, especially dry hair.

After the step (i) of application to the keratinous fibers of the sequenced polymer, or of a cosmetic composition containing it, and before carrying out the step (ii) of heating the keratinous fibers, the polymer can be left sequenced or the composition containing it applied for a period ranging from 1 to 60 minutes, preferably from 2 to 50 minutes, preferably from 5 to 45 minutes. The exposure time can be carried out at a temperature ranging from 15 ° C to 45 ° C, preferably at room temperature (25 ° C).

The composition described above is advantageously applied to the keratin fibers in an amount ranging from 0.1 to 10 grams, preferably from 0.2 to 5 grams of composition per gram of keratin fibers.

After application of the composition to the keratinous fibers, the latter may be dewatered to remove the excess of composition.

The treatment method according to the invention may be implemented during and / or after, preferably after, an additional cosmetic treatment process for keratinous fibers, such as a temporary shaping process (shaping with curlers, curling iron, hair straightener) or a durable shaping process (permanent, straightening) or a process for dyeing or bleaching keratin fibers.

The treatment method according to the invention can also be implemented post-treatment of a cosmetic treatment process.

In particular, the treatment method is implemented in post-treatment of a method of staining, bleaching, straightening and / or a permanent process.

According to the process according to the invention, a mixture is prepared, in particular extemporaneous, of the block polymer of maleic anhydride, of the liposoluble polyol compound and of the amine catalyst, and the mixture is applied to the keratinous fibers, in particular to the hair.

The composition used according to the invention is generally suitable for topical application to keratinous fibers, and therefore generally comprises a physiologically acceptable medium, that is to say a medium compatible with the skin and / or its integuments. It is preferably a cosmetically acceptable medium, that is to say which has a pleasant color, odor and feel and that does not generate unacceptable discomfort (tingling, tightness, redness), likely to divert the consumer from using this composition.

According to a preferred embodiment of the invention, the composition comprising the block polymer of maleic anhydride may contain a hydrocarbon oil. The hydrocarbon oil is a liquid oil at room temperature (25 ° C).

Hydrocarbon oil is understood to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. The hydrocarbon oil may be volatile or non-volatile. Preferably, the hydrocarbon oil is volatile. The hydrocarbon-based oil may be chosen from: hydrocarbon-based oils having 8 to 14 carbon atoms, and in particular: C 8 -C 14 branched alkanes, such as C 8 -C 14 isoalkanes of petroleum origin (also called isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names Isopars' or permetyls, - linear alkanes, for example such as the n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11 ) and n-tridecane (C13) obtained in Examples 1 and 2 of Application WO2008 / 155059 from Cognis, and mixtures thereof. short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate; plant origin such as triglycerides consisting of esters of fatty acids and of glycerol whose fatty acids may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or alternatively caprylic / capric acid triglycerides, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, synthetic ethers having from 10 to 40 carbon atoms. carbon; linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof; synthetic esters, such as oils; of formula R ^ OORa wherein R ^ represents the residue of a linear or branched fatty acid having from 1 to 40 carbon atoms and R2 represents a particularly branched hydrocarbon chain containing from 1 to 40 carbon atoms provided that R ^ + R2 is> 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoates, hexyl laurate, adipate, and the like. diisopropyl, isononyl isononanoate, 2-ethyl hexyl palmitate, isostearyl isostearate, 2-hexyl decyl laurate, 2-octyl decyl palmitate, 2-octyl myristate, dodecyl, heptanoates, octanoates, decanoates or castor oleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters, branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol and oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

Advantageously, the hydrocarbon oil is apolar (thus formed only of carbon and hydrogen atoms). The hydrocarbon oil is preferably chosen from hydrocarbon-based oils having 8 to 14 carbon atoms, in particular the apolar oils described above.

Preferentially, the hydrocarbon oil is isododecane.

The composition comprising the polymer may contain, in addition to the hydrocarbon oil, a silicone oil. The term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The silicone oil can be volatile or non-volatile.

The term "volatile oil", an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular, having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), 10 mmHg).

The term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa.

As volatile silicone oils, mention may be made of volatile linear or cyclic silicone oils, especially those having a viscosity <8 centistokes (cSt) (8 × 10 -6 m 2 / s), and having, in particular, from 2 to 10 atoms silicon, and in particular from 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms. As the volatile silicone oil that may be used in the invention, mention may be made, in particular, of dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

Non-volatile silicone oils that may be mentioned are non-volatile, linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

Advantageously, the composition may comprise a hydrocarbon oil in a content ranging from 60 to 100% by weight of the total weight of the oils present in the composition and from 0 to 40% by weight of silicone oil. According to a preferred embodiment of the invention, the composition contains as oil only a hydrocarbon oil. Preferably, the hydrocarbon oil is volatile.

The composition according to the invention may comprise a cosmetic additive chosen from perfumes, preservatives, fillers, UV filters, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, anti-inflammatory agents and free radicals, polymers, thickeners, dyestuffs, dandruff active agents.

According to one embodiment, the composition according to the invention is an anhydrous composition. By anhydrous composition is meant a composition containing less than 2% by weight of water, or even less than 0.5% of water, and especially free of water. If necessary, such small amounts of water may in particular be brought by ingredients of the composition which may contain residual amounts.

Of course, those skilled in the art will take care to choose this or these optional additional compounds and / or their amount in such a way that the anti-wrinkle properties of the composition according to the invention are not, or not substantially, impaired by the addition envisaged. The invention will now be described with reference to the following examples given for illustrative and non-limiting.

Example 1: Isobornyl methacrylate / isobornyl acrylate copolymer (35/35 by weight) -isobutyl co-acrylate / maleic anhydride (25/5 by weight)

In a 1-liter jacketed reactor equipped with a stirring anchor 1 liter of isododecane was introduced and the temperature was increased from 25 ° C. to 90 ° C. in 1 hour.

105 g of isobornyl methacrylate, 105 g of isobornyl acrylate and 1.8 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel) were then added over 1 hour. . The reaction mixture was stirred for 1 hour at 90 ° C.

75 g of isobutyl acrylate, 15 g of maleic anhydride and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane were then introduced over 30 minutes.

The reaction mixture was stirred for 3 hours at 90 ° C, then the mixture was cooled to room temperature (25 ° C) and diluted by the addition of 150 g of isododecane.

There was thus obtained a 50% solution of active polymer material in isododecane.

The resulting polymer has a number average molecular weight (Mn) of 18,000 and a weight average molecular weight (Mw) of 290,200; with an Ip = 8.9.

Comparative Examples 2 to 7:

The 6 compositions described below were prepared.

For each composition, all ingredients were mixed together at room temperature (25 ° C) in a glass vial and then the composition was heated to 150 ° C using a multi-well stirrer for 10 minutes. minutes. The state of the composition was then observed by inverting the flask upside down to thereby determine if the mixture reacted with a crosslinking reaction of the polymer (the crosslinking inducing a rise in the viscosity of the initial mixture).

The following results were obtained:

Diol 1: hydrogenated dihydroxy polybutene G -1000 from Nisso (hydroxyl number: 60-75 KOH mg / average number = number average molecular weight = 1500)

Diol 2: PDMS-OH KF-6001 from Shin Estu (hydroxyl number = 62 mgKOH / g, viscosity at 25 ° C. = 45 mm 2 / s

The results obtained show that the compositions according to the invention (Examples 3, 4, 6, 7) have thickened after heating, which proves that the crosslinking reaction of the polymer with the diol has indeed taken place.

The same test carried out without carrying out the heating step for 10 minutes at 150 ° C. leads to all-fluid compositions: without the heating step, the crosslinking of the polymer does not occur.

Examples 8 to 10 Comparative

The following three compositions were prepared:

Diol 3: 1,12-dodecanediol

Hair locks were treated according to the following protocol:

2.9 g natural Caucasian hair locks were used.

The locks were washed with Ultra Gentle Chamomile shampoo (from La Scad) by applying 1.2 g of shampoo on a lock of wet hair. The wick was then rinsed, then wrung out and then dried with the helmet at 60 ° C for 10 minutes.

5.4 g of the test composition were then applied to the lock of hair. Then the wick was dried at 60 ° C (with the helmet) for 15 minutes and then the heated straightener was applied at 210 ° C by making 15 passes along the length of the wick (each pass of about 4 seconds) . The quality of the attachment of the wick was evaluated.

Then wash with water by immersing the lock of hair treated in water (at room temperature 25 ° C) for 5 minutes. The wick was then wrung and then dried with a helmet at 60 ° C for 15 minutes. The quality of the fixation of the lock of hair was again evaluated.

Then we combed the wick by performing 8 passes of the comb and evaluated again the quality of the fixation.

For comparison of the effect of the heating step made with the curling iron heated to 210 ° C, the same protocol is carried out on another lock of hair but without effecting the application of the curling iron.

The quality of the fixation of the lock of hair was evaluated by observing the more or less rigid aspect of the wick: the wick is taken at one of its ends with the fingers and the wick is put upside down in holding it at the bottom; we then observe the shape of the wick: either the wick keeps its shape which means that the wick is very well fixed; either the wick is deformed (under the effect of weightlessness) which means that the wick is not well fixed.

The quality of the fixation of the lock of hair was evaluated according to the following notation: Wick without fixation: - Wick with weak fixation: + Wick with medium fixation: ++ Wick with very good fixation: +++

The following results were obtained:

The results obtained show that the locks of Examples 8, 9 and 10 treated with the process according to the invention have good fixing properties before and after washing with water, and also after combing. These properties are superior to those of the wicks of Examples 8 ', 9' and 10 'which have not undergone a heating step with the curling iron.

Claims

1. A cosmetic process for treating keratin fibers, comprising: (i) a step of applying to the keratinous fibers of an extemporaneous mixture of a block polymer of maleic anhydride, or a cosmetic composition comprising it, of a liposoluble polyol compound or a cosmetic composition containing it, and an amine catalyst; said block polymer comprising: at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C and obtained from at least one (meth) acrylate monomer of formula CH2 = C (Ri) -COOR2 wherein R 1 is H or methyl, R 2 is C 4 -C 12 cycloalkyl; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one maleic anhydride monomer and at least one (meth) acrylate monomer of formula CH2 = C (R 1) -COOR 3 wherein R 1 is H or methyl, R 3 is unsubstituted C 1 -C 6 alkyl, linear or branched, with the exception of tert-butyl, or methoxyethyl, (ii) step of heating the keratin fibers at a temperature ranging from 90 ° C to 250 ° C; steps (i) and (ii) being performed at the same time, or separately in the order (i) and then (ii).

2. Method according to claim 1, characterized in that the first block of the block polymer is obtained from at least one acrylate monomer of formula CH 2 CHCH-COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 to C12 cycloalkyl group; and optionally an additional monomer chosen from linear or branched C4-C22 alkyl (meth) acrylates.

3. Method according to the preceding claim, characterized in that for the first block of the block polymer said acrylate monomer and said methacrylate monomer are in mass proportions acrylate / methacrylate between 30: 70 and 70: 30, preferably between 40: 60 and 60:40, especially between 45:55 and 55:45.

4. Method according to one of claims 2 or 3, characterized in that the first block of the block polymer is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

5. Method according to any one of the preceding claims, characterized in that the proportion of the first block in the block polymer ranges from 60 to 80% by weight of the polymer, more preferably from 65 to 75%.

6. Process according to any one of the preceding claims, characterized in that the second block of the block polymer comprises a monomer chosen from isobutyl acrylate, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate, or mixtures thereof, and preferably isobutyl acrylate.

7. Process according to any one of the preceding claims, characterized in that, for the second block of the block polymer, maleic anhydride and said (meth) acrylate monomer are in mass proportions of maleic anhydride / (meth) acrylate ranging from 1 to 10, preferably ranging from 2 to 9, in particular ranging from 3 to 8, or even from 4 to 7.

8. Method according to any one of the preceding claims, characterized in that the second block of the sequenced polymer comprises an additional silicone monomer of formula (I):

9. Process according to any one of the preceding claims, characterized in that the proportion of the second block in the block polymer ranges from 20 to 40% by weight of the polymer, more preferably from 25 to 35% by weight.

10. Method according to one of the preceding claims, characterized in that said sequenced polymer comprises an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block, in particular is a random polymer.

11. Method according to one of the preceding claims, characterized in that said sequenced polymer has a polydispersity index of the sequenced polymer is greater than 2, preferably ranging from 3 to 11.

12. Method according to one of the preceding claims, characterized in that the block polymer of maleic anhydride is present in the composition applied on the keratin materials in a content ranging from 0.1 to 40% by weight, relative to total weight of the composition resulting from extemporaneous mixing, preferably from 0.5% to 35% by weight, and preferably from 1% to 30% by weight, and more preferably from 10% to 30% by weight.

13. Method according to one of the preceding claims, characterized in that the liposoluble polyol is a nonpolymeric organic compound of formula (II): W (OH) n (II) wherein n denotes an integer greater than or equal to 2 preferably between 2 and 10, preferably between 2 and 5 W, denotes a linear or branched or saturated or unsaturated C8-C30 multivalent radical, W which may also contain one or more functions chosen from among the functions ether, thioether, ester, ketone, amide.

14. Method according to one of the preceding claims, characterized in that the liposoluble polyol is a hydrocarbon-based diol Cs-Cs> s> in particular selected from 1-10-decanediol, 1,12-dodecanediol, 1 , 14-tetradecanediol, and preferentially 1,12-dodecanediol.

15. Method according to one of the preceding claims, characterized in that the polyol is chosen from polyolefins diols, polydimethylsiloxane diols, polyesters diols, preferably chosen from polybutadienes hydrogenated diols, and polydimethylsiloxane diols of formula (IV) :

(IV) wherein: R1 = divalent C2-C10 alkylene group X = covalent bond or -O-R2- group with R2 = C2-C0 alkylene n = 1 to 100, preferably 5 to 50, and preferably 10 to 30, preferably

16. Method according to one of the preceding claims, characterized in that the liposoluble polyol is implemented in a molar ratio OH group of the liposoluble polyol / maleic anhydride group of the acrylic polymer ranging from 0.01 to 10, preferably from 0.1 to 5, preferably ranging from 0.1 to 2, and more preferably ranging from 0.1 to 1.

17. Process according to one of the preceding claims, characterized in that the amine catalyst is chosen from amine-functional or aminidine-functional or guanidine-functional catalysts, preferably diisopropylethylamine.

18. Method according to one of the preceding claims, characterized in that the amine catalyst is present in a content ranging from 0.1 to 0.5% by weight, relative to the total weight of the composition derived from said mixture, preferably ranging from 0.1 to 0.2% by weight.

19. Method according to any one of the preceding claims, characterized in that the composition comprises a hydrocarbon oil, preferably an apolar hydrocarbon oil having 8 to 14 carbon atoms, preferably isododecane.

20. Process according to any one of the preceding claims, characterized in that the mixture of the composition comprising the block polymer of maleic anhydride and of the liposoluble polyol, or of the composition containing it, and the aminated catalyst is carried out in a time between 1 minute and 24 hours before application to the keratinous fibers, and preferably between 5 and 30 minutes.

21. Method according to one of the preceding claims, characterized in that the heating step is carried out at a temperature ranging from 100 to 230 ° C, preferably from 190 ° C to 230 ° C

22. Method according to one of the preceding claims, characterized in that the heating step is performed by means of an iron.

23. Method according to one of the preceding claims, characterized in that it comprises an additional step of drying the keratinous fibers after step (i) and before step (ii), preferably at a temperature ranging from at 70 ° C.

24. Kit comprising: a first composition comprising a block polymer of maleic anhydride as defined in one of claims 1 to 12 and optionally a physiologically acceptable medium, and a second composition comprising a liposoluble polyol compound as defined in one of claims 1 and 13 to 16 and optionally a physiologically acceptable medium, the first composition or the second composition comprising an amine catalyst as defined in one of claims 1, 17, 18, the first and second compositions being each conditioned in a separate packaging set.

25. Cosmetic composition obtained by mixing a block polymer of maleic anhydride as defined in one of claims 1 to 11 or of a composition containing it and comprising a physiologically acceptable medium, a liposoluble polyol compound such as defined in one of claims 1 and 13 to 16 or a composition containing it and comprising a physiologically acceptable medium, and an amine catalyst as defined in one of claims 1, 17, 18.

26. Polymer obtainable by reaction of a liposoluble polyol compound as defined in one of Claims 1 and 13 to 16 with an acrylic maleic anhydride polymer as defined in one of Claims 1 to 11. .